KR20240019038A - Resin composition, cured product, resin film, prepreg, laminated body, and material for electronic circuit board - Google Patents

Abstract

The present invention provides a conjugated diene-based copolymer, etc. from which a cured product having a low dielectric constant and low dielectric loss tangent and excellent tensile strength can be obtained.
A resin composition containing the following component (I) and at least one component selected from the group consisting of the following components (II) to (IV).
Ingredient (I):
A random copolymer block (C) mainly composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit,
A polymer block (A) mainly composed of vinyl aromatic monomer units and/or a polymer block (B) mainly composed of conjugated diene monomer units.
With
A conjugated diene-based copolymer that satisfies the following conditions (i), (ii), and (iii).
<Condition (i)>
The weight average molecular weight of the conjugated diene-based copolymer is 35,000 or more.
<Condition (ii)>
The amount of vinyl aromatic monomer units in the random copolymer block (C) is 45% by mass or more.
<Condition (iii)>
The amount of vinyl aromatic monomer units in the conjugated diene-based copolymer is 45% by mass or more and 90% or less.
Component (II): Radical initiator
Component (III): Polar resin (excluding component (I))
Component (IV): Hardener (excluding component (II))

Description

Resin compositions, cured products, resin films, prepregs, laminates, and materials for electronic circuit boards {RESIN COMPOSITION, CURED PRODUCT, RESIN FILM, PREPREG, LAMINATED BODY, AND MATERIAL FOR ELECTRONIC CIRCUIT BOARD}

The present invention relates to resin compositions, cured products, resin films, prepregs, laminates, and materials for electronic circuit boards.

In recent years, with significant progress in information network technology and the expansion of services utilizing information networks, increased information capacity and faster processing speed have been required for electronic devices.

In order to meet these demands, materials with low dielectric loss are required for materials for various boards such as printed boards and flexible boards.

Conventionally, in order to obtain materials with low dielectric loss, thermosetting resins such as epoxy resins or thermoplastic resins such as polyphenylene ether resins with low dielectric constant and/or low dielectric loss tangent and excellent mechanical properties such as strength have been used as main ingredients. One resin cured product has been studied and disclosed.

However, conventionally disclosed materials still have room for improvement in terms of low dielectric constant and low dielectric loss tangent, and when used for printed circuit boards, there is a problem that the amount of information and processing speed are limited.

For the purpose of improving these problems, various rubber components have conventionally been proposed as modifiers for thermosetting resins and thermoplastic resins as described above.

For example, in Patent Document 1, as a modifier for low dielectric loss tangent and low dielectric constant of polyphenylene ether resin, a copolymer of a vinyl aromatic compound and an olefinic alkene compound and its hydrogenated product, and a vinyl aromatic compound alone At least one type of elastomer selected from the group consisting of polymers is disclosed.

Additionally, Patent Document 2 discloses a styrene-based elastomer as a modifier for lowering the dielectric loss tangent and lowering the dielectric constant of the epoxy resin.

Japanese Patent Publication No. 2021-147486 Japanese Patent Publication No. 2020-15861

However, the resin composition using the modifier disclosed in Patent Documents 1 and 2 does not yet have sufficient low dielectric constant and low dielectric loss tangent, and the addition of the modifier lowers the tensile strength and does not provide sufficient strength. There is a problem.

Therefore, the purpose of the present invention is to provide a resin composition that yields a cured product with a low dielectric constant and low dielectric loss tangent and excellent tensile strength.

The present inventors have conducted intensive studies to solve the problems of the prior art described above, and as a result, a cured product of a resin composition containing a conjugated diene-based copolymer having a predetermined structure has a low dielectric constant and low dielectric loss tangent, and also has excellent strength characteristics. After finding out this, we came to complete the present invention.

That is, the present invention is as follows.

[1] A resin composition containing the following component (I) and at least one component selected from the group consisting of the following components (II) to (IV).

Ingredient (I):

A random copolymer block (C) mainly composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit,

A polymer block (A) mainly composed of vinyl aromatic monomer units and/or a polymer block (B) mainly composed of conjugated diene monomer units.

With

A conjugated diene-based copolymer that satisfies the following conditions (i), (ii) and (iii),

<Condition (i)>

The weight average molecular weight of the conjugated diene-based copolymer is 35,000 or more.

<Condition (ii)>

The amount of vinyl aromatic monomer units in the random copolymer block (C) is 45% by mass or more.

<Condition (iii)>

The amount of vinyl aromatic monomer units in the conjugated diene-based copolymer is 45% by mass or more and 90% or less.

Component (II): Radical initiator

Component (III): Polar resin (excluding component (I))

Component (IV): Hardener (excluding component (II))

[2] The resin composition according to [1], wherein the unsaturated bond derived from the conjugated diene monomer unit of the conjugated diene copolymer is hydrogenated.

[3] Contains the above component (III),

The resin composition according to [1] or [2], wherein the component (III) is at least one selected from the group consisting of epoxy resin, polyimide resin, polyphenylene ether resin, liquid crystal polyester resin, and fluorine resin. .

[4] A cured product of the resin composition according to any of [1] to [3].

[5] A resin film containing the resin composition according to any one of [1] to [3].

[6] Description,

The resin composition according to any of [1] to [3]

A prepreg that is a complex of .

[7] The prepreg according to [6], wherein the base material is glass cloth.

[8] A laminate comprising the resin film according to [5] and a metal foil.

[9] A laminate comprising a cured product of the prepreg according to [6] or [7] and a metal foil.

[10] A material for an electronic circuit board containing the cured product described in [4].

According to the present invention, it is possible to provide a resin composition from which a cured product having a low dielectric constant and low dielectric loss tangent and excellent strength characteristics can be obtained.

Hereinafter, an embodiment for carrying out the present invention (hereinafter referred to as “this embodiment”) will be described in detail.

In addition, the following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents, and the present invention can be implemented with various modifications within the scope of the gist.

[Conjugated diene copolymer]

The conjugated diene-based copolymer of the present embodiment includes a random copolymer block (C) mainly composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit (hereinafter sometimes referred to as polymer block (C)), and a vinyl aromatic monomer unit. Polymer block (A) mainly composed of monomer units (hereinafter sometimes referred to as polymer block (A)) and/or polymer block (B) mainly composed of conjugated diene monomer units (hereinafter referred to as polymer block (B)) It may be written as).

The conjugated diene-based copolymer of this embodiment satisfies the following conditions (i) to (iii).

<Condition (i)>

The weight average molecular weight of the conjugated diene-based copolymer is 35,000 or more.

<Condition (ii)>

The amount of vinyl aromatic monomer units in the polymer block (C) is 45% by mass or more.

<Condition (iii)>

The quantity of vinyl aromatic monomer in the said conjugated diene polymer is 45 mass % or more and 90 % or less.

According to the conjugated diene-based copolymer of this embodiment, a cured product with a low dielectric constant and low dielectric loss tangent and excellent strength characteristics is obtained.

The conjugated diene monomer unit refers to a structural unit derived from the conjugated diene compound in the polymer formed by polymerization of the conjugated diene compound.

A conjugated diene compound is a diolefin having a pair of conjugated double bonds.

The conjugated diene compound is not limited to the following, but examples include 1,3-butadiene, 2-methyl-1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-penta. Diene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-cyclohexadiene, etc.

Among these, 1,3-butadiene and isoprene are preferable, and 1,3-butadiene is more preferable. 1,3-Butadiene and isoprene are widely used and easy to obtain, are advantageous from a cost standpoint, and are also easy to copolymerize with styrene, which is widely used as a vinyl aromatic compound described later.

These may be used individually or in combination of two or more types.

The conjugated diene compound may be a compound using biotechnology.

The vinyl aromatic monomer unit refers to a structural unit derived from a vinyl aromatic compound in a polymer formed by polymerization of a vinyl aromatic compound.

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

These may be used individually or in combination of two or more types.

The weight average molecular weight of the conjugated diene-based copolymer of this embodiment is 35,000 or more. When the weight average molecular weight is 35,000 or more, a conjugated diene-based copolymer with high strength is obtained, and the strength of the resin composition described later and/or the cured product of the resin composition is also improved. From the above-mentioned viewpoint, the weight average molecular weight of the conjugated diene copolymer is 35,000 or more, preferably 40,000 or more, more preferably 45,000 or more, more preferably 50,000 or more, and even more preferably 55,000 or more. or more, particularly preferably 60,000 or more, particularly preferably 65,000 or more. In addition, when the weight average molecular weight is 35,000 or more, the conjugated diene-based copolymer tends to exist as a solid without fluidity rather than as a liquid. Therefore, it is preferable because it is easy to mold into a shape such as a pellet that meets the requirements for handling during transportation or processing.

The upper limit of the weight average molecular weight is not particularly limited, but in the method for producing a resin composition described later, a method of dissolving each component in a solvent and then mixing them to produce a resin film or prepreg is common, so the solubility in the solvent From the viewpoint, the weight average molecular weight is preferably 300,000 or less, more preferably 200,000 or less, more preferably 150,000 or less, even more preferably 130,000 or less, and particularly preferably 100,000 or less. Examples of the range of weight average molecular weight include 35,000 to 300,000, 40,000 to 200,000, 45,000 to 150,000, 50,000 to 130,000, and 55,000 to 100,000. .

The weight average molecular weight can be measured by the method described in the Examples described later, and the molecular weight of the peak of the chromatogram obtained by measurement by gel permeation chromatography (GPC) is used as a calibration curve (standard curve) obtained from the measurement of commercially available standard polystyrene. This is the weight average molecular weight (Mw) determined based on (prepared using the peak molecular weight of polystyrene).

Molecular weight distribution is the ratio (Mw/Mn) of the weight average molecular weight (Mw) and the weight average molecular weight (Mn).

The molecular weight distribution of the single peak measured by GPC of the conjugated diene-based copolymer of the present embodiment is preferably 5.0 or less, more preferably 4.0, from the viewpoint of preventing deterioration of handleability due to mixing of low molecular weight polymers described later. or less, more preferably 3.0 or less, and even more preferably 2.5 or less.

The weight average molecular weight and molecular weight distribution of the conjugated diene-based copolymer of this embodiment can be controlled within the above numerical range by adjusting polymerization conditions such as monomer addition amount, addition timing, polymerization temperature, and polymerization time.

The conjugated diene-based copolymer of the present embodiment includes a polymer block (C) mainly composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit, and a polymer block (B) mainly composed of a conjugated diene monomer unit and/or a vinyl aromatic monomer. It has a polymer block (A) mainly composed of units.

The polymer block (A) is mainly composed of vinyl aromatic monomer units. This “mainly” means that no other monomer is intentionally added.

The polymer block (B) is mainly composed of conjugated diene monomer units. This “mainly” means that no other monomer is intentionally added.

The polymer block (C) has vinyl aromatic monomer units and conjugated diene monomer units. The polymer block (C) has vinyl aromatic monomer units and conjugated diene monomer units intentionally added, and can be clearly distinguished from polymer blocks (A) and (B). The conjugated diene-based copolymer of the present embodiment increases the polarity of the conjugated diene-based copolymer beyond the range that can be provided by controlling the amount of vinyl aromatic monomer and/or the hydrogenation rate described above, and component (II) and components described later. In order to provide compatibility and/or reactivity with (III) and component (IV) and/or adhesion to metal foil, polymer blocks (A) to (C) other than the above-mentioned polymer blocks (A) to (C) are used within the range that does not impair dielectric performance. , you may have a copolymer block (D) in which another compound and a conjugated diene compound and/or a vinyl aromatic compound are copolymerized.

For example, when the conjugated diene-based copolymer of the present embodiment containing the copolymer block (D) is produced by anionic polymerization, methyl methacrylate (MMA) is copolymerized with a vinyl aromatic compound or a conjugated diene compound. It is possible, when MMA is contained, the polarity of the conjugated diene-based copolymer of the present embodiment increases, and the above-mentioned compatibility and/or reactivity and/or adhesiveness with metal foil tend to improve, but the conjugated diene-based copolymer The permittivity and/or dielectric loss tangent tend to worsen.

Component (II) described later: radical initiator, component (III): polar resin, and component (IV): curing agent preferably have a polar group. From the viewpoint of solubility parameters, vinyl aromatic monomer units have higher compatibility with component (II), component (III), and component (IV) than conjugated diene monomer units. Component (II), component (III), and component (IV) are compatible with the conjugated diene-based copolymer, so that the resin composition and/or cured product of the present embodiment described later is reduced in mobility and/or polarized by the external electric field. This is suppressed, the dielectric loss tangent/or dielectric constant of the cured product of the resin composition described later is improved, and the strength is improved.

Additionally, unsaturated bonds derived from conjugated diene monomers are known to have radical reactivity. Through a radical reaction due to an unsaturated bond derived from the above-mentioned compatible and conjugated diene monomers, the conjugated diene-based copolymer is compatible and/or combined with component (II), component (III), and component (IV) described later, and conjugated diene-based copolymer By bonding the copolymers together, the network formed by component (II), component (III), and component (IV) and the network formed by the conjugated diene copolymer are in a compatible cured state, thereby improving the dielectric performance and the dielectric properties of the cured product of the resin composition. Strength improves.

The amount of vinyl aromatic monomer in the conjugated diene-based copolymer is 45% by mass or more, more preferably 50% by mass or more, and still more preferably 55% by mass or more from the viewpoint of compatibility and reactivity mentioned above. By setting the amount of vinyl aromatic monomer in the conjugated diene-based copolymer to 45% by mass or more, sufficient compatibility is achieved, and the cured product shows good strength and/or dielectric performance. The upper limit is 90% by mass or less, preferably 85% by mass or less, and more preferably 80% by mass or less from the viewpoint of reactivity with component (II), component (III) and component (IV). When the amount is 90% by mass or less, the unsaturated bond derived from the conjugated diene monomer unit is contained to a certain extent in the conjugated diene-based copolymer and has reactivity, thereby improving the strength and/or dielectric performance of the cured resin composition. Examples of the range of the amount of vinyl aromatic monomer in the conjugated diene copolymer include 45 mass% to 90 mass%, 50 mass% to 85 mass%, and 55 mass% to 80 mass%.

By having a copolymer block (polymer block (C)) of a conjugated diene monomer unit and a vinyl aromatic monomer unit, the conjugated diene-based copolymer increases the polarity of the entire polymer. That is, if the vinyl aromatic content in the polymer is constant, the vinyl aromatic exists as a more dispersed polymer block (C) rather than as a localized polymer block (A), which has the effect of increasing polarity throughout the polymer. can be expected. As a result, the conjugated diene-based copolymer is introduced as a whole into the network formed by component (II), component (III), and component (IV), which will be described later, and the dielectric performance and strength of the cured product of the resin composition, which will be described later, are improved. Therefore, the conjugated diene-based copolymer has a polymer block (C), and the amount of vinyl aromatic monomer units in the polymer block (C) is 45% by mass or more, preferably 50% by mass or more, more preferably 55% by mass. % or more, more preferably 60 mass% or more. When the amount of vinyl aromatic monomer in the polymer block (C) is 45% by mass or more, sufficient compatibility is achieved and the cured product exhibits sufficient strength and/or dielectric performance. The upper limit of the amount of vinyl aromatic monomer units in the polymer block (C) is not particularly limited, but may be, for example, 95% by mass, 90% by mass, 85% by mass, or 80% by mass. Examples of the range of the amount of vinyl aromatic monomer units in the polymer block (C) include 45 mass% to 95 mass%, 50 mass% to 90 mass%, 55 mass% to 85 mass%, and 60 mass%. % or more and 80 mass% or less can be mentioned.

The compatibility of polymer block (C) with component (II), component (III), and component (IV) described later is higher than that of polymer block (A) mainly composed of vinyl aromatic monomer units because conjugated diene monomer units are copolymerized. low. In addition, the radical reactivity of the conjugated diene monomer unit is superior to that of the polymer block (C) due to the steric hindrance of the vinyl aromatic monomer unit. The polymer block (C) may have high compatibility and may have high radical reactivity depending on the content of vinyl aromatic monomer units, etc., so from the viewpoint of ensuring sufficient compatibility and/or reactivity as the conjugated diene-based copolymer as a whole, When the polymer block (C) has low compatibility, it is preferable to combine it with a block with high compatibility, and when the polymer block (C) has low compatibility, it is preferable to combine it with a block with high reactivity. From the above-mentioned viewpoint, from the viewpoint of sufficiently securing compatibility and reactivity and enabling the cured product to exhibit dielectric performance and strength, the conjugated diene-based copolymer includes a polymer block (C), a polymer block (A), and/or a polymer block ( B) has

In addition, the amount of polymer block (C) in the conjugated diene copolymer is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, from the viewpoint of compatibility described above. Preferably it is 40 mass% or more, especially preferably 50 mass% or more, and especially preferably 60 mass% or more. The upper limit of the amount of polymer block (C) in the conjugated diene-based copolymer is not particularly limited, but may be, for example, 90% by mass, 85% by mass, 80% by mass, or 75% by mass. As a range of the amount of polymer block (C) in a conjugated diene-based copolymer, for example, 10 mass% or more and 90 mass% or less, 20 mass% or more and 85 mass% or less, 30 mass% or more and 85 mass% or less, and 40 mass%. % or more and 80 mass% or less, 50 mass% or more and 80 mass% or less, and 60 mass% or more and 75 mass% or less.

In the conjugated diene-based copolymer in this embodiment, the unsaturated bond derived from the conjugated diene monomer unit may be hydrogenated. From the viewpoint of storage stability of the composition (varnish) before the curing process of the resin composition, the conjugated diene copolymer is preferably hydrogenated, and the hydrogenation rate is preferably 5% or more, more preferably 10% or more, More preferably 15% or more, even more preferably 20% or more, particularly preferably 25% or more, particularly preferably 30% or more. The upper limit of the hydrogenation rate is not particularly limited, but from the viewpoint of the reactivity of the conjugated diene-based copolymer, the hydrogenation rate is preferably 95% or less, more preferably 90% or less, more preferably 85% or less, and even more preferably is 80% or less, particularly preferably 75% or less, particularly preferably 70% or less. The range of the hydrogenation rate is, for example, 5% to 95%, 10% to 90%, 15% to 85%, 20% to 80%, 25% to 75%, and 30% to 70%. % or less may be mentioned.

The content of each monomer unit constituting the conjugated diene-based copolymer used in the resin composition of the present embodiment is determined by a method using a nuclear magnetic resonance (NMR) device using the conjugated diene-based copolymer of the present embodiment as a sample ( It can be measured by the method described in Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54,685 (1981) (hereinafter referred to as “NMR method”).

The conjugated diene monomer unit consists of a unit (a) derived from a 1,2-bond and/or a 3,4-bond, and a unit (b) derived from a 1,4-bond, where the unit (a) is a unit It is known to have higher radical reactivity than (b). From the viewpoint of improving the above-mentioned reactivity, when the total content of the conjugated diene monomer units of the conjugated diene-based copolymer is 100%, the content of the more reactive unit (a) (sometimes expressed as the amount of vinyl bonds) is 10% or more is preferable, more preferably 15% or more, more preferably 20% or more, even more preferably 25% or more, particularly preferably 30% or more, especially preferably 35% or more, even more preferably 35% or more. Preferably it is 40% or more. In particular, when the conjugated diene-based copolymer contains a polymer block (A) and a polymer block (C) (does not have a polymer block (B)), the amount of vinyl bonds is preferably 15% or more from the viewpoint of the above-mentioned reactivity. And, more preferably 25% or more, further preferably 35% or more, and even more preferably 45% or more. The upper limit of the amount of vinyl bonds is not particularly limited, but may be, for example, 95%, 90%, 85%, or 80%. The range of the vinyl bond amount is, for example, 10% to 95%, 15% to 90%, 20% to 85%, 25% to 80%, 30% to 75%, 35% to 75%. % or less, and 40% or more and 70% or less.

The content of unit (a) can be controlled to the above-mentioned numerical range by using a regulator such as a polar compound in the polymerization process of the conjugated diene-based copolymer, and can be calculated by the method described in the Examples described later.

Examples of the regulator include tertiary amine compounds and ether compounds. It is preferred to use tertiary amine compounds.

A tertiary amine compound is a compound of the formula R1R2R3N (where R1, R2, and R3 are a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a tertiary amino group).

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-dipiperidinoethane, trimethylaminoethylpiperazine, N,N,N' ,N",N"-pentamethylethylenetriamine, N,N'-dioctyl-p-phenylenediamine, etc.

The amount of the regulator added is preferably 0.1 mol or more, more preferably 0.5 mol or more, and still more preferably 1.0 mol or more, per 1 mol of the polymerization initiator described later. In addition, when the content of unit (a) is 80% or more, the amount of the adjuster added is preferably 0.15 mol or more, more preferably 0.5 mol or more, and even more preferably 1.0 mol or more per 1 mol of the polymerization initiator described later. am.

The method for hydrogenating the conjugated diene copolymer is not particularly limited, and a known method can be applied.

In the case of hydrogenation reaction, a known hydrogenation catalyst can be used.

As a hydrogenation catalyst, for example, (1) a supported heterogeneous hydrogenation catalyst in which metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, etc., (2) Ni, Co, Fe, So-called Ziegler-type hydrogenation catalysts using organic acid salts such as Cr or transition metal salts such as acetylacetone salts and reducing agents such as organoaluminum, (3) so-called organometallic compounds such as organometallic compounds such as Ti, Ru, Rh, and Zr; Homogeneous hydrogenation catalysts such as complexes can be mentioned.

As a hydrogenation catalyst, specifically, Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-37970, Japan. The hydrogenation catalyst described in Patent Publication No. 1-53851 and Japanese Patent Publication No. 2-9041 can be used.

Preferred hydrogenation catalysts include titanocene compounds and/or reducing organometallic compounds.

As the titanocene compound, a compound described in Japanese Patent Application Laid-Open No. 8-109219 can be used. The titanocene compound is not limited to the following, but includes, for example, a (substituted) cyclopentadienyl skeleton such as biscyclopentadienyltitanium dichloride or monopentamethylcyclopentadienyltitanium trichloride, an indenyl skeleton, or Examples include compounds having at least one ligand having a fluorenyl skeleton. The titanocene compound may contain the above skeleton either individually or in combination of two types.

Examples of the reducing organometallic compound include, but are not limited to, organoalkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.

These may be used individually or in combination of two or more types.

The hydrogenation rate of the hydrogenated conjugated diene-based copolymer of this embodiment can be controlled within the above-mentioned numerical range by timely adjusting the reaction temperature, reaction time, hydrogen supply amount, catalyst amount, etc. in the hydrogenation method. The temperature during the hydrogenation reaction is preferably 55 to 200°C, more preferably 60 to 170°C, and still more preferably 65 to 160°C. Additionally, the pressure of hydrogen used in the hydrogenation reaction is 0.1 to 15 MPa, preferably 0.2 to 10 MPa, and more preferably 0.3 to 5 MPa. Additionally, the hydrogenation reaction time is usually 3 minutes to 10 hours, preferably 10 minutes to 5 hours.

The hydrogenation reaction can be used as a batch process, a continuous process, or a combination thereof.

[Method for producing hydrogenated conjugated diene copolymer]

The hydrogenated conjugated diene-based copolymer of the present embodiment is, for example, subjected to living anionic polymerization in a hydrocarbon solvent using a polymerization initiator such as an organic alkali metal compound, and then, if necessary, subjected to a hydrogenation reaction. It can be manufactured.

The hydrocarbon solvent is not limited to the following, but 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; etc. can be mentioned.

Polymerization initiators include organic alkali metal compounds, such as aliphatic hydrocarbon alkali metal compounds, aromatic hydrocarbon alkali metal compounds, and organic amino alkali metal compounds, which are generally known to have anionic polymerization activity toward conjugated diene compounds and vinyl aromatic compounds. . Examples of alkali metals include lithium, sodium, and potassium.

Examples of organic alkali metal compounds include aliphatic and aromatic lithium hydrocarbon compounds having 1 to 20 carbon atoms, such as compounds containing one lithium per molecule, dilithium compounds containing multiple lithium per molecule, Trilithium compounds and tetralithium compounds are included.

As organic alkali metal compounds, specifically, n-propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-pentyl lithium, n-hexyl lithium, benzyl lithium, phenyl lithium, tolyl lithium, di. Examples include reaction products of isopropenylbenzene and sec-butyllithium, and reaction products of divinylbenzene, sec-butyllithium, and a small amount of 1,3-butadiene. In addition, 1-(t-butoxy)propyllithium disclosed in US Patent No. 5,708,092, a lithium compound in which 1 to several molecules of isoprene monomer are inserted to improve its solubility, and 1 disclosed in British Patent No. 2,241,239. -Alkyl lithium containing siloxy groups such as (t-butyldimethylsiloxy)hexyl lithium, alkyl lithium containing amino groups disclosed in U.S. Patent No. 5,527,753, and amino lithium such as lithium digisopropylamide and lithium hexamethyldisilazide. You can also use

As a method of polymerizing a vinyl aromatic compound and a conjugated diene compound using an organic alkali metal compound as a polymerization initiator, a conventionally known method can be applied.

The polymerization method may be, for example, batch polymerization, continuous polymerization, or a combination thereof. In particular, batch polymerization is suitable for obtaining a uniform polymer.

The polymerization temperature is preferably 0°C to 180°C, and more preferably 30°C to 150°C.

The polymerization time varies depending on conditions, but is usually within 48 hours, and is preferably 0.1 to 10 hours.

Additionally, as the atmosphere of the polymerization system, an inert gas atmosphere such as nitrogen gas is preferable.

The polymerization pressure can be set to a pressure range that can maintain the monomer and solvent in the liquid phase in the above temperature range, and is not particularly limited. In addition, care must be taken to ensure that impurities that inactivate the catalyst and living polymer, such as water, oxygen, carbon dioxide gas, etc., are not mixed into the polymerization system.

In addition, at the end of the polymerization process, a coupling reaction may be performed by adding a necessary amount of a bifunctional or higher coupling agent. The coupling rate is preferably 40% or less, more preferably 30% or less, and even more preferably 20% or less. It is more preferable that it is % or less and does not contain a coupling agent.

As a bifunctional coupling agent, conventionally known ones can be applied and are not particularly limited.

Examples of bifunctional coupling agents include trimethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dichlorodimethoxysilane, and dichlorodiethoxysilane. , alkoxysilane compounds such as trichloromethoxysilane and trichloroethoxysilane, dihalogen compounds such as dichloroethane, dibromoethane, dimethyldichlorosilane, and dimethyldibromosilane, methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalate ester. Acid esters such as these are mentioned.

In addition, as a trifunctional or more polyfunctional coupling agent, conventionally known ones can be applied and are not particularly limited.

Examples of trifunctional or higher polyfunctional coupling agents include trihydric or higher polyalcohols, epoxidized soybean oil, diglycidylbisphenol A, and 1,3-bis(N-N'-diglycidylaminomethyl)cyclo. polyhydric epoxy compounds such as hexane; A silicon halide compound represented by the formula R ₄ -nSiX _n (where R represents a hydrocarbon group having 1 to 20 carbon atoms, -Butylsilyl trichloride, silicon tetrachloride and their bromides, etc.; A tin halide compound represented by the formula R ₄ -nSnX _n (where R is a hydrocarbon group having 1 to 20 carbon atoms, -Polyvalent halogen compounds such as butyltin trichloride and tin tetrachloride can be mentioned. Additionally, dimethyl carbonate, diethyl carbonate, etc. may be used.

The hydrogenation reaction for the conjugated diene-based copolymer can be performed by a known method using a known hydrogenation catalyst, as described above.

From the solution of the conjugated diene copolymer of the present embodiment obtained as described above, catalyst residues can be removed as needed, and the conjugated diene copolymer can be separated from the solution.

The polymerization initiator when producing a hydrogenated conjugated diene-based copolymer by anionic living polymerization and the compound containing a metal atom in the hydrogenation catalyst in the hydrogenation reaction react with moisture in the air in a solvent removal process, etc. to produce a predetermined metal. A compound is produced and tends to remain in the water-addition conjugated diene-based copolymer. When these compounds are included in the cured product, the dielectric constant and dielectric loss tangent tend to increase, and furthermore, in electronic material applications, ion migration tends to occur.

The remaining metal compounds include compounds containing metal atoms contained in the polymerization initiator and hydrogenation catalyst, for example, titanium oxide, amorphous titanium oxide, orthotitanic acid or metatitanic acid, titanium hydroxide, nickel hydroxide, and nickel monoxide. , oxides of each atom such as lithium oxide, lithium hydroxide, cobalt oxide, cobalt hydroxide, and complex oxides of each atom and different metals such as lithium titanate, barium titanate, strontium titanate, nickel titanate, and nickel/iron oxide. I can hear it.

From the viewpoint of making it difficult for the above-mentioned low dielectric constant, low dielectric loss tangent, and ion migration to occur, the residual amount of the metal compound in the conjugated diene-based copolymer of the present embodiment is preferably 150 ppm or less as the residual metal amount, and is more preferable. Preferably it is 130 ppm or less, more preferably 100 ppm or less, and even more preferably 90 ppm or less. Specific remaining metals generally include Ti, Ni, Li, Co, etc.

As a method for reducing the amount of residual metal in the conjugated diene-based copolymer, known methods can be applied and are not particularly limited. For example, a method of neutralizing the hydrogenation catalyst residue by adding water and carbon dioxide gas after the hydrogenation reaction of the conjugated diene-based copolymer; A method of neutralizing the hydrogenation catalyst residue by adding an acid in addition to water and carbon dioxide gas is included. Specifically, the method described in Japanese Patent Application No. 2014-557427 can be applied. Even if such a metal removal method is used, since water containing the hydroxide of the metal compound is mixed during the desolvation process of the conjugated diene-based copolymer, the metal compound is generally contained in an amount of about 1 to 15 ppm. Therefore, with respect to the amount of metal added in the manufacturing process of the conjugated diene copolymer, it is preferable to remove 20% or more, more preferably 30% or more, more preferably 40% or more, and even more preferably 40% or more. Preferably, 50% or more is removed, and even more preferably, 60% or more is removed.

In addition, it is possible to reduce the amount of residual metal in the conjugated diene-based copolymer used in the resin composition of the present embodiment by reducing the amount of the polymerization initiator and hydrogenation catalyst to be added. However, if the amount of the polymerization initiator is reduced, the conjugated diene-based copolymer As the molecular weight of the diene-based copolymer increases, it tends to cause deterioration of the solvent solubility of the resin composition, which will be described later, and deterioration of the handleability due to an increase in the viscosity of the resin composition solution. Additionally, when performing a hydrogenation reaction, if the amount of hydrogenation reaction catalyst is reduced, the hydrogenation reaction time becomes longer and the hydrogenation reaction temperature becomes higher, which tends to significantly reduce productivity.

As a method of separating the solvent when taking out the conjugated diene-based polymer from a solution of the conjugated diene-based copolymer, for example, a poor solvent for the hydrogenated conjugated diene-based copolymer such as acetone or alcohol is added to the reaction solution after hydrogenation. A method of recovering the conjugated diene-based copolymer by precipitating it by adding a polar solvent; A method of pouring the reaction solution into boiling water while stirring and removing and recovering the solvent by steam stripping; A method of directly heating the conjugated diene-based copolymer solution and distilling off the solvent may be included.

Additionally, stabilizers such as various phenol-based stabilizers, phosphorus-based stabilizers, sulfur-based stabilizers, and amine-based stabilizers can be added to the conjugated diene-based copolymer.

In the manufacturing process of the conjugated diene-based copolymer of this embodiment, the process of forming a “polar group” may be performed within a range that does not impair dielectric properties.

The polar group is not limited to the following, but includes, for example, hydroxyl group, carboxyl group, carbonyl group, thiocarbonyl group, acid halide group, acid anhydride group, carboxylic acid group, thiocarboxylic acid group, aldehyde group, thioaldehyde group, carboxylic acid ester group. , amide group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothiocyanate group, halogenation. An atomic group containing at least one type of functional group selected from the group consisting of a silicon group, a silanol group, an alkoxy silicon group, a tin halide group, a boronic acid group, a boron-containing group, a boronic acid base, an alkoxy tin group, and a phenyl tin group. there is.

A polar group can be formed by reacting a modifier with a conjugated diene-based copolymer.

The denaturing agent is not limited to the following, but examples include tetraglycidyl methoxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, ε-caprolactone, δ-valerolactone, and 4-meth. Toxybenzophenone, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethylphenoxysilane, bis(γ-glycidoxypropyl)methylpropoxysilane , 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N,N'-dimethylpropylene urea, N-methylpyrrolidone, maleic acid, maleic anhydride , maleic anhydride, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, glycidyl methacrylic acid ester, crotonic acid, etc.

As a method for forming a polar group in the conjugated diene-based copolymer, a known method can be applied and is not particularly limited.

For example, a melt-kneading method or a method of reacting each component by dissolving or dispersing it in a solvent or the like can be mentioned.

In addition to the method using the above-described denaturant, a method of polymerizing by anionic living polymerization using a polymerization initiator having a functional group or an unsaturated monomer having a functional group can also be applied.

In addition, a method of performing modification by adding a modifier that forms a functional group at the living end of the polymer or a modifier containing a functional group, and a method of reacting an organic alkali metal compound such as an organic lithium compound to a conjugated diene copolymer (metallation reaction) There is also a method of adding a modifier having a functional group to the conjugated diene polymer to which an organic alkali metal has been added.

[Resin composition]

The resin composition of this embodiment contains the conjugated diene-based copolymer (component (I)) of this embodiment and at least one component selected from the group consisting of the following components (II) to (IV).

Component (II): Radical initiator

Component (III): Polar resin (excluding component (I))

Component (IV): Hardener (excluding component (II))

From the viewpoint of low dielectric constant, low dielectric loss tangent, and flexibility of the resin composition of this embodiment and its cured product, the resin composition of this embodiment has component (I): conjugated diene-based copolymer, and component (II): radical. It is preferred to include an initiator.

(Component (II): radical initiator)

As a radical initiator, a conventionally known one can be used, for example, a thermal radical initiator.

The thermal radical initiator is not limited to the following, but examples include diisopropylbenzene hydroperoxide (Percumyl P), cumene hydroperoxide (Percumyl H), t-butyl hydroperoxide (Perbutyl H), etc. hydroperoxide, α,α-bis(t-butylperoxy-m-isopropyl)benzene (perbutyl P), dicumyl peroxide (percumyl D), 2,5-dimethyl-2,5-bis (t-butylperoxy)hexane (perhexa25B), t-butylcumyl peroxide (perbutyl C), di-t-butyl peroxide (perbutyl D), 2,5-dimethyl-2,5-bis Dialkyl peroxides such as (t-butylperoxy)hexyne-3 (perhexyne 25B) and t-butylperoxy-2-ethylhexanoate (perbutylO), ketone peroxides, and n-butyl- Peroxyketals such as 4,4-di-(t-butylperoxy)valerate (perhexaV), organic peroxides such as diacyl peroxides, peroxydicarbonates, and peroxyesters, 2 ,2-azobisisobutylnitrile, 1,1'-(cyclohexane-1-1-carbonitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis Azo compounds such as (2,4-dimethylvaleronitrile) can be mentioned.

These may be used individually by 1 type, or 2 or more types may be used.

(Component (III): Polar Resin)

The resin composition of the present embodiment has the viewpoint of providing performance such as adhesion to a predetermined substrate within a range that does not impair the dielectric performance of the cured product, and component (III): polar resin (excluding component (I)) ) is preferably contained. By containing a polar resin, the resin composition of this embodiment tends to have excellent adhesion to a predetermined substrate.

When component (III) is a polar resin having radical reactivity, the amount of the above-mentioned component (II) radical initiator can be arbitrarily adjusted appropriately, or component (II) may not be added.

As component (III), a polar resin having radical reactivity is, for example, a homopolymer of a compound containing at least one vinyl group and/or a halogen element, or a homopolymer of a compound containing the vinyl group and/or a halogen element. and copolymers of the compound with any other compound. From the viewpoint of dielectric performance, it is preferable that it is a polymer having a vinyl group.

The polymer having a vinyl group may be a polymer containing a repeating unit having a vinyl group, a polymer of a compound having a vinyl group and a polar group, or a polymer having a vinyl group obtained by reacting each polar group of a compound having a polar group.

Compounds having a vinyl group and a polar group are not limited to the following, but examples include (meth)acrylic acid (in the present invention, "(meth)acrylic refers to methacrylic or acrylic"), maleic acid, and monoalkyl maleic acid. Carboxyl group-containing vinyl monomers such as esters and fumaric acids, sulfonic group-containing vinyl monomers such as vinyl sulfonic acid, (meth)allylsulfonic acid, methyl vinyl sulfonic acid, and styrene sulfonic acid, hydroxystyrene, N-methylol (meth)acrylamide, and hydroxyethyl Vinyl monomers containing hydroxyl groups such as (meth)acrylate and hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, 2-acrylic Vinyl monomers containing phosphoric acid groups such as royloxyethylphosphonic acid, hydroxystyrene, N-methylol (meth)acrylamide, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, polyethylene glycol (meth) Vinyl monomers containing hydroxy groups such as acrylates 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, and vinyl monomers containing nitrile groups such as (meth)acrylonitrile, cyanostyrene, and cyanoacrylate. and epoxy group-containing vinyl monomers such as glycidyl methacrylate, tetrahydrofurfuryl (meth)acrylate, and p-vinylphenylphenyl oxide.

Compounds containing a halogen element are not limited to the following, but examples include vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, brominated styrene, dichlorostyrene, chloromethylstyrene, and tetrafluorostyrene. , chloroprene, etc.

(Ingredient (IV): Hardener)

The above-mentioned component (III): When the radical reactivity of the polar resin is low, from the viewpoint of reactivity, the resin composition of the present embodiment preferably contains component (IV): a curing agent (excluding component (II)). .

Component (IV) curing agent usually has the function of curing the resin composition by reacting with component (III): polar resin.

Component (III) and component (IV) “react” means that the polar groups of each component have a covalent bond. When polar groups react with each other, for example, when OH of the carboxyl group is eliminated, the original polar group changes or disappears, but when a covalent bond is formed as a result, it is included in the definition of polar groups showing "reactivity" with each other.

Component (IV): The curing agent preferably has at least two polar groups in one molecule chain that can react with the functional groups of component (III): polar resin from the viewpoint of the curing function.

Component (IV) may be used individually or in combination of two or more types.

The types of polar groups possessed by component (III) and component (IV) are not particularly limited, but include, for example:

A combination of an epoxy group with any selected from the group consisting of a carboxyl group, a carbonyl group, an ester group, an imidazole group, a hydroxyl group, an amino group, a mercaptan group, a benzoxazine group, a carbodiimide group, and a phenolic hydroxyl group;

A combination of any one selected from the group consisting of an amino group, a carboxyl group, a carbonyl group, a hydroxyl group, an acid anhydride group, a sulfonic acid group, and an aldehyde group;

A combination of any one selected from the group consisting of an isocyanate group, hydroxyl group, carboxylic acid, and phenolic hydroxyl group;

A combination of an acid anhydride group and a hydroxy group;

A combination of any one selected from the group consisting of a silanol group, a hydroxy group, and a carboxylic acid group;

A combination of halogen and any selected from the group consisting of carboxylic acid group, carboxylic acid ester group, amino group, phenol group and thiol group;

A combination of an alkoxy group and any selected from the group consisting of a hydroxy group, an alkoxide group, and an amino group;

A combination of a maleimide group and a cyanate group;

etc. can be mentioned.

Whether the bond of these polar groups is component (III) or component (IV) can be arbitrarily selected.

Additionally, in cases where the polar group of component (III) and the polar group of component (IV) do not react directly, the case where they can react by adding a curing accelerator such as a catalyst is also included in the definition of showing “reactivity.”

For example, when component (III) is a polar resin having an epoxy group and component (IV) is a curing agent having an acid anhydride group, usually the reactivity of the epoxy group and the acid anhydride group is very low, but the compound having an amino group can be cured. By adding it as an accelerator, the epoxy group and amino group of component (III) react, and some or all of the epoxy groups of component (III) become hydroxyl groups. The resin composition is cured when this hydroxyl group reacts with the acid anhydride group of the component (IV) curing agent.

The amount ratio of the polar resin of component (III) and the curing agent of component (IV) is a molar ratio of polar groups from the viewpoint of reactivity, and the polar group of component (III): the polar group of component (IV) = 1:0.01 to 1:20. It is preferable, more preferably 1:0.05 to 1:15, and even more preferably 1:0.1 to 1:10.

Component (IV): The curing agent is a curing agent having an ester group, for example, EXB9451, EXB9460, EXB, 9460S, HPC8000-65T, HPC8000H-65TM, EXB8000L-65TM, EXB8150-65T, EXB9416-70BK manufactured by DIC, Examples include YLH1026, DC808, YLH1026, YLH1030, and YLH1048 manufactured by Mitsubishi Chemical Corporation.

As a curing agent having a hydroxyl group, for example, MEH-7700, MEH-7810, MEH-7851, NHN, CBN, GPH manufactured by Nippon Kayaku Co., Ltd., and SN170, SN170, SN180, SN190, and SN475 manufactured by Nippon Kayaku Co., Ltd. , SN485, SN495, SN-495V, SN375, TD-2090, LA-7052, LA-7054, LA-1356, LA-3018-50P, EXB-9500 manufactured by DIC.

Examples of the curing agent having a benzoxazine group include ODA-BOZ manufactured by JFE Chemical, HFB2006M manufactured by Showa Kobunshi Corporation, and P-d and F-a manufactured by Shikoku Kasei Kogyo.

Examples of the curing agent having an isocyanate group include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylenecyanate), and 4,4'-methylenebis(2,6-dimethyl. phenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate) Natephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanate) Bifunctional cyanate resins such as phenyl)thioether and bis(4-cyanatephenyl)ether; Polyfunctional cyanate resins derived from phenol novolac, cresol novolac, etc.; Prepolymers in which some of these cyanate resins are triazined; etc. can be mentioned. Commercially available products include PT30, PT60, ULL-950S, BA230, and BA230S75 manufactured by Lonza Japan.

Examples of the curing agent having a carbodiimide group include V-03 and V-07 manufactured by Nisshinbo Chemical Co., Ltd.

Examples of the curing agent having an amino group include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, and 4,4'-diamino. Diphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl -4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4- Hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-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. You can. Commercially available products include KAYABOND C-200S, KAYABOND C-100, KAYABOND A-A, KAYABOND A-B, KAYABOND A-S manufactured by Nippon Kayaku, and Epicure W manufactured by Mitsubishi Chemical.

Additionally, from the viewpoint of reactivity, the amino group is preferably a primary amine and/or a secondary amine, and more preferably a primary amine.

Examples of the curing agent having an acid anhydride group include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, and trialkyltetra. Hydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride , pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenyl. Sulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C ] Polymeric acid anhydrides such as furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and styrene-maleic acid resin copolymerized with styrene and maleic acid.

Additionally, a compound having at least two structures having the above-mentioned radical reactivity also has the function of curing the resin composition by reacting with component (III). These compounds can also be used as curing agents for component (IV).

Examples of compounds having at least two structures with radical reactivity include triallyl isocyanurate (Tyke manufactured by Mitsubishi Chemical Corporation), tris(2-hydroxyethyl) isocyanurate, diallyl fumarate, and adiph. and allyl monomers such as diallyl acid, triallyl citrate, and diallyl hexahydrophthalate.

When the resin composition of the present embodiment contains component (III), the polar resin of component (III) includes epoxy resin, polyimide resin, polyphenylene ether resin, and liquid crystal polyester resin from the viewpoint of adhesiveness. and at least one selected from the group consisting of fluorine resins.

More preferably, it is at least one selected from the group consisting of epoxy resin, polyimide resin, and polyphenylene ether resin.

The polyimide resin may be one that has an imide bond in the repeating unit and falls into the category called polyimide resin. For example, the structure of a general polyimide obtained by polycondensation (imide bond) of tetracarboxylic acid or its dianhydride and diamine is given. From the viewpoint of curability, it is preferable to have an unsaturated group at the terminal of the polyimide structure described above. Examples of the polyimide resin having an unsaturated group at the terminal include maleimide type polyimide resin, nadiimide type polyimide resin, and allylnadiimide type polyimide resin.

Tetracarboxylic acid or its dianhydride is not limited to the following, but examples include aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aliphatic tetracarboxylic dianhydride. These may be used individually or in combination of two or more types.

The diamine is not particularly limited, but examples include aromatic diamines, alicyclic diamines, and aliphatic diamines commonly used in the synthesis of polyimide. These may be used individually, or two or more types may be used together.

In addition, in at least one of the tetracarboxylic acid or its dianhydride or diamine, a fluorine group, a trifluoromethyl group, a hydroxyl group, a sulfone group, a carbonyl group, a heterocyclic ring, or a long-chain alkyl group is added from the viewpoint of low dielectric constant and low dielectric loss tangent. , allyl group, etc. may have one or more functional groups selected from the group consisting of at least one functional group.

In addition, as the polyimide resin, a commercially available polyimide resin may be used, for example, Neofullim (registered trademark) C-3650 (manufactured by Mitsubishi Gas Chemical Co., Ltd., brand name), C-3G30. (manufactured by Mitsubishi Gas Chemical Co., Ltd., brand name), Copper C-3450 (manufactured by Mitsubishi Gas Chemical Co., Ltd., brand name), Copper P500 (manufactured by Mitsubishi Gas Chemical Co., Ltd., brand name), BT (bismaleimide) ·Triazine) resin (manufactured by Mitsubishi Gas Chemical Co., Ltd.), JL-20 (manufactured by Nippon Rika Corporation, brand name) (varnishes made of such polyimide resins may contain silica), manufactured by Nippon Rika Corporation. Rica Coat SN20, Rica Coat PN20, Pyre-ML manufactured by I.S.T, UPIA-AT, UPIA-ST, UPIA-NF, UPIA-LB manufactured by Ube Kosan Corporation, PIX-1400, PIX-3400, PI2525 manufactured by Hitachi Kasei Corporation. , PI2610, HD-3000, AS-2600, HPC-5000, HPC-5012, HPC-1000, HPC-5020, HPC-3010, HPC-6000, HPC-9000, HCI-7000 manufactured by Showa Denko Co., Ltd. , HCI-1000S, HCI-1200E, HCI-1300, BMI-2300 manufactured by Daiwa Kasei Kogyo Co., Ltd., and MIR-3000 manufactured by Nippon Kayaku Co., Ltd.

The polyphenylene ether resin that is component (III) may be one that falls into the category called polyphenylene ether resin and contains a phenylene ether unit as a repeating structural unit. Such polyphenylene ether-based resin may be a homopolymer having a phenylene ether unit, or may contain other structural units other than the phenylene ether unit.

As a homopolymer having a phenylene ether unit, there is no particular limitation as to whether the phenylene group in the phenylene unit has a substituent. Substituents include, for example, acrylic groups such as ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, and tert-butyl group, cyclic alkyl groups such as cyclohexyl group, vinyl group, allyl group, and isopropenyl group, 1-butenyl group, 1-pentenyl group, p-vinylphenyl group, p-isopropenylphenyl group, m-vinylphenyl group, m-isopropenylphenyl group, o-vinylphenyl group, o-isopropenylphenyl group, p-vinylbenzyl group, p-isopropenylbenzyl group, m-vinylbenzyl group, m-isopropenylbenzyl group, o-vinylbenzyl group, o-isopropenylbenzyl group, p-vinylphenylethenyl group, p-vinylphenyl Prophenyl group, p-vinylphenylbutenyl group, m-vinylphenylethenyl group, m-vinylphenylpropenyl group, m-vinylphenylbutenyl group, o-vinylphenylethenyl group, o-vinylphenylpropenyl group, o-vinyl Unsaturated bond-containing substituents such as phenylbutenyl group, methacryl group, acrylic group, 2-ethylacryl group, and 2-hydroxymethylacryl group, hydroxyl group, carboxyl group, carbonyl group, thiocarbonyl group, acid halide group, acid anhydride group, carboxylic acid group, Boxylic acid group, thiocarboxylic acid group, aldehyde group, thioaldehyde group, carboxylic acid ester group, amide group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group. , thioepoxy group, sulfide group, isocyanate group, isothiocyanate group, silicon halide group, silanol group, alkoxy silicon group, tin halide group, boronic acid group, boron-containing group, boronic acid base, alkoxy tin group and phenyl tin group. and functional group-containing substituents such as these. From the viewpoint of curability, it is preferable to have an arbitrary polar group for the purpose of having radical reactivity and/or reactivity with the component (IV) curing agent.

The polyphenylene ether resin as component (III) preferably has a molecular weight of 100,000 or less, more preferably 50,000 or less, and even more preferably 10,000 or less from the viewpoint of curability of the resin composition of the present embodiment. In addition, the polyphenylene ether-based resin may have a linear structure or a crosslinked or branched structure.

The liquid crystal polyester resin that is component (III) may be a polyester that forms an anisotropic melt phase and falls within the category called liquid crystal polyester resin.

For example, "X7G" by Eastman Kodak, Xyday (Xyda) by Tatoko, Econol by Sumitomo Chemical, Vectra by Celanese, etc. are mentioned.

The fluorine-based resin that is component (III) can be anything that falls into the category called fluorine-based resin, and is an olefin-based polymer containing a fluorine group.

Examples of the fluorine-based resin include polytetrafluoroethylene, perfluoroalkoxyalkane, ethylene-tetrafluoroethylene copolymer, perfluoroethylene-propene copolymer, polyvinylidene fluoride, and polychlorotrifluoro. Ethylene, ethylene-chlorotrifluoroethylene copolymer, etc. can be mentioned.

The epoxy resin that is component (III) may be any that falls into the category called an epoxy resin, and from the viewpoint of strength, it is preferable that it has two or more epoxy groups in one molecule.

Epoxy resins may be used individually or in combination of two or more types.

Examples of the epoxy resin include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, and trisphenol type epoxy resin. Resin, naphthol novolac type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl Diester-type epoxy resin, cresol novolak-type epoxy resin, biphenyl-type epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane-type epoxy resin, cyclohexanedimethanol-type epoxy resin, naph. tylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc.; can be mentioned.

In addition, when using an epoxy resin as component (III) from the viewpoint of reactivity, it is preferable to also contain a component (IV) curing agent. In this case, examples of the polar group possessed by the component (IV) curing agent include carboxyl group, imidazole group, hydroxyl group, amino group, mercaptan group, benzoxazine group, and carbodiimide group. From the viewpoint of reactivity, carboxyl group and imida group A sol group, a hydroxyl group, a benzoxazine group, and a carbodiimide group are preferable, and from the viewpoint of dielectric performance, a hydroxyl group, a carboxyl group, an imidazole group, a benzoxazine group, and a carbodiimide group are more preferable, and still more preferably a hydroxyl group, a carboxyl group, and a carbodiimide group. It's mid-season.

In addition, when using two or more types of polar resins with different radical reactivity as component (III), from the viewpoint of curability, it is preferable to use component (II): radical initiator and component (IV): curing agent together. For example, when using a maleimide-type polyimide resin with excellent radical reactivity and a bisphenol A epoxy resin without radical reactivity as component (III), from the viewpoint of curability, component (II) radical initiator and the above-mentioned components (IV) It is desirable to add a hardener.

In addition, component (III): When using a polar resin with a high melting point and high rigidity as the polar resin, the resin composition of this embodiment does not need to contain component (IV). Examples of the polar resin with high melting point and high rigidity as component (III) include fluorine resins such as liquid crystal polyester resin and polytetrafluoroethylene.

Because component (III) has a high melting point and high rigidity, it tends to have the strength required for practical use even when component (IV) is not contained.

(Content of components (I) to (IV))

The resin composition of this embodiment contains a conjugated diene polymer (component (I)) and at least one component selected from the group consisting of components (II) to (IV) described above.

The content is preferably within the following numerical range, based on 100 parts by mass of component (I).

Component (II): 0.01 parts by mass to 200 parts by mass, more preferably 0.05 parts by mass to 150 parts by mass, even more preferably 0.10 parts by mass to 100 parts by mass.

Component (III): 5 parts by mass to 2000 parts by mass, more preferably 10 parts by mass to 1000 parts by mass, even more preferably 30 parts by mass to 500 parts by mass.

Component (IV): 5 parts by mass to 2000 parts by mass, more preferably 10 parts by mass to 1000 parts by mass, even more preferably 30 parts by mass to 500 parts by mass.

(Ingredient (V): Additive)

The resin composition of this embodiment may further contain various additives such as a curing accelerator, filler, and flame retardant as component (V).

Additionally, component (I) included as an additive in the conjugated diene copolymer is the same as component (V) of the resin composition.

As a curing accelerator, it is added for the purpose of promoting the reactivity between the above-mentioned components, and conventionally known ones can be used. Examples include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators.

A hardening accelerator may be used individually by one type, or may be used in combination of two or more types.

Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenyl borate, n-butylphosphonium tetraphenyl borate, tetrabutylphosphonium decanoate, and (4-methylphenyl)triphenyl. Examples include phosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,-tris(dimethylaminomethyl)phenol, 1, Examples include 8-diazabicyclo(5,4,0)-undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene are preferred.

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Midazole, 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-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium Trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s- Triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazineisocyanuric acid adduct, 2-phenylimidazoleisocyanuric acid addition Water, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2 -a] Imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and imidazole compounds and epoxy resins Adduct forms include, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

As an imidazole-type hardening accelerator, a commercial item may be used, for example, P200-H50 manufactured by Mitsubishi Chemical Corporation, etc.

Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, and diphenylguanidine. , trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n octadecyl biguanide, 1,1-dimethyl biguanide, 1,1 -diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc., dicyandiamide, 1 , 5,7-triazabicyclo[4.4.0]deca-5-ene is preferred.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin.

Specific examples of organometallic complexes include organic cobalt complexes such as cobalt (II) acetylacetonato and cobalt (III) acetylacetonato, organic copper complexes such as copper (II) acetylacetonato, and zinc (II) acetylacetonato. Examples include organic zinc complexes, organic iron complexes such as iron(III) acetylacetonato, organic nickel complexes such as nickel(II) acetylacetonato, and organic manganese complexes such as manganese(II) acetylacetonato.

Examples of organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

The filler is not limited to the following, but includes, for example, silica, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, calcium sulfate, barium sulfate, carbon black, glass fiber, glass beads, glass balloon, glass flake, graphite. Inorganic fillers such as titanium oxide, potassium titanate whiskers, carbon fiber, alumina, kaolin clay, silicic acid, calcium silicate, quartz, mica, talc, clay, zirconia, potassium titanate, alumina, metal particles; Organic fillers such as wood chips, wood powder, pulp, and cellulose nanofibers can be mentioned.

These may be used individually by 1 type, or may be used in combination of plurality.

The shape of these fillers may be flaky, spherical, granular, powdery, irregular, etc., and is not particularly limited.

The resin composition or cured product of the present embodiment is often exposed to high temperatures during molding, etc., and in order to prevent the molded body from being deformed due to shrinkage due to temperature changes, the filler preferably has a small coefficient of linear expansion. . From the viewpoint of lowering the coefficient of linear expansion, silica is preferable as a filler, and examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica.

Flame retardants include, for example, halogen-based flame retardants such as bromine compounds, phosphorus-based flame retardants such as aromatic compounds, metal hydroxides, alkylsulfonates, antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, hexabromobenzene, and decabromodiphenyl. and flame retardants containing aromatic bromine compounds such as ethane, 4,4-dibromobiphenyl, and ethylenebistetrabromophthalimide.

These flame retardants are used individually or in combination of two or more types.

Among the above flame retardants, so-called flame retardant auxiliaries are also included, which have a low flame retardancy development effect on their own, but exhibit a synergistically superior effect when used in combination with other flame retardants.

Fillers and flame retardants can also be of a type that has previously been surface treated with a surface treatment agent such as a silane coupling agent.

Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. Ringer, etc. can be mentioned. These may be used individually by 1 type, or may be used in combination of plurality.

Other additives are not particularly limited as long as they are commonly used in mixing resin compositions and/or cured products.

The other additives include, but are not limited to, pigments and/or colorants such as carbon black and titanium oxide; Lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, and ethylenebisstearoamide; Hyeong-Je Lee; Plasticizers such as organic polysiloxanes, fatty acid esters such as phthalic acid esters, adipic acid ester compounds, and azelaic acid ester compounds, and mineral oil; Antioxidants such as hindered phenol-based and phosphorus-based heat stabilizers; Hindered amine-based light stabilizer; Benzotriazole-based ultraviolet absorbers; antistatic agent; organic fillers; thickener; antifoaming agent; leveling agent; Resin additives such as adhesion imparting agents; Other additives or mixtures thereof may be included.

From the viewpoint of the above-mentioned low dielectric constant and low dielectric loss tangent, it tends to be preferable that the resin composition of this embodiment contains no pigment, colorant, lubricant, mold release agent, or antistatic agent.

The resin composition in this embodiment may be one in which each component is melt-kneaded, or each component may be dissolved in a soluble solvent and stirred (hereinafter referred to as “varnish”), but varnish is preferable from the viewpoint of handleability.

Examples of the solvent constituting the varnish include ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, and γ-butyrolactone; Acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, and diethyl glycol monoacetate; Carbitols such as cellosolve and butylcarbitol; aromatic hydrocarbons such as toluene and xylene; and amide-based solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. Organic solvents may be used individually, or may be used in combination of two or more types.

(Method for producing resin composition)

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

For example, a method of melting and kneading each component using a general mixer such as a Banbury mixer, single-screw extruder, twin-screw extruder, conider, or multi-screw extruder, dissolving or dispersing each component, and then heating the solvent. removal methods, etc., and from the viewpoint of processability for molded bodies suitable for materials for electronic circuit boards such as prepregs and sheets, which will be described later, a method of dissolving or dispersing and mixing each component and then removing the solvent by heating is preferable.

[Hardened product]

The cured product of this embodiment contains the conjugated diene-based copolymer of this embodiment described above.

In addition, the cured product of the present embodiment is a cured product of the resin composition of the present embodiment, and is obtained by subjecting the resin composition to a curing reaction at an arbitrary temperature and time. “Curing” is a concept that includes an aspect (semi-curing) in which, in addition to completely curing, only a part of the resin composition is cured and uncured components are included.

In the manufacturing process of the laminate described later, a step of further curing the cured product may be performed.

The reaction temperature in the curing process of the cured product of this embodiment is preferably 80°C or higher, more preferably 100°C or higher, and even more preferably 120°C or higher. As reaction time, 10 to 240 minutes is preferable, 20 to 230 minutes is more preferable, and 30 to 220 minutes is still more preferable. When the resin composition of this embodiment is a varnish, it is preferable to perform a curing reaction after removing the solvent. The drying method may be carried out by conventionally known methods such as heating and hot air spraying, and is preferably carried out at a temperature lower than the curing reaction temperature. The amount of solvent in the resin composition is preferably 10% by mass or less, more preferably 5% by mass or less. It is dried so that it reduces to less than % by mass.

[Resin film]

The resin film of this embodiment contains the resin composition of this embodiment.

The resin film of this embodiment is obtained, for example, by spreading the varnish containing the resin composition of this embodiment described above into a uniform thin film on a predetermined support, performing a drying treatment, and removing the solvent. Such a resin film can be wound into a roll and stored.

The resin film of this embodiment may have a structure in which a predetermined protective film is laminated, and in this case, it can be used by peeling the protective film.

[Prepreg]

The prepreg of this embodiment includes a base material and the resin composition of this embodiment impregnated or applied to this base material. That is, the prepreg of this embodiment is a composite of the resin composition of this embodiment and a base material.

The prepreg is, for example, impregnated with a varnish that is the resin composition of the present embodiment, by impregnating a substrate such as glass cloth with the varnish of the resin composition of the present embodiment, or by applying the resin composition of the present embodiment onto the substrate by the drying method described above. Obtained by removing the solvent.

As a base material, for example, various glass cloths such as roving cloth, cloth, chopped mat, and surfacing mat; Asbestos cloth, metal fiber cloth and other synthetic or natural inorganic fiber cloth; Woven or non-woven fabrics obtained from liquid crystalline fibers such as wholly aromatic polyamide fibers, wholly aromatic polyester fibers, and polybenzoxazole fibers; Natural fiber fabrics such as cotton cloth, linen cloth, and felt; natural cellulose-based substrates such as carbon fiber cloth, kraft paper, cotton paper, and cloth obtained from paper-glass blend yarn; Examples include porous polytetrafluoroethylene films, but glass cloth is preferred from the viewpoint of dielectric performance.

These base materials are used individually or in combination of two or more types.

It is preferable that it is 30-80 mass %, and, as for the ratio of the solid content containing the resin composition of this embodiment in a prepreg, it is more preferable that it is 40-70 mass %. When the above ratio is 30% by mass or more, insulation reliability tends to be more excellent when the prepreg is used for electronic substrates, etc. When the above ratio is 80% by mass or less, mechanical properties such as rigidity tend to be more excellent in applications such as electronic boards.

[Laminate]

The laminated body of this embodiment has the resin film and metal foil mentioned above. In addition, the laminate of this embodiment can also be configured to include the cured product of the prepreg described above and the metal foil.

The laminate of the present embodiment includes, for example, a step (a) of forming a resin layer by laminating a resin film containing the resin composition of the present embodiment on a base material to obtain a prepreg, and heating the resin layer. It can be manufactured through a step (b) of pressurizing and flattening to obtain a cured prepreg, and a step (c) of further forming a predetermined wiring layer containing metal foil on the resin layer.

In step (a), the method of laminating the resin film on the substrate is not particularly limited, but examples include a multi-stage press, vacuum press, normal pressure laminator, and a method of laminating using a laminator that heats and presses under vacuum. A method using a laminator that heats and presses under vacuum is preferred.

In the method of using this laminator, even if the target electronic circuit board has fine wiring circuits on the surface, there are no voids and the circuits can be filled with resin. Additionally, the laminate may be batch type or continuous type using rolls or the like.

The substrate is not limited to the following, but examples include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, polyphenylene ether substrates, and fluororesin substrates. The surface on which the resin layer of the base material is laminated may be roughened in advance, and the number of base material layers is not limited.

In the step (b), the resin film and the base material laminated in the step (a) are flattened by heating and pressing. Conditions can be arbitrarily adjusted depending on the type of substrate or the composition of the resin film, but for example, the range of temperature 100 to 300°C, pressure 0.2 to 20 MPa, and time 30 to 180 minutes is preferable.

In the step (c), a predetermined wiring layer containing metal foil is formed on the resin layer produced by heating and pressing the resin film and the base material. The formation method is not particularly limited and includes conventionally known methods, for example, etching methods such as subtractive methods, semi-additive methods, etc.

In the subtractive method, an etching resist layer of a shape corresponding to the desired pattern shape is formed on a metal layer, and through subsequent development, the metal layer in the area from which the resist was removed is removed by dissolving it in a chemical solution, thereby forming the desired wiring. How to form it.

The semi-additive method involves forming a metal film on the surface of a resin layer by an electroless plating method, forming a plating resist layer with a shape corresponding to a desired pattern on the metal film, and then forming a metal layer by electrolytic plating. This is a method of forming the desired wiring layer by removing the unnecessary electroless plating layer with a chemical solution or the like.

Additionally, holes such as via holes may be formed in the resin layer as needed, and the method of forming the holes is not particularly limited and a conventionally known method can be used. As a method for forming holes, for example, NC drill, carbon dioxide gas laser, UV laser, YAG laser, plasma, etc. can be used.

[Metal clad laminate]

The laminate of the present embodiment described above may be plate-shaped or may be a flexible laminate having flexibility.

The laminate of this embodiment may be a metal-clad laminate.

The metal clad laminate is obtained by laminating the resin composition of this embodiment or the prepreg of this embodiment and metal foil and curing it, and a part of the metal foil is removed from the metal clad laminate.

The metal-clad laminate preferably has a form in which a cured prepreg (also called “cured material composite”) and metal foil are laminated and in close contact, and is suitably used as a material for electronic circuit boards.

Examples of metal foil include aluminum foil and copper foil, and among these, copper foil is preferable because it has low electrical resistance.

The cured product of the prepreg combined with the metal foil may be one sheet or plural sheets, and the metal foil is overlapped on one or both sides of the cured product depending on the application and processed into a laminated board.

As a method of manufacturing the above-mentioned laminated board, for example, a prepreg composed of the resin composition of the present embodiment and a base material is formed, this is overlapped with metal foil, and then the resin composition is cured, so that the cured product of the prepreg and the metal foil are laminated. There is a method of obtaining a laminated board.

One particularly preferred use of the above laminate is printed wiring boards. It is preferable that at least part of the metal foil of the printed wiring board is removed from the metal clad laminate.

The printed wiring board can be produced by using the prepreg of this embodiment described above by pressure heat molding. As a base material, the same thing as described above for the prepreg can be used. By containing the resin composition of the present embodiment, the printed wiring board has excellent strength and electrical properties (low dielectric constant and low dielectric loss tangent), and can further suppress variations in electrical properties due to environmental changes, and has excellent insulation reliability. and mechanical properties.

[Materials for electronic circuit boards]

The material of the electronic circuit board of this embodiment includes a cured product of the resin composition of this embodiment.

The material for an electronic circuit board of this embodiment can be produced using the resin composition and/or varnish of this embodiment described above.

The material for the electronic circuit board of this embodiment is selected from the group consisting of a cured product of the above-described resin composition, a resin film containing the resin composition of this embodiment or a cured product thereof, and a prepreg that is a composite of a base material and a resin composition. Includes at least something that is The material for an electronic circuit board of this embodiment can be used as a printed wiring board provided with a metal foil with resin.

[Example]

Hereinafter, the present embodiment will be described in detail through specific examples and comparative examples, but the present invention is not limited at all to the following examples and comparative examples.

In addition, the structure of the hydrogenated conjugated diene-based copolymer or the non-hydrogenated conjugated diene-based copolymer (component (I)) (hereinafter sometimes referred to as conjugated diene-based copolymer) of the following Examples and Comparative Examples Methods for identification and measurement of physical properties are shown below.

[Method for identifying the structure and measuring physical properties of conjugated diene copolymers]

((1) Content of vinyl aromatic monomer unit of conjugated diene copolymer)

Using the conjugated diene-based copolymer before hydrogenation, the content of the vinyl aromatic monomer unit in the copolymer was measured using an ultraviolet spectrophotometer (UV-2450, manufactured by Shimadzu Seisakusho).

((2) Vinyl bond amount of conjugated diene copolymer)

Using the conjugated diene-based copolymer before hydrogenation, the amount of vinyl bonds was measured using an infrared spectrophotometer (FT/IR-230, manufactured by Nippon Bunko Co., Ltd.).

The amount of vinyl bonds in the copolymer was calculated by the Hampton method.

((3) Molecular weight and coupling rate of conjugated diene copolymer)

The molecular weight of the conjugated diene copolymer of component (I) before modification and before hydrogenation was measured by GPC [equipment: LC-10 (manufactured by Shimadzu Seisakusho), column: TSKgelGMHXL (4.6 mm x 30 cm)]. .

Tetrahydrofuran was used as a solvent.

The measurement conditions were performed at a temperature of 35°C.

The molecular weight is the weight average molecular weight obtained by using the molecular weight of the peak of the chromatogram using a calibration curve (prepared using the peak molecular weight of standard polystyrene) obtained from the measurement of commercially available standard polystyrene.

In addition, when there are multiple peaks in a chromatogram, the molecular weight was set as the average molecular weight determined from the molecular weight of each peak and the composition ratio of each peak (determined from the area ratio of each peak in the chromatogram).

Additionally, using the molecular weight distribution (Mw/Mn) measured by GPC, the coupling rate was determined using the peak area before coupling and the peak area after coupling.

((4) Hydrogenation rate of double bond of conjugated diene monomer unit of conjugated diene copolymer)

Component (I) after hydrogenation: A hydrogenated conjugated diene-based copolymer was used, and the hydrogenation rate of the double bond of the conjugated diene monomer unit was measured using a nuclear magnetic resonance device (DPX-400, manufactured by BRUKER).

((5) Amount of vinyl aromatic monomer and ratio of conjugated diene monomer in polymer block (C))

Each time the vinyl aromatic compound (styrene) and/or conjugated diene compound (butadiene) constituting each polymer block were added to the reaction furnace, the polymerization solution before addition was sampled. Approximately 20 mL of the sampled polymer solution was injected into a 100 mL bottle sealed with 0.50 mL of n-propylbenzene and approximately 20 mL of toluene as internal standards to prepare a sample for measurement. Samples for measurement were measured using a gas chromatograph (GC-14B, manufactured by Shimadzu Seisakusho) equipped with a packed column carrying Apiezon grease, and the residue in the polymer solution was determined from the previously obtained calibration curve of butadiene monomer and styrene monomer. The amount of monomer was determined, and it was confirmed that the polymerization rate of butadiene monomer and/or styrene monomer was 100%. Therefore, the composition ratio of the vinyl aromatic monomer and the conjugated diene monomer unit in the polymer block (C) was set to the same value as the weight ratio of the added vinyl aromatic monomer and the conjugated diene monomer unit.

In addition, the polymerization rate of butadiene was measured at a constant temperature of 90°C, and the polymerization rate of styrene was measured under conditions of a temperature increase of 90°C (hold for 10 minutes) to 150°C (10°C/min).

[Hydrogenated or non-hydrogenated conjugated diene copolymers (sometimes collectively referred to as conjugated diene copolymers), materials for resin compositions]

(Preparation of hydrogenation catalyst)

In the production examples and comparative production examples described later, the hydrogenation catalyst used when producing the hydrogenated conjugated diene-based copolymer was prepared by the following method.

A reaction vessel equipped with a stirring device was purged with nitrogen, and 1 liter of dried and purified cyclohexane was added thereto.

Next, 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added. While sufficiently stirring, an n-hexane solution containing 200 mmol of trimethylaluminum was added, and the mixture was allowed to react at room temperature for about 3 days. As a result, a hydrogenation catalyst was obtained.

(Component (I): Conjugated diene copolymer)

A conjugated diene-based copolymer of a vinyl aromatic compound and a conjugated diene compound was prepared as follows.

The structure and physical properties of each conjugated diene copolymer are shown in Tables 1 and 2.

<(Production Example 1) Conjugated diene-based copolymer (1)>

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration 20% by mass) containing 20 parts by mass of styrene was added.

Next, 0.040 parts by mass of n-butyllithium per 100 parts by mass of all monomers and 0.2 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and polymerization was performed at 70°C for 15 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 32 parts by mass of butadiene and 48 parts by mass of styrene was added, and polymerization was performed at 70°C for 40 minutes.

Next, 0.5 mol of ethyl benzoate was added per 1 mol of n-butyllithium, and reaction was performed at 70°C for 10 minutes. After that, methanol was added to stop the polymerization reaction.

The conjugated diene-based block copolymer (1) obtained as described above has a styrene content of 68% by mass, a vinyl aromatic monomer amount of 60% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 19.0×10 ⁴ , 1,2. The content of unit (a) derived from -bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 25%, and the coupling rate was 50%.

<(Production Example 2): Hydrogenated conjugated diene-based copolymer (2)>

The same operation as Production Example (1) was performed to obtain conjugated diene-based copolymer (2). Using the obtained conjugated diene-based copolymer (2), the hydrogenation catalyst prepared as above was added at 90 ppm based on Ti per 100 parts by mass of the conjugated diene-based block copolymer, and hydrogen was added at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. The reaction was performed for about 0.3 hours, and hydrogenated conjugated diene-based block copolymer (2) was obtained.

The hydrogenated conjugated diene-based block copolymer (2) obtained as described above has a styrene content of 68% by mass, a vinyl aromatic monomer amount of 60% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 18.9 × 10 ⁴ , 1. The content of unit (a) derived from 2-bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 26%, coupling rate was 49%, and hydrogenation rate was 30%.

<(Production Example 3): Hydrogenated conjugated diene-based copolymer (3)>

The same operation as Production Example (1) was performed to obtain conjugated diene-based copolymer (3). Using the obtained conjugated diene-based copolymer (3), the hydrogenation catalyst prepared as above was added at 90 ppm based on Ti per 100 parts by mass of the conjugated diene-based block copolymer, and hydrogen was added at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. The reaction was performed for about 1.25 hours, and hydrogenated conjugated diene-based block copolymer (3) was obtained.

The hydrogenated conjugated diene-based block copolymer (3) obtained as described above has a styrene content of 68% by mass, a vinyl aromatic monomer amount of 60% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 19.0 × 10 ⁴ , 1. The content of unit (a) derived from 2-bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 26%, coupling rate was 50%, and hydrogenation rate was 98%.

<(Production Example 4): Hydrogenated conjugated diene-based copolymer (4)>

The same operation as in Production Example 2 was performed except that 0.3 mol of ethyl benzoate was added per 1 mol of n-butyllithium.

The hydrogenated conjugated diene-based block copolymer (4) obtained as described above has a styrene content of 68% by mass, a vinyl aromatic monomer amount of 60% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 19.0 × 10 ⁴ , 1. The content of unit (a) derived from 2-bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 26%, coupling rate was 30%, and hydrogenation rate was 30%.

<(Production Example 5) Conjugated diene-based copolymer (5)>

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration 20% by mass) containing 10 parts by mass of styrene was added.

Next, 0.050 parts by mass of n-butyllithium per 100 parts by mass of all monomers and 0.15 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and polymerization was performed at 70°C for 7 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 35 parts by mass of butadiene and 45 parts by mass of styrene was added, and polymerization was performed at 70°C for 40 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 10 parts by mass of styrene was added, and polymerization was performed at 70°C for 7 minutes. After that, methanol was added to stop the polymerization reaction.

The conjugated diene-based block copolymer (5) obtained as described above has a styrene content of 65% by mass, a vinyl aromatic monomer amount of 56% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 15.1×10 ⁴ , 1,2. The content of unit (a) derived from -bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 15%.

<(Production Example 6) Hydrogenated conjugated diene-based copolymer (6)>

The same operation as in Production Example (5) was performed to obtain conjugated diene-based copolymer (6). Using the obtained conjugated diene-based copolymer (6), the hydrogenation catalyst prepared as above was added at 90 ppm based on Ti per 100 parts by mass of the conjugated diene-based block copolymer, and hydrogen was added at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. The reaction was performed for about 0.30 hours, and hydrogenated conjugated diene-based block copolymer (6) was obtained.

The hydrogenated conjugated diene-based block copolymer (6) obtained as described above has a styrene content of 65% by mass, a vinyl aromatic monomer amount of 56% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 15.0 × 10 ⁴ , 1. The content of unit (a) derived from 2-bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 16%, and the hydrogenation rate was 31%.

<(Production Example 7) Hydrogenated conjugated diene-based copolymer (7)>

The same operation as in Production Example (5) was performed to obtain conjugated diene-based copolymer (7). Using the obtained conjugated diene-based copolymer (7), the hydrogenation catalyst prepared as above was added at 90 ppm based on Ti per 100 parts by mass of the conjugated diene-based block copolymer, and hydrogen was added at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. The reaction was performed for about 1.25 hours, and hydrogenated conjugated diene-based block copolymer (7) was obtained.

The hydrogenated conjugated diene-based block copolymer (7) obtained as described above has a styrene content of 65% by mass, a vinyl aromatic monomer amount of 56% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 15.0 × 10 ⁴ , 1. The content of unit (a) derived from 2-bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 15%, and the hydrogenation rate was 99%.

<(Production Example 8) Conjugated diene-based copolymer (8)>

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration 20% by mass) containing 10 parts by mass of styrene was added.

Next, 0.045 parts by mass of n-butyllithium per 100 parts by mass of all monomers and 0.15 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and polymerization was performed at 70°C for 7 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 17 parts by mass of butadiene and 10 parts by mass of styrene was added, and polymerization was performed at 70°C for 15 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 21 parts by mass of butadiene and 34 parts by mass of styrene was added and polymerization was performed at 70°C for 30 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 8 parts by mass of styrene was added, and polymerization was performed at 70°C for 5 minutes. After that, methanol was added to stop the polymerization reaction.

The conjugated diene block copolymer (8) obtained as described above has a styrene content of 62% by mass, a vinyl aromatic monomer amount of 54% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 17.1×10 ⁴ , 1,2. The content of unit (a) derived from -bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 20%.

<(Production Example 9) Hydrogenated conjugated diene-based copolymer (9)>

The same operation as in Production Example 8 was performed to obtain conjugated diene-based copolymer (9).

Using the conjugated diene-based copolymer (9) obtained as described above, the hydrogenation catalyst prepared as described above was added at 90 ppm based on Ti per 100 parts by mass of the conjugated diene-based block copolymer, and the hydrogen pressure was 0.7 MPa and the temperature was 80%. A hydrogenation reaction was performed at °C for about 0.35 hours to obtain a hydrogenated conjugated diene-based block copolymer (9).

The hydrogenated conjugated diene-based block copolymer (9) obtained as described above has a styrene content of 62% by mass, a vinyl aromatic monomer amount of 54% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 17.0 × 10 ⁴ , 1. The content of unit (a) derived from 2-bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 20%, and the hydrogenation rate was 35%.

<(Production Example 10) Hydrogenated conjugated diene-based copolymer (10)>

The same operation as in Production Example 8 was performed to obtain conjugated diene-based copolymer (10).

Using the conjugated diene-based copolymer (10) obtained as above, the hydrogenation catalyst prepared as above was added at 90 ppm based on Ti per 100 parts by mass of the conjugated diene-based block copolymer, and the hydrogen pressure was 0.7 MPa and the temperature was 80%. A hydrogenation reaction was performed at °C for about 1.25 hours to obtain a hydrogenated conjugated diene-based block copolymer (10).

The hydrogenated conjugated diene-based block copolymer (10) obtained as described above has a styrene content of 62% by mass, a vinyl aromatic monomer amount of 54% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 17.0 × 10 ⁴ , 1. The content of unit (a) derived from 2-bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 21%, and the hydrogenation rate was 98%.

<(Production Example 11) Hydrogenated conjugated diene-based copolymer (11)>

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration 20% by mass) containing 5 parts by mass of styrene was added.

Next, 0.13 parts by mass of n-butyllithium per 100 parts by mass of all monomers and 1.0 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and polymerization was performed at 60°C for 5 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 30 parts by mass of butadiene and 50 parts by mass of styrene was added, and polymerization was performed at 60°C for 40 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 15 parts by mass of butadiene was added, and polymerization was performed at 60°C for 40 minutes. After that, methanol was added to stop the polymerization reaction.

The conjugated diene-based block copolymer (11) obtained as described above has a styrene content of 55% by mass, a vinyl aromatic monomer amount of 63% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 6.5×10 ⁴ , 1,2. The content of unit (a) derived from -bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 60%.

Using the obtained conjugated diene-based copolymer (11), the hydrogenation catalyst prepared as above was added at 90 ppm based on Ti per 100 parts by mass of the conjugated diene-based block copolymer, and hydrogen was added at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. The reaction was performed for about 0.3 hours, and hydrogenated conjugated diene-based block copolymer (11) was obtained. The hydrogen addition rate was 30%.

<(Production Example 12) Hydrogenated conjugated diene-based copolymer (12)>

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration 20% by mass) containing 15 parts by mass of butadiene was added.

Next, 0.13 parts by mass of n-butyllithium per 100 parts by mass of all monomers and 1.0 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and polymerization was performed at 70°C for 15 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 20 parts by mass of butadiene and 50 parts by mass of styrene was added and polymerization was performed at 70°C for 30 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 15 parts by mass of butadiene was added, and polymerization was performed at 60°C for 15 minutes. After that, methanol was added to stop the polymerization reaction.

The conjugated diene-based block copolymer (12) obtained as described above has a styrene content of 50% by mass, a vinyl aromatic monomer amount of 71% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 6.4×10 ⁴ , 1,2. The content of unit (a) derived from -bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 60%.

Using the obtained conjugated diene-based copolymer (12), the hydrogenation catalyst prepared as above was added at 90 ppm based on Ti per 100 parts by mass of the conjugated diene-based block copolymer, and hydrogen was added at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. The reaction was performed for about 0.3 hours, and hydrogenated conjugated diene-based block copolymer (12) was obtained. The hydrogen addition rate was 31%.

<(Production Example 13) Hydrogenated conjugated diene-based copolymer (13)>

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration 20% by mass) containing 7.5 parts by mass of butadiene was added.

Next, 0.087 parts by mass of n-butyllithium per 100 parts by mass of all monomers and 1.0 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and polymerization was performed at 60°C for 7 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 5 parts by mass of butadiene and 75 parts by mass of styrene was added, and polymerization was performed at 60°C for 25 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 7.5 parts by mass of butadiene was added, and polymerization was performed at 60°C for 7 minutes. After that, methanol was added to stop the polymerization reaction.

The conjugated diene-based block copolymer (13) obtained as described above has a styrene content of 75% by mass, a vinyl aromatic monomer amount of 94% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 8.0×10 ⁴ , 1,2. The content of unit (a) derived from -bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 74%.

Using the obtained conjugated diene-based copolymer (13), the hydrogenation catalyst prepared as above was added at 90 ppm based on Ti per 100 parts by mass of the conjugated diene-based block copolymer, and hydrogen was added at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. The reaction was performed for about 0.3 hours, and hydrogenated conjugated diene-based block copolymer (13) was obtained. The hydrogen addition rate was 30%.

<(Production Example 14) Hydrogenated conjugated diene-based copolymer (14)>

Except that the hydrogenation reaction time was 1.25 hours, the same operation as in Production Example 13 was performed to obtain hydrogenated conjugated diene-based copolymer (14).

The hydrogenated conjugated diene-based block copolymer (14) obtained as described above has a styrene content of 75% by mass, a vinyl aromatic monomer amount of 94% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 8.0 × 10 ⁴ , 1. The content of unit (a) derived from 2-bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 74%, and the hydrogenation rate was 99%.

<(Production Example 15) Hydrogenated conjugated diene-based copolymer (15)>

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration 20% by mass) containing 5 parts by mass of butadiene was added.

Next, 0.099 parts by mass of n-butyllithium per 100 parts by mass of all monomers and 0.8 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and polymerization was performed at 60°C for 20 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 5 parts by mass of butadiene and 85 parts by mass of styrene was added, and polymerization was performed at 60°C for 30 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 5 parts by mass of butadiene was added, and polymerization was performed at 60°C for 20 minutes. Afterwards, methanol was added to stop the polymerization reaction.

The conjugated diene-based block copolymer (15) obtained as described above has a styrene content of 85% by mass, a vinyl aromatic monomer amount of 94% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 6.4×10 ⁴ , 1,2. The content of unit (a) derived from -bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 61%.

Using the obtained conjugated diene-based copolymer (15), the hydrogenation catalyst prepared as above was added at 90 ppm based on Ti per 100 parts by mass of the conjugated diene-based block copolymer, and hydrogen was added at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. The reaction was performed for about 0.3 hours, and hydrogenated conjugated diene-based block copolymer (15) was obtained. The hydrogen addition rate was 29%.

<(Production Example 16) Hydrogenated conjugated diene-based copolymer (16)>

Except that the hydrogenation reaction time was 0.15 hours, the same operation as in Production Example 9 was performed to obtain a hydrogenated conjugated diene-based copolymer (16).

The hydrogenated conjugated diene-based block copolymer (16) obtained as described above has a styrene content of 62% by mass, a vinyl aromatic monomer amount of 54% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 16.9 × 10 ⁴ , 1. The content of unit (a) derived from 2-bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 20%, and the hydrogenation rate was 15%.

<(Production Example 17) Hydrogenated conjugated diene-based copolymer (17)>

Except that the hydrogenation reaction time was 1.00 hours, the same operation as in Production Example 9 was performed to obtain a hydrogenated conjugated diene-based copolymer (17).

The hydrogenated conjugated diene-based block copolymer (17) obtained as described above has a styrene content of 62% by mass, a vinyl aromatic monomer amount of 54% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 17.0 × 10 ⁴ , 1. The content of unit (a) derived from 2-bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 21%, and the hydrogenation rate was 85%.

<(Production Example 18) Hydrogenated conjugated diene-based copolymer (18)>

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration 20 mass%) containing 15 mass parts of styrene was added.

Next, 0.045 parts by mass of n-butyllithium per 100 parts by mass of all monomers and 0.15 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and polymerization was performed at 70°C for 7 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 17 parts by mass of butadiene and 5 parts by mass of styrene was added, and polymerization was performed at 70°C for 15 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 21 parts by mass of butadiene and 29 parts by mass of styrene was added and polymerization was performed at 70°C for 30 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 13 parts by mass of styrene was added, and polymerization was performed at 70°C for 5 minutes. Afterwards, methanol was added to stop the polymerization reaction.

The conjugated diene-based block copolymer (18) obtained as described above has a styrene content of 62% by mass, a vinyl aromatic monomer amount of 47% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 17.1×10 ⁴ , 1,2. The content of unit (a) derived from -bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 20%.

Using the obtained conjugated diene-based copolymer (18), the hydrogenation catalyst prepared as above was added at 90 ppm based on Ti per 100 parts by mass of the conjugated diene-based block copolymer, and hydrogen was added at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. The reaction was performed for about 0.3 hours, and hydrogenated conjugated diene-based block copolymer (18) was obtained. The hydrogen addition rate was 31%.

<(Comparative Preparation Example 1) Hydrogenated conjugated diene-based copolymer (19)>

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration 20% by mass) containing 42 parts by mass of styrene was added.

Next, 0.040 parts by mass of n-butyllithium per 100 parts by mass of all monomers and 0.15 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and polymerization was performed at 70°C for 30 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 35 parts by mass of butadiene and 23 parts by mass of styrene was added, and polymerization was performed at 70°C for 20 minutes.

Next, 0.5 mol of ethyl benzoate was added per 1 mol of n-butyllithium, and reaction was performed at 70°C for 10 minutes. After that, methanol was added to stop the polymerization reaction.

The conjugated diene-based block copolymer (19) obtained as described above has a styrene content of 65% by mass, a vinyl aromatic monomer amount of 40% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 19.0×10 ⁴ , 1,2. The content of unit (a) derived from -bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 15%, and the coupling rate was 50%.

Using the obtained conjugated diene-based copolymer (19), the hydrogenation catalyst prepared as above was added at 90 ppm based on Ti per 100 parts by mass of the conjugated diene-based block copolymer, and hydrogen was added at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. The reaction was performed for about 0.3 hours, and hydrogenated conjugated diene-based block copolymer (19) was obtained. The hydrogen addition rate was 30%.

<(Comparative Preparation Example 2) Conjugated diene-based copolymer (20)>

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration 20% by mass) containing 21 parts by mass of styrene was added.

Next, 0.050 parts by mass of n-butyllithium per 100 parts by mass of all monomers and 0.15 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and polymerization was performed at 70°C for 30 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 35 parts by mass of butadiene and 23 parts by mass of styrene was added, and polymerization was performed at 70°C for 30 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 21 parts by mass of styrene was added, and polymerization was performed at 70°C for 30 minutes. After that, methanol was added to stop the polymerization reaction.

The conjugated diene-based block copolymer (20) obtained as described above has a styrene content of 65% by mass, a vinyl aromatic monomer amount of 40% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 15.1×10 ⁴ , 1,2. The content of unit (a) derived from -bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 16%.

<(Comparative Preparation Example 3) Hydrogenated conjugated diene-based copolymer (21)>

The same operation as Comparative Production Example 2 was performed to obtain conjugated diene-based copolymer (21).

Using the obtained conjugated diene-based copolymer (21), the hydrogenation catalyst prepared as above was added at 90 ppm based on Ti per 100 parts by mass of the conjugated diene-based block copolymer, and hydrogen was added at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. The reaction was performed for about 0.3 hours, and hydrogenated conjugated diene-based block copolymer (21) was obtained.

The hydrogenated conjugated diene-based block copolymer (21) obtained as described above has a styrene content of 65% by mass, a vinyl aromatic monomer amount of 40% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 15.0 × 10 ⁴ , 1. The content of unit (a) derived from 2-bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 16%, and the hydrogenation rate was 30%.

<(Comparative Preparation Example 4) Hydrogenated conjugated diene-based copolymer (22)>

Conjugated diene-based copolymer (22) was obtained by performing the same operation as Comparative Production Example 3 except that the hydrogenation reaction time was 1.25 hours.

The hydrogenated conjugated diene-based block copolymer (22) obtained as described above has a styrene content of 65% by mass, a vinyl aromatic monomer amount of 40% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 15.0 × 10 ⁴ , 1. The content of unit (a) derived from 2-bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 15%, and the hydrogenation rate was 98%.

<(Comparative Preparation Example 5) Hydrogenated conjugated diene-based copolymer (23)>

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration 20 mass%) containing 30 mass parts of styrene was added.

Next, 0.13 parts by mass of n-butyllithium per 100 parts by mass of all monomers and 1.0 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and polymerization was performed at 60°C for 5 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 37.5 parts by mass of butadiene and 25 parts by mass of styrene was added, and polymerization was performed at 60°C for 35 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 7.5 parts by mass of butadiene was added, and polymerization was performed at 60°C for 7 minutes. After that, methanol was added to stop the polymerization reaction.

The conjugated diene-based block copolymer (23) obtained as described above has a styrene content of 55% by mass, a vinyl aromatic monomer amount of 40% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 6.5×10 ⁴ , 1,2. The content of unit (a) derived from -bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 60%.

Using the obtained conjugated diene-based copolymer (23), a hydrogenation catalyst prepared as described above was added at 90 ppm based on Ti per 100 parts by mass of the conjugated diene-based block copolymer, and hydrogen was added at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. The reaction was performed for about 0.3 hours, and hydrogenated conjugated diene-based block copolymer (23) was obtained. The hydrogen addition rate was 30%.

<(Comparative Preparation Example 6) Hydrogenated conjugated diene-based copolymer (24)>

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration 20% by mass) containing 10 parts by mass of butadiene was added.

Next, 0.13 parts by mass of n-butyllithium per 100 parts by mass of all monomers and 1.0 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and polymerization was performed at 70°C for 10 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 50 parts by mass of butadiene and 30 parts by mass of styrene was added, and polymerization was performed at 70°C for 30 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 10 parts by mass of butadiene was added, and polymerization was performed at 60°C for 10 minutes. After that, methanol was added to stop the polymerization reaction.

The conjugated diene-based block copolymer (24) obtained as described above has a styrene content of 30% by mass, a vinyl aromatic monomer amount of 50% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 6.4×10 ⁴ , 1,2. The content of unit (a) derived from -bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 60%.

Using the obtained conjugated diene-based copolymer (24), the hydrogenation catalyst prepared as above was added at 90 ppm based on Ti per 100 parts by mass of the conjugated diene-based block copolymer, and hydrogen was added at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. The reaction was performed for about 0.3 hours, and hydrogenated conjugated diene-based block copolymer (24) was obtained. The hydrogen addition rate was 30%.

<(Comparative Preparation Example 7) Hydrogenated conjugated diene-based copolymer (25)>

Batch polymerization was performed using a tank reactor (inner volume 10 L) equipped with a stirring device and a jacket.

First, a cyclohexane solution (concentration 20% by mass) containing 7.5 parts by mass of styrene was added.

Next, 0.051 parts by mass of n-butyllithium per 100 parts by mass of all monomers and 0.15 mol of tetramethylethylenediamine (TMEDA) per 1 mol of n-butyllithium were added, and polymerization was performed at 70°C for 10 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 50 parts by mass of butadiene and 35 parts by mass of styrene was added, and polymerization was performed at 70°C for 40 minutes.

Next, a cyclohexane solution (concentration 20% by mass) containing 7.5 parts by mass of styrene was added, and polymerization was performed at 70°C for 10 minutes. After that, methanol was added to stop the polymerization reaction.

The conjugated diene-based block copolymer (25) obtained as described above has a styrene content of 50% by mass, a vinyl aromatic monomer amount of 41% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 16.0×10 ⁴ , 1,2. The content of unit (a) derived from -bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 20%.

Using the obtained conjugated diene-based copolymer (25), the hydrogenation catalyst prepared as above was added at 90 ppm based on Ti per 100 parts by mass of the conjugated diene-based block copolymer, and hydrogen was added at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. The reaction was performed for about 1.25 hours, and hydrogenated conjugated diene-based block copolymer (25) was obtained. The hydrogen addition rate was 99%.

<(Comparative Preparation Example 8) Hydrogenated conjugated diene-based copolymer (26)>

Conjugated diene-based copolymer (26) was obtained by performing the same operation as Production Example (7) except that n-butyllithium was adjusted to 0.26 parts by mass based on 100 parts by mass of all monomers.

The hydrogenated conjugated diene-based block copolymer (26) obtained as described above has a styrene content of 65% by mass, a vinyl aromatic monomer amount of 56% by mass in 100 parts by mass of the polymer block (C), and a weight average molecular weight of 3.0 × 10 ⁴ , 1. The content of unit (a) derived from 2-bond and/or 3,4-bond (amount of vinyl bond: unit (a)/butadiene) was 15%, and the hydrogenation rate was 99%.

(Component (II): radical initiator)

Perbutyl P-90 (manufactured by Nichiyu Co., Ltd.)

Percumil D (manufactured by Nichiyu Co., Ltd.)

(Component (III): Polar Resin)

<Epoxy Resin>

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

<Polyimide resin>

Bis(3-ethyl-5-methyl-4-maleimide phenyl)methane (BMI-70) (manufactured by K·I Kasei Co., Ltd.)

4,4'-Bismaleimide diphenylmethane (BMI-H) (manufactured by K·I Kasei Co., Ltd.)

<Polyphenylene ether resin (PPE resin)>

PPE resin was polymerized as follows.

A 1.5 liter jacketed reactor equipped with a sparger for introducing oxygen-containing gas at the bottom of the reactor, a stirring turbine blade and baffle, and a reflux cooler in the vent gas line at the top of the reactor, 0.2512 g of cupric chloride dihydrate, 1.1062 g 35% hydrochloric acid, 3.6179 g of di-n-butylamine, 9.5937 g of N,N,N',N'-tetramethylpropanediamine, 211.63 g of methanol and 493.80 g of n-butanol, 5 mol% of 2 , 180.0 g of 2,6-dimethylphenol containing 2-bis(3,5-dimethyl-4-hydroxyphenyl)propane was added. The composition mass ratio of the solvent used was n-butanol:methanol=70:30. Then, while vigorously stirring, oxygen was started to be introduced from the sparger into the reactor at a rate of 180 mL/min, while the polymerization temperature was adjusted by passing a heat medium through the jacket to maintain 40°C. The polymerization liquid gradually took the form of a slurry. When the polyphenylene ether reached the desired number average molecular weight, the aeration of the oxygen-containing gas was stopped, and the obtained polymerization mixture was warmed to 50°C. Next, hydroquinone (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added in small portions, and warming at 50°C was continued until the polyphenylene ether in the slurry turned white. Next, 720 g of a methanol solution containing 6.5% by mass of 36% hydrochloric acid was added, filtered, and repeatedly washed with methanol to obtain wet polyphenylene ether. Next, it was vacuum dried at 100°C to obtain dry polyphenylene ether. ηsp/c was 0.103 dl/g, and the yield was 97%.

To measure ηsp/c, the above-described polyphenylene ether was used as a 0.5 g/dl chloroform solution, and the reduced viscosity (ηsp/c) at 30°C was determined using an Ubbelode viscometer. The unit is dl/g.

The obtained polyphenylene ether was modified as follows.

152.5 g of polyphenylene ether and 152.5 g of toluene were mixed and heated to about 85°C. Then, 2.1 g of dimethylaminopyridine was added. When all of the solid had dissolved, 18.28 g of methacrylic anhydride was added little by little. The obtained solution was maintained at 85°C for 3 hours while continuously mixing. The solution was then cooled to room temperature to obtain a toluene solution of methacrylate-blocked polyphenylene ether. For the obtained toluene solution, 1000 mL small amounts of methanol at 10°C were added dropwise to a cylindrical 3L SUS container equipped with a homogenizer for stirring. The obtained powder was filtered, washed with methanol, and dried at 85°C under nitrogen for 18 hours.

<Phenoxy resin>

YP-50 (manufactured by Nittetsu Chemicals)

(Ingredient (IV): Hardener)

Cyanate ester-based hardener 2,2-bis(4-cyanate phenyl)propane (manufactured by Tokyo Kasei Co., Ltd.)

Diamine-based hardener 4,4'-diaminodiphenylmethane (manufactured by Tokyo Kasei Co., Ltd.)

1-Benzyl-2-phenylimidazole (Tokyo Kasei High School Co., Ltd.)

Phenol-based hardener KA-1163 (manufactured by DIC Corporation)

Triallyl isocyanurate (TAICTM) (manufactured by Mitsubishi Chemical Corporation)

[Method for measuring physical properties of resin composition]

((1) Dielectric loss tangent and permittivity)

The dielectric loss tangent and dielectric constant at 10 GHz were measured using the cavity resonance method.

As a measurement device, a network analyzer (N5230A, manufactured by Agilent Technologies) and a cavity resonator (Cavity Resornator CP series) manufactured by Kanto Denshi Oyo Kaihatsu Corporation were used.

For the measurement sample, a test piece of 2.6 mm in width x 80 mm in length was cut from the cured film described later, and this was used as the measurement sample.

Using the dielectric loss tangent and dielectric constant obtained above, the following examples and comparative examples were evaluated according to the following criteria.

<Evaluation criteria in (Examples 1 to 22) and (Comparative Examples 1 to 9)>

It was evaluated based on the difference in dielectric loss tangent and dielectric constant between Comparative Example 1, which does not contain a conjugated diene copolymer, and each Example or Comparative Example (Comparative Example 1 - each Example or Comparative Example).

dielectric loss tangent

◎: 0.025 or more

○: 0.020 or more, less than 0.025

△: 0.015 or more, less than 0.020

×: less than 0.015 (including equal values and negative differences)

permittivity

◎: 0.25 or more

○: 0.20 or more, less than 0.25

△: 0.15 or more, less than 0.20

×: less than 0.15 (including equal values and negative differences)

<Evaluation criteria in (Examples 23 to 34) and (Comparative Examples 10 to 27)>

The difference in dielectric loss tangent and dielectric constant between Comparative Example 10, which does not contain a conjugated diene copolymer, and each Example or Comparative Example was evaluated (Comparative Example 10 - each Example or Comparative Example).

dielectric loss tangent

◎: 0.00090 or more

○: 0.00080 or more, less than 0.00090

△: 0.00070 or more, less than 0.00080

×: less than 0.00070 (including equal values and negative differences)

permittivity

◎: 0.25 or more

○: 0.20 or more, less than 0.25

△: 0.15 or more, less than 0.20

×: less than 0.15 (including equal values and negative differences)

<Evaluation criteria in (Examples 35 to 52) and (Comparative Examples 28 to 36)>

The difference in dielectric loss tangent and dielectric constant between Comparative Example 28, which does not contain a conjugated diene copolymer, and each Example and Comparative Example (Comparative Example 28 - each Example or Comparative Example) was evaluated.

dielectric loss tangent

◎: 0.00070 or more

○: 0.00060 or more, less than 0.00070

△: 0.00050 or more, less than 0.00060

×: less than 0.00050 (including equal values and negative differences)

permittivity

◎: 0.12 or more

○: 0.10 or more, less than 0.12

△: 0.08 or more, less than 0.10

×: less than 0.08 (including equal values and negative differences)

((2) Strength (tensile strength))

A sheet of the cured product containing the resin composition described later was punched into a JIS 1 dumbbell shape and subjected to a tensile test at room temperature at a tensile speed of 1 mm/min to calculate the tensile strength (unit: MPa).

Using the tensile strength obtained above, the following examples and comparative examples were evaluated based on the following criteria.

<Evaluation criteria in (Examples 1 to 22) and (Comparative Examples 1 to 9)>

The difference in tensile strength between Comparative Example 1, which does not contain a conjugated diene copolymer, and each Example or Comparative Example was evaluated (Comparative Example 1 - Each Example or Comparative Example).

tensile strength

◎: 0.7 times or more

○: 0.5 times or more, less than 0.7 times

△: 0.3 times or more, less than 0.5 times

×: less than 0.3 times

<Evaluation criteria in (Examples 23 to 34) and (Comparative Examples 10 to 27)>

The difference in tensile strength between Comparative Example 10, which does not contain a conjugated diene copolymer, and each example or comparative example was evaluated (Comparative Example 10 - each example or comparative example).

tensile strength

◎: 0.7 times or more

○: 0.5 times or more, less than 0.7 times

△: 0.3 times or more, less than 0.5 times

×: less than 0.3 times

<Evaluation criteria in (Examples 35 to 52) and (Comparative Examples 28 to 36)>

The difference in tensile strength between Comparative Example 28, which does not contain a conjugated diene copolymer, and each example or comparative example was evaluated (Comparative Example 28 - each example or comparative example).

tensile strength

◎: 0.7 times or more

○: 0.5 times or more, less than 0.7 times

△: 0.3 times or more, less than 0.5 times

×: less than 0.3 times

[Production of resin composition]

(Examples 1 to 22), (Comparative Examples 1 to 9)

Component ratios and physical properties are shown in Tables 3 to 5 below.

First, the phenol-based curing agent and the phenoxy resin were added to toluene, stirred, and dissolved to prepare a varnish with a concentration of 20% by mass to 50% by mass.

As for the phenol-based hardener, prepare a phenol-based hardener solution with a concentration of 50% by mass using methyl ethyl ketone (a premium product manufactured by Wako Junyaku Co., Ltd.) as a solvent, add it to the varnish, and stir to prepare the varnish. did.

For the phenoxy resin, prepare a phenoxy resin solution with a concentration of 25% by mass using cyclohexanone (a premium product manufactured by Wako Junyaku Co., Ltd. was used as is) as a solvent, add it to the varnish, and stir to prepare a varnish. did.

The varnish was applied onto the release-treated Kapton film at a speed of 30 mm/sec, and then dried at 100°C for 30 minutes in a blow dryer under a nitrogen stream to obtain a film.

The obtained film was subjected to a curing reaction at 200°C for 90 minutes using a blow dryer under a nitrogen stream to obtain a cured film.

The cured film was provided as an evaluation sample.

(Examples 23 to 34), (Comparative Examples 10 to 27)

First, polyimide resin, which is a polar resin, and cyanate ester-based curing agent and/or diamine-based curing agent were dissolved at 160°C in the mixing ratio shown in Tables 6 and 7 below, and reacted with stirring for 6 hours to produce bismaleimide triazine resin. Oligomer was obtained.

The obtained bismaleimide triazine resin oligomer was dissolved in toluene, and the remaining components were added, stirred, and dissolved to prepare a varnish with a concentration of 20% by mass to 50% by mass.

The varnish was applied at a speed of 30 mm/sec on the release-treated Kapton film. After that, it was dried at 100°C for 30 minutes using a blow dryer under a nitrogen stream to obtain a film.

The film was cured in a blow dryer under a nitrogen stream at 200°C for up to 90 minutes to obtain a cured film.

The cured film was provided as an evaluation sample.

(Examples 35 to 52), (Comparative Examples 28 to 36)

Component ratios and physical properties are shown in Tables 8 and 9 below.

First, each component was added to toluene (a premium product manufactured by Wako Junyaku Co., Ltd. was used as is), stirred, and dissolved to prepare a varnish with a concentration of 20% by mass to 50% by mass.

The varnish was applied onto the release-treated Kapton film at a speed of 30 mm/sec, and then dried at 100°C for 30 minutes in a blow dryer under a nitrogen stream to obtain a film. The obtained film was cured at 200°C for 90 minutes in a blow dryer under a nitrogen stream to obtain a cured film.

The cured film was provided as an evaluation sample.

It became clear that the cured product using the hydrogenated conjugated diene copolymer of the examples had an excellent balance of dielectric performance and strength. It was found that the cured product of the present invention is suitable for use in printed wiring boards using glass cloth and metal laminated boards.

The hydrogenated conjugated diene-based copolymer, resin composition, and cured product of the present invention have industrial applicability as materials for films, prepregs, electronic circuit boards, and next-generation communication boards.

Claims (10)

A resin composition containing the following component (I) and at least one component selected from the group consisting of the following components (II) to (IV).
Ingredient (I):
A random copolymer block (C) mainly composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit,
A polymer block (A) mainly composed of vinyl aromatic monomer units and/or a polymer block (B) mainly composed of conjugated diene monomer units.
With
A conjugated diene-based copolymer that satisfies the following conditions (i), (ii), and (iii).
<Condition (i)>
The weight average molecular weight of the conjugated diene-based copolymer is 35,000 or more.
<Condition (ii)>
The amount of vinyl aromatic monomer units in the random copolymer block (C) is 45% by mass or more.
<Condition (iii)>
The amount of vinyl aromatic monomer units in the conjugated diene-based copolymer is 45% by mass or more and 90% or less.
Component (II): Radical initiator
Component (III): Polar resin (excluding component (I))
Component (IV): Hardener (excluding component (II)) The resin composition according to claim 1, wherein the unsaturated bond derived from the conjugated diene monomer unit of the conjugated diene copolymer is hydrogenated. 2. The method of claim 1, comprising component (III),
A resin composition wherein the component (III) is at least one member selected from the group consisting of epoxy resin, polyimide resin, polyphenylene ether resin, liquid crystal polyester resin, and fluorine resin. A cured product of the resin composition according to any one of claims 1 to 3. A resin film comprising the resin composition according to any one of claims 1 to 3. With equipment,
The resin composition according to any one of claims 1 to 3.
A prepreg that is a complex of . The prepreg according to claim 6, wherein the substrate is glass cloth. A laminate comprising the resin film according to claim 5 and metal foil. A laminate comprising a cured product of the prepreg according to claim 6 and a metal foil. A material for an electronic circuit board comprising the cured product according to claim 4.