JP2021138795A - Resin composition and solution of the same - Google Patents

Abstract

To provide a thermosetting resin composition which is excellent in low dielectric characteristics in a high-frequency region even with simple operation and a cured product of the same, and a laminate for an electric/electronic circuit composed of the composition.SOLUTION: A resin composition contains at least one thermosetting resin selected from modified cyclic polyolefin, an epoxy resin, an acrylic resin, a phenol resin, a polyphenylene ether resin, a polyimide resin and a bismaleimide resin, and further contains a curing agent. A weight average molecular weight (Mw) of the modified cyclic polyolefin is 60,000 or less, the modified cyclic polyolefin is cyclic polyolefin that is a modified body of an unsaturated carboxylic acid and/or its anhydride, and the cyclic polyolefin is composed of a hydrogenated block copolymer that is a hydrogenate of a block copolymer including at least one aromatic vinyl monomer unit and at least one conjugated diene monomer unit.SELECTED DRAWING: None

Description

The present invention relates to a resin composition having excellent low-dielectric properties, a cured resin composition having excellent low-dielectric properties using the same, and a laminated board for electric / electronic circuits.

Generally, an electric / electronic circuit board is obtained by stacking a sheet (prepreg) impregnated with a resin on a base material such as paper or glass, which is called a copper-clad laminate (CCL), and heat-treating it under pressure. Mainly, copper foil is applied to the surface of the insulating plate, or a flexible printed circuit board (FPC), in which an insulating adhesive layer is formed on a base film and a conductor foil such as copper is laminated on the insulating adhesive layer. used.

Here, as the prepreg resin and the insulating adhesive layer, thermosetting resins such as epoxy resin, acrylic resin, phenol resin, polyphenylene ether resin, polyimide resin, and bismaleimide resin are used, and after lamination, they are thermoset by heating and pressurizing. , A circuit board with excellent heat resistance, adhesiveness, water resistance, mechanical strength, and electrical characteristics.
In recent years, multi-layer circuit boards used in electrical and electronic equipment have become smaller, lighter, and more sophisticated, and are further multi-layered, high-density, thin, lightweight, reliable, and molded. Improvement of workability is required.

Low dielectric properties are an important performance required for materials for electrical and electronic components such as laminated boards for electrical and electronic circuits and resin materials. In recent years, in order to improve the amount of information transmission and the speed, the communication frequency has been increased, and among them, the increase of transmission loss (α) has become a big issue. The lower the value of this transmission loss (α), the less the attenuation of the information signal, and the higher the reliability of communication can be ensured.
Since the transmission loss (α) is proportional to the frequency (f), α becomes large in communication in the high frequency region, which leads to a decrease in reliability. As a method of suppressing the transmission loss (α), there is a method of reducing the dielectric loss tangent (tan δ) in which α is proportional, as in the frequency (f). For high-speed transmission of communication signals, a material having a low dielectric loss tangent (tan δ), that is, a material having a low dielectric property is required.

For example, epoxy resins are widely used as resins for circuit boards because of their excellent adhesiveness and heat resistance, but various improvements and inventions have been made because of their large tan δ.
For example, Patent Document 1 discloses an epoxy resin in which a third component is introduced into a polyphenylene ether-modified epoxy resin, and Patent Document 2 discloses an ester-modified epoxy resin.

Japanese Unexamined Patent Publication No. 2019-052278 JP-A-2017-193649

However, in any of the resins described in Patent Document 1 and Patent Document 2, the tan δ is still insufficient in the high frequency region.
Therefore, an object of the present invention is to provide a thermosetting resin composition having excellent low dielectric properties in a high frequency region even with a simple operation, a cured product thereof, and a laminated board for an electric / electronic circuit made of the composition. It is in.

As a result of diligent studies to solve the above problems, the present inventor has found that the above problems can be solved by using a specific modified cyclic polyolefin and preparing a resin composition blended with a thermosetting resin. ..
That is, the present invention has the following features.

[1] A resin composition containing a modified cyclic polyolefin, at least one thermosetting resin selected from an epoxy resin, an acrylic resin, a phenol resin, a polyphenylene ether resin, a polyimide resin and a bismaleimide resin, and a curing agent. The modified cyclic polyolefin has a weight average molecular weight (Mw) of 60,000 or less, and the modified cyclic polyolefin is a cyclic polyolefin that is a modified product of an unsaturated carboxylic acid and / or an anhydride thereof. , A resin composition comprising a hydride block copolymer which is a hydride of a block copolymer containing at least one aromatic vinyl monomer unit and at least one conjugated diene monomer unit.

[2] The hydrogenated block copolymer is a hydride of a polymer block composed of a hydrogenated aromatic vinyl polymer block unit, which is a hydride of a polymer block composed of the aromatic vinyl monomer unit, and a conjugated diene monomer unit. Having a hydrogenated conjugated dienepolymer block unit, the hydrogenated block copolymer has at least two of the hydrogenated aromatic vinyl polymer block units and at least one of the hydrogenated conjugated dienepolymer block units, [ 1] The resin composition according to.
[3] The hydrogenated aromatic vinyl polymer block unit has a hydrogenation level of 90% or more, and the hydrogenation-conjugated diene polymer block unit has a hydrogenation level of 95% or more, according to [2]. Resin composition.

[4] The resin composition according to any one of [1] to [3], wherein the modified cyclic polyolefin has a modification rate of 0.1 to 2% by mass with an unsaturated carboxylic acid and / or an anhydride thereof. thing.
[5] The resin composition according to any one of [1] to [4], wherein the modified cyclic polyolefin has a dielectric loss of less than 0.001 at a measurement frequency of 10 GHz.
[6] The content of the modified cyclic polyolefin is 10 to 60% by mass (relative to the entire resin composition), and the total content of the thermosetting resin and the curing agent is 40 to 90% by mass (resin composition). The resin composition according to any one of [1] to [5], which is (for the entire product).

[7] A resin composition solution prepared by dissolving the resin composition according to any one of [1] to [6] in an organic solvent at a solid content concentration of 10 to 90% by mass.
[8] A cured resin composition obtained by curing the resin composition according to any one of [1] to [6].
[9] A laminated board for an electric / electronic circuit, which comprises the resin composition according to any one of [1] to [6].
[10] The cured resin composition according to [8], wherein the dielectric loss at a measurement frequency of 10 GHz is less than 0.01.
[11] The laminated board for an electric / electronic circuit according to [9], wherein the dielectric loss at a measurement frequency of 10 GHz is less than 0.01.

[12] A method for producing a cured resin composition by removing the solvent of the resin composition solution according to [7] and then curing the solution.
[13] A method for producing a laminate for an electric / electronic circuit by removing the resin composition solvent of the solution according to [7] and then curing the solution.
[14] The method for producing a cured resin composition according to [12], wherein the dielectric loss at a measurement frequency of 10 GHz is less than 0.01.
[15] The method for producing a laminate for an electric / electronic circuit according to [13], wherein the dielectric loss at a measurement frequency of 10 GHz is less than 0.01.

By using the resin composition of the present invention, it is possible to provide a cured film having an extremely low tan δ, which is suitable for a laminated board for a circuit board suitable for high-speed, high-density communication with little transmission loss.

The present invention will be described in detail below, but the following description is an example of an embodiment of the present invention, and the present invention is not limited to the following description as long as the gist of the present invention is not exceeded.
In the following, when the expression "~" is used, it shall be used as an expression including the numerical values or physical property values before and after it.

<Resin composition>
The present invention relates to a resin composition containing a modified cyclic polyolefin, a specific thermosetting resin, and a curing agent.

[Thermosetting resin]
The thermosetting resin used in the present invention is at least one thermosetting resin selected from epoxy resin, acrylic resin, phenol resin, polyphenylene ether resin, polyimide resin and bismaleimide resin.
All of these thermosetting resins are obtained by known techniques.

Epoxy resin is the most widely used resin, and various structures and techniques are disclosed. For example, it is disclosed in Japanese Patent Application Laid-Open No. 8-333437, Japanese Patent Application Laid-Open No. 2005-97473, and Japanese Patent Application Laid-Open No. 2019-172996.

As the phenol resin, a vinylbenzylated phenol compound as described in Japanese Patent No. 6025952 can be used.
As the polyphenylene ether resin, a resin having a reactive functional group added to the terminal as described in JP-A-2017-47648 can be used.

As the polyimide resin, those obtained from the tetracarboxylic acid component and the diamine component as described in Japanese Patent Application Laid-Open No. 2018/079707 can be used.
As the bismaleimide resin, bismaleimide as described in Japanese Patent Application Laid-Open No. 2001-028367 can be used.

[Curing agent]
The curing agent used in the present invention represents, for example, a substance that contributes to a cross-linking reaction and / or a chain length extension reaction between epoxy groups of an epoxy resin.
In the present invention, even if it is usually called a "curing accelerator", if it is a substance that contributes to the cross-linking reaction and / or the chain length extension reaction between the epoxy groups of the epoxy resin, it is regarded as a curing agent. ..

The curing agent used for the epoxy resin is not particularly limited, and any curing agent generally known as an epoxy resin curing agent can be used.
Examples of the curing agent used for the acrylic resin, phenol resin, and bismaleimide resin include phenol-based curing agents, amide-based curing agents, imidazoles, and active ester-based curing agents from the viewpoint of enhancing heat resistance.
These curing agents may be used alone or in combination of two or more.

As the curing agent used for the polyphenylene ether resin, a curing agent for three-dimensionally cross-linking the polyphenylene ether can be used. Specifically, as the cross-linking type curing agent, a polyfunctional vinyl compound, a vinylbenzyl ether compound, an allyl ether compound, or a trialkenyl isocyanurate can be used.

Polyfunctional vinyl compounds include divinylbenzene, divinylnaphthalene, and divinylbiphenyl. Vinylbenzyl ether compounds are synthesized by the reaction of phenol and vinylbenzyl chloride. Allyl ether compounds are synthesized by the reaction of styrene monomer, phenol, and allyl chloride. Trialkenyl isocyanurate has good compatibility, and triallyl isocyanurate or triallyl cyanurate can be used.

Examples of the curing agent used for the polyimide resin include imidazole compounds such as 1,2-dimethylimidazole, heterocyclic compounds containing a nitrogen atom such as isoquinoline, and basic compounds such as triethylamine and triethanolamine.

[Other ingredients]
As another component that can be added to the resin composition of the present invention, a catalyst of a thermosetting resin can be used. The catalyst may be any thermosetting resin alone or any compound having a catalytic ability to accelerate the reaction between the thermosetting resin and the curing agent.

For example, examples of epoxy resins include tertiary amines, cyclic amines, imidazoles, organic phosphorus compounds, and quaternary ammonium salts. For polyphenylene ether resin, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexine, excess Benzoyl oxide, 3,3', 5,5'-tetramethyl-1,4-diphenoquinone, chloranyl, 2,4,6-tri-t-butylphenoxyl, t-butylperoxyisopropyl monocarbonate, azobisisobuty An oxidizing agent such as benzene can be used. Here, if necessary, a metal carboxylic acid salt or the like may be added to further accelerate the curing reaction.

The resin composition of the present invention may contain components other than those listed above for the purpose of further improving its functionality. For example, thermosetting resins, photocurable resins, curing accelerators (excluding those included in "curing agents"), UV inhibitors, antioxidants, coupling agents, plasticizers, fluxes, flame retardants, etc. Examples thereof include colorants, dispersants, emulsifiers, low elasticity agents, diluents, defoamers, ion trapping agents, inorganic fillers, and organic fillers.

[Content rate of each component]
The content of the modified cyclic polyolefin in the resin composition is preferably 10 to 60% by mass, more preferably 30 to 50% by mass, based on the entire resin composition (100% by mass).
When the content of the modified cyclic polyolefin is at least the above lower limit, a sufficient effect of reducing the dielectric loss is exhibited, which is preferable. Further, when it is not more than the above upper limit, it is preferable because sufficient heat resistance and mechanical strength of the cured product can be obtained.

The total content of the thermosetting resin and the curing agent in the resin composition is preferably 40 to 90% by mass, preferably 50 to 70% by mass, based on the entire resin composition (100% by mass). More preferable.
When the contents of the thermosetting resin and the curing agent are at least the above lower limit, various properties of the thermosetting resin are not impaired, which is preferable. Further, if it is not more than the above upper limit, the dielectric loss does not deteriorate, which is preferable.

The content of the curing agent is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the thermosetting resin. It is more preferably 90 parts by mass or less, and further preferably 80 parts by mass or less.
When the thermosetting resin is an epoxy resin, the content of the curing agent is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the epoxy resin. The lower limit is more preferably 20 parts by mass or more. Further, the upper limit thereof is more preferably 90 parts by mass or less, and further preferably 80 parts by mass or less.
When the content of the curing agent is within the above range, the epoxy resin is sufficiently crosslinked, and the desired heat resistance and mechanical strength are exhibited.

<Modified cyclic polyolefin>
The modified cyclic polyolefin of the present invention is a modified version of the cyclic polyolefin described later with an unsaturated carboxylic acid and / or an anhydride thereof. The modification operation of this cyclic polyolefin will be described later.

The lower limit of the weight average molecular weight (hereinafter, abbreviated as “Mw”) of the modified cyclic polyolefin is preferably 10,000 or more, more preferably 15,000 or more. The upper limit of Mw is preferably 60,000 or less, preferably 30,000 or less.
When the Mw of the modified cyclic polyolefin is at least the above lower limit, heat resistance and dielectric properties are improved, which is preferable. Further, when Mw is not more than the above upper limit, the solubility in an organic solvent is good, which is preferable.
The Mw of the modified cyclic polyolefin is determined by gel permeation chromatography (GPC) measurement, and the specific measurement method thereof is as described in the section of Examples.

The Mw of the modified cyclic polyolefin can be controlled by the amount of the organic peroxide used when modifying the cyclic polyolefin.
The modification operation of the cyclic polyolefin will be described later. Further, in the same manner as the modification operation of the cyclic polyolefin, Mw was changed by blending the modified cyclic polyolefin with an organic peroxide, blending the mixture, putting it into a kneader and an extruder, and extruding while heating, melting and kneading. A modified cyclic polyolefin can be obtained.

When the cyclic polyolefin or the modified cyclic polyolefin is treated with an organic peroxide, the carbon-hydrogen bond of the hydrogenation-conjugated dienepolymer block unit, which is one of the block units constituting the cyclic polyolefin or the modified cyclic polyolefin, is once cleaved. From the generated carbon radical structure, carbon-carbon bond cleavage accompanied by β-hydrogen desorption occurs to cause a low molecular weight, and a low molecular weight modified cyclic polyolefin can be obtained from a high molecular weight cyclic polyolefin or a modified cyclic polyolefin. ..
This operation may be performed after the denaturation or at the same time as the denaturation. That is, since the molecular weight is reduced at the same time as the denaturation, it is possible to reduce the molecular weight at the same time as the denaturation by adding a large amount of organic peroxide.

<Characteristics of modified cyclic polyolefin>
The modified cyclic polyolefin used in the present invention is characterized by having a sufficiently low dielectric loss.
By adding a small amount of the modified cyclic polyolefin, it is possible to suppress the dielectric loss of the entire resin composition, and it is expected that the signal transmission efficiency will be improved when the laminated board for electric / electronic circuits is used.

The dielectric loss of the modified cyclic polyolefin at a measurement frequency of 10 GHz is preferably less than 0.001, more preferably less than 0.0005.
The dielectric loss of cyclic polyolefins tends to be slightly exacerbated by modification with unsaturated carboxylic acids and / or anhydrides thereof. Therefore, in order to keep the dielectric loss low, it is necessary to control the modification rate as described later.

<Modification operation of cyclic polyolefin>
Next, the modification operation of the cyclic polyolefin will be described. This denaturing operation is carried out by adding an unsaturated carboxylic acid and / or an anhydride thereof as a denaturing agent to the cyclic polyolefin and reacting the cyclic polyolefin.

Examples of the unsaturated carboxylic acid and / or its anhydride as the modifier include acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, and itaconic acid. Examples thereof include unsaturated carboxylic acids such as citraconic acid, crotonic acid, isocrotonic acid and nadic acids, and anhydrides thereof.
Specific examples of the acid anhydride include maleic anhydride, citraconic anhydride, and nagic anhydride.
Examples of nadic acids or anhydrides thereof include endosis-bicyclo [2.2.1] hept-2,3-dicarboxylic acid (nadic acid ™) and methyl-endosis-bicyclo [2.2.1] hept. Examples thereof include -5-ene-2,3-dicarboxylic acid (methylnadic acid ™) and its anhydrides.

Among these unsaturated carboxylic acids and / or anhydrides thereof, acrylic acid, maleic acid, nadic acid, maleic anhydride, and nadic acid anhydride are preferable.
As the unsaturated carboxylic acid and / or its anhydride, one type may be used alone, or two or more types may be used in combination.

A modified cyclic polyolefin can be obtained by modifying the cyclic polyolefin with the unsaturated carboxylic acid and / or its anhydride. As the denaturation method, solution denaturation, melt denaturation, solid phase denaturation by irradiation with electron beam or ionizing radiation, denaturation in a supercritical fluid, or the like is preferably used.
Among them, melt modification having excellent equipment and cost competitiveness is preferable, and melt kneading modification using an extruder having excellent continuous productivity is more preferable.
Examples of the device used at this time include a single-screw extruder, a twin-screw extruder, a Banbury mixer, and a roll mixer. Of these, single-screw extruders and twin-screw extruders with excellent continuous productivity are preferable.

In general, modification of cyclic polyolefins with unsaturated carboxylic acids and / or anhydrides thereof cleaves the carbon-hydrogen bonds of hydrocarbon-conjugated dienepolymer block units, which are one of the block units that make up cyclic polyolefins, and carbon radicals. Is generated, and an unsaturated functional group is added to this by a graft reaction.
As the source of carbon radicals, in addition to the above-mentioned electron beam and ionizing radiation, a method of raising the temperature or a radical generator such as an organic peroxide, an inorganic peroxide, or an azo compound can also be used. As the radical generator, it is preferable to use an organic peroxide from the viewpoint of cost and operability.

Examples of the azo compound include azobisisobutyronitrile, azobisdimethylvaleronitrile, azobis (2-methylbutyronitrile), and diazodinitrophenol.
Examples of the inorganic peroxide include hydrogen peroxide, potassium peroxide, sodium peroxide, calcium peroxide, magnesium peroxide, and barium peroxide.

Examples of the organic peroxide include those contained in the hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy ester and ketone peroxide group.
Specifically, hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide; dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylper). Dialkyl peroxides such as oxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3; diacyl peroxides such as lauryl peroxide and benzoyl peroxide; t-butylperoxyacetate. , T-Butylperoxybenzoate, peroxyesters such as t-butylperoxyisopropylcarbonate; ketone peroxides such as cyclohexanone peroxides.
One of these radical generators may be used alone, or two or more of these radical generators may be used in combination.

[Melting kneading modification]
A commonly used operation for melt-kneading modification is to mix cyclic polyolefin, unsaturated carboxylic acid and / or its anhydride, and organic peroxide, put them into a kneader or extruder, and extrude while heating, melt-kneading, and kneading. Then, the molten resin coming out of the tip die is cooled in a water tank or the like to obtain a modified cyclic polyolefin.

The blending ratio of the cyclic polyolefin and the unsaturated carboxylic acid and / or its anhydride is 0.2 to 5 parts by mass of the unsaturated carboxylic acid and / or its anhydride with respect to 100 parts by mass of the cyclic polyolefin.
When the blending ratio of the unsaturated carboxylic acid and / or its anhydride with respect to the cyclic polyolefin is not more than the above lower limit, a predetermined modification rate necessary for achieving the effect of the present invention can be obtained. Further, when it is not more than the above upper limit, unreacted unsaturated carboxylic acid and / or its anhydride does not remain, which is also preferable as a dielectric property.

The blending ratio of the unsaturated carboxylic acid and / or its anhydride and the organic peroxide is 20 to 100 parts by mass of the organic peroxide with respect to 100 parts by mass of the unsaturated carboxylic acid and / or its anhydride. It is a department.
When the compounding ratio of the organic peroxide to the unsaturated carboxylic acid and / or its anhydride is at least the above lower limit, a predetermined modification rate necessary for achieving the effect of the present invention can be obtained. Further, when it is not more than the above upper limit, the cyclic polyolefin is not deteriorated and the hue is not deteriorated.

Further, as the melt-kneading modification condition, for example, in a single-screw extruder and a twin-screw extruder, it is preferable to extrude at a temperature of 150 to 300 ° C.

[Reduced molecular weight of modified cyclic polyolefin]
When the molecular weight of the modified cyclic polyolefin is reduced, the blending ratio of the modified cyclic polyolefin and the organic peroxide is 0.01 to 2 parts by mass with respect to 100 parts by mass of the modified cyclic polyolefin. ..
Further, as the melt-kneading modification condition, for example, in a single-screw extruder and a twin-screw extruder, it is preferable to extrude at a temperature of 150 to 300 ° C.

[Denaturation rate]
The modification rate of the modified cyclic polyolefin with the unsaturated carboxylic acid and / or its anhydride is preferably 0.1 to 2% by mass.
When the modification rate is at least the above lower limit, the compatibility with a thermosetting resin such as epoxy is good, and as a result, the coating film strength is improved, which is preferable. Further, when it is not more than the above upper limit, there is no generation of odor and deterioration of color, and the solubility in an organic solvent is also good.
The modification rate of the modified cyclic polyolefin can be measured by ^{1 HNMR after the modified cyclic polyolefin is methylesterified.}

<Cyclic polyolefin>
The cyclic polyolefin used as a raw material for the modified cyclic polyolefin used in the present invention comprises a hydrogenated block copolymer which is a hydride of a block copolymer containing at least one aromatic vinyl monomer unit and at least one conjugated diene monomer unit.
The hydrogenated block copolymer is a hydrogenated product of a hydrogenated aromatic vinyl polymer block unit, which is a hydride of a polymer block composed of the aromatic vinyl monomer unit, and hydrogen, which is a hydride of a polymer block composed of the conjugated diene monomer unit. It has a compound conjugated diene polymer block unit.
Further, the hydrogenated block copolymer has at least two hydrogenated aromatic vinyl polymer block units and at least one hydrogenated conjugated diene polymer block unit.

The cyclic polyolefin used in the present invention is preferably made of the hydrogenated block copolymer from the viewpoint of transparency and dielectric properties, specifically, low dielectric loss (tangent).
As will be described later, the term "block" as used herein refers to a polymerized segment of a copolymer that represents microlayer separation from structurally or structurally different polymerized segments of the copolymer. For this reason, for example, "having at least two block units" means that the hydrogenated block copolymer has at least two polymerized segments of the copolymer representing microlayer separation from structurally or structurally different polymerized segments. Say that.

The aromatic vinyl monomer used as a raw material for the aromatic vinyl monomer unit is a monomer represented by the general formula (1).

ここでＲは、水素又はアルキル基、Ａｒはフェニル基、ハロフェニル基、アルキルフェニル基、アルキルハロフェニル基、ナフチル基、ピリジニル基又はアントラセニル基である。

Here, R is a hydrogen or an alkyl group, Ar is a phenyl group, a halophenyl group, an alkylphenyl group, an alkylhalophenyl group, a naphthyl group, a pyridinyl group or an anthrasenyl group.

The alkyl group may be mono- or multiple-substituted with a functional group such as a halo group, a nitro group, an amino group, a hydroxy group, a cyano group, a carbonyl group and a carboxyl group. The alkyl group preferably has 1 to 6 carbon atoms.
The Ar is preferably a phenyl group or an alkylphenyl group, more preferably a phenyl group.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene (including all isomers, especially p-vinyltoluene), ethylstyrene, propylstyrene, butylstyrene, vinylbiphenyl, vinylnaphthalene, and vinylanthracene. (All isomers), and mixtures thereof.

The conjugated diene monomer may be a monomer having two conjugated double bonds, and is not particularly limited.
Examples of the conjugated diene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2-methyl-1,3 pentadiene and similar compounds, and mixtures thereof.

Polybutadiene, which is a polymer of 1,3-butadiene, has either an 1,2 configuration that gives an equivalent of 1-butene repeating units by hydrogenation, or a 1,4 configuration that gives an equivalent of ethylene repeating units by hydrogenation. Can be included.

The hydrogenated block copolymer composed of the aromatic vinyl monomer and the conjugated diene monomer containing 1,3-butadiene is included in the hydrogenated block copolymer used in the present invention. Preferably, the hydrogenated block copolymer is a functional group-free block copolymer.
By the way, "without functional groups" means that there are no functional groups in the block copolymer, that is, groups containing elements other than carbon and hydrogen.

Preferred examples of the hydrogenated aromatic vinyl polymer block unit include hydrogenated polystyrene, and preferred examples of the hydrogenated conjugated diene polymer block unit include hydrogenated polybutadiene.
A preferred embodiment of the hydrogenated block copolymer is a hydrogenated triblock or pentablock copolymer of styrene and butadiene, preferably free of any other functional or structural modifiers.

A "block" is defined as a polymerization segment of a copolymer that represents microlayer separation from structurally or compositionally different polymerization segments of the copolymer. Microlayer separation occurs due to the immiscibility of the polymerized segments in the block copolymer.
It should be noted that microlayer separation and block copolymers are widely discussed in "Block Copolymers-Designer Soft Materials", February 1999, pp. 32-38 of PHYSICS TODAY.

The content of the hydrogenated aromatic vinyl polymer block unit is preferably 50 to 99 mol%, more preferably 60 to 90 mol% with respect to the cyclic polyolefin.
If the ratio of hydrogenated aromatic vinyl polymer block units is at least the above lower limit, the rigidity does not decrease, and if it is at least the above upper limit, brittleness does not deteriorate.

The content of the hydrogenated conjugated diene polymer block unit is preferably 1 to 50 mol%, more preferably 10 to 40 mol% with respect to the cyclic polyolefin.
If the ratio of hydrogenated conjugated diene polymer block units is not less than the above lower limit, brittleness does not deteriorate, and if it is not more than the above upper limit, rigidity does not decrease.

As described above, the polyolefin according to the present invention is a "cyclic polyolefin", and the "cyclic" is an alicyclic formed by hydrogenation of an aromatic ring possessed by the hydrogenated aromatic vinyl polymer block unit. It refers to the formula structure.

The hydrogenated block copolymers of the present invention are triblock, multiblock, tapered blocks such as SBS, SBSBS, SIS, SISIS, and SISBS (where S stands for polystyrene, B stands for polybutadiene, and I stands for polyisoprene). And produced by hydrogenation of block copolymers, including star block copolymers.

The hydrogenated block copolymers of the present invention contain a segment consisting of an aromatic vinyl polymer at each end. Therefore, the hydrogenated block copolymer of the present invention will have at least two hydrogenated aromatic vinyl polymer block units. Then, at least one hydrogenated conjugated diene polymer block unit will be provided between the two hydrogenated aromatic vinyl polymer block units.

The pre-hydrogenation block copolymer constituting the hydrogenation block may contain several additional blocks, which may be attached to any position on the triblock polymer backbone. Thus, the linear block includes, for example, SBS, SBSB, SBBSS, and SBBSSB. The copolymer may be branched and the polymerization chain may be attached at any position along the backbone of the copolymer.

The lower limit of Mw of the hydrogenated block copolymer is preferably 10,000 or more, more preferably 20,000 or more. The upper limit of Mw is preferably 120,000 or less, more preferably 100,000 or less, further preferably 95,000 or less, particularly preferably 90,000 or less, most preferably 85,000 or less, and extremely preferably 80. It is less than 000.
If Mw is not less than the above lower limit, the mechanical strength does not decrease, and if it is not more than the above upper limit, the solvent solubility of the obtained modified cyclic polyolefin is improved.
Mw herein is determined by measurement of GPC.

The hydrogenation level of the block copolymer is preferably 90% or more for the hydrogenated aromatic vinyl polymer block unit, 95% or more for the hydrogenated conjugated diene polymer block unit; and more preferably 95% or more for the hydrogenated aromatic vinyl polymer block unit. , Hydrogen-conjugated diene polymer block unit is 99% or more; more preferably hydrogenated aromatic vinyl polymer block unit is 98% or more, hydrogen-conjugated diene polymer block unit is 99.5% or more; particularly preferably hydrogenated aromatic The vinyl polymer block unit is 99.5% or more, and the hydrogenated conjugated diene polymer block unit is 99.5% or more.
Such high levels of hydrogenation are preferred in order to reduce dielectric loss.
The hydrogenation level of the hydrogenated aromatic vinyl polymer block unit indicates the rate at which the aromatic vinyl polymer block unit is saturated by hydrogenation, and the hydrogenation level of the hydrogenation-conjugated diene polymer block unit is the conjugated diene. Shows the rate at which a polymer block unit is saturated by hydrogenation.

The hydrogenation level of the hydrogenated aromatic vinyl polymer block unit and the hydrogenation level of the hydrogenation-conjugated diene polymer block unit are determined using proton NMR.

The melt flow rate (MFR) of the cyclic polyolefin of the present invention is not particularly limited, but is usually 0.1 g / 10 minutes or more, preferably 0.5 g / 10 minutes or more from the viewpoint of the molding method and the appearance of the molded product. be. Further, it is usually 200 g / 10 minutes or less, preferably 100 g / 10 minutes or less, and more preferably 50 g / 10 minutes or less from the viewpoint of material strength.
The MFR was measured according to ISO R1133 under the conditions of a measurement temperature of 230 ° C. and a measurement load of 2.16 kg.

As the cyclic polyolefin, one type may be used alone, or two or more types may be used in combination.
As the cyclic polyolefin of the present invention, a commercially available one can be used, and specific examples thereof include Mitsubishi Chemical Corporation: Zelas (registered trademark).

<Resin composition solution>
The resin composition of the present invention can be dissolved in an organic solvent to prepare a resin composition solution.
In the present invention, it is possible to use an organic solvent in the step of producing the resin composition, and when a highly viscous product is generated during the reaction of the resin composition, an organic solvent is additionally added to continue the reaction. You can also do it.
When an organic solvent is added during the reaction, the organic solvent may be removed or further added after the reaction is completed.

When the resin composition is used as a solution, the solid content concentration is preferably 10 to 90% by mass.
Here, the "solid content" means a component excluding the organic solvent, and includes not only a solid resin component but also a semi-solid or a viscous liquid substance.

Examples of the organic solvent used here include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate; ethers such as ethylene glycol monomethyl ether; N, N-dimethylformamide, Amides such as N, N-dimethylacetamide; alcohols such as methanol and ethanol; alkanes such as hexane and cyclohexane; aromatics such as toluene and xylene can be mentioned.
These organic solvents may be used alone or in combination of two or more.

<Cured resin composition>
The cured resin composition obtained by curing the resin composition of the present invention has an excellent balance of heat resistance, low water absorption, and low dielectric properties, and exhibits good cured physical properties.
The term "curing" as used herein means that the resin composition is intentionally cured by heat and / or light, and the degree of curing may be controlled according to desired physical properties and applications.
The degree of curing may be complete curing or semi-curing, but for example, the reaction rate of the thermosetting resin portion is usually 5 to 95%.

The curing method for curing the resin composition of the present invention to obtain a cured product varies depending on the blending components and the blending amount in the resin composition, but all of them can be carried out in accordance with the conditions described in the above-mentioned prior arts.
For example, when the thermosetting resin is an epoxy resin, heating conditions of 80 to 280 ° C. for 60 to 360 minutes can be mentioned. This heating is preferably carried out in two stages of primary heating at 80 to 160 ° C. for 10 to 90 minutes and secondary heating at 120 to 200 ° C. for 60 to 150 minutes, and the glass transition temperature (Tg) is high. In a compounding system that exceeds the temperature of the secondary heating, it is preferable to further perform the tertiary heating at 150 to 280 ° C. for 60 to 120 minutes.
Performing secondary heating and tertiary heating in this way is preferable from the viewpoint of reducing curing defects and residual solvent.

When the thermosetting resin is polyphenylene ether, it is preferable to heat it at 170 to 230 ° C. for an appropriate time.
Further, when the thermosetting resin is a bismaleimide resin, it is preferable to perform primary curing at 200 to 400 ° C. and then completely cure at 400 to 500 ° C.

When producing a semi-cured product, it is preferable to proceed the curing reaction of the resin composition to the extent that the shape can be maintained by heating or the like. When the resin composition contains a solvent, most of the solvent is usually removed by a method such as heating, depressurization, or air drying, but 5% by mass or less of the solvent may remain in the semi-cured product. ..

[Characteristics of cured resin composition]
The cured resin composition of the present invention is characterized by having a sufficiently low dielectric loss.
The dielectric loss of the cured resin composition at a measurement frequency of 10 GHz is preferably less than 0.01, more preferably less than 0.008. The lower the dielectric loss, the higher the transmission efficiency and speed of the electric signal when the circuit board is used, which is preferable.

[Manufacturing of cured resin composition]
The cured resin composition can be produced by removing the solvent from the solution of the resin composition and then curing the cured product by the above method.
By using the resin composition of the present invention, the dielectric loss of the cured resin composition obtained by this method can satisfy the above range.

<Use>
The resin composition of the present invention is excellent in film forming property. In addition, it has the effect of providing a cured product having excellent heat resistance and low dielectric properties and further excellent low water absorption. Therefore, it can be applied to various fields such as adhesives, paints, materials for civil engineering and construction, insulating materials for electrical and electronic parts, and particularly as insulating castings, laminated materials, sealing materials, etc. in the electrical and electronic fields. It is useful.

As an example of the use of the resin composition of the present invention, a copper foil laminated board, a flexible printed circuit board, a multilayer printed wiring board, a laminated board for electric / electronic circuits such as a capacitor, a film-like adhesive, an adhesive such as a liquid adhesive, etc. , Semiconductor encapsulant material, underfill material, interchip fill for 3D-LSI, insulating sheet, prepreg, heat dissipation substrate, but are not limited thereto.

<Laminated body containing conductive metal layer>
The resin composition of the present invention can be made into a conductive metal layer-containing laminate by forming a layer made of this resin composition on the conductive metal layer.
This conductive metal layer-containing laminate is a laminate of the resin composition film layer and the conductive metal layer of the present invention, and is a laminate of the resin composition film layer and the conductive metal layer of the present invention. If there is, it can be used as an electric / electronic circuit, a circuit having a capacitor, or the like.
A layer composed of two or more kinds of resin compositions may be formed in the conductive metal layer-containing laminate, and the resin composition of the present invention may be used in at least one layer. Further, two or more kinds of conductive metal layers may be formed.

The conductive metal layer-containing laminate can be obtained by a coating method such as directly coating a resin composition solution on the conductive metal or immersing the conductive metal in the resin composition solution, or as a base. A resin composition-containing material obtained by a coating method such as applying a resin composition solution to a core material, or immersing the core material in a resin composition solution, is laminated on a conductive metal. This can be produced by obtaining a laminate, removing the solvent at the stage of lamination or after lamination, and then curing by the method described above.

Examples of the core material include non-woven fabrics and cloths using inorganic and / or organic fiber materials such as glass fiber, polyester fiber, aramid fiber, cellulose, and nanofiber cellulose.

By using the resin composition of the present invention, the dielectric loss of the conductive metal layer-containing laminate obtained by this method can satisfy the above range.

[Electrical / electronic circuit laminate]
When the conductive metal layer-containing laminate is an electric / electronic circuit laminate, the thickness of the layer made of the resin composition in the electrical / electronic circuit laminate is usually about 10 to 200 μm. The thickness of the conductive metal layer is usually about 0.2 to 70 μm.

The laminated board for electric / electronic circuits of the present invention is characterized in that the dielectric loss is sufficiently low.
The dielectric loss of the laminated board for electric / electronic circuits at a measurement frequency of 10 GHz is preferably less than 0.01, more preferably less than 0.008. The lower the dielectric loss, the higher the transmission efficiency and speed of the electric signal when the circuit board is used, which is preferable.

[Conductive metal]
Examples of the conductive metal in the laminated plate for electric / electronic circuits include metals such as copper and aluminum, and alloys containing these metals. In the present invention, as the conductive metal layer of the laminated plate for an electric / electronic circuit, a metal foil of these metals or a metal layer formed by plating or sputtering can be used.

[Manufacturing method of laminated boards for electrical and electronic circuits]
Specific examples of the method for manufacturing the laminated board for electric / electronic circuits in the present invention include the following methods.
(1) A non-woven fabric or cloth using an inorganic and / or organic fiber material such as glass fiber, polyester fiber, aramid fiber, cellulose, nanofiber cellulose, etc. is impregnated with the resin composition of the present invention or a solution containing the same. When a solution is used, the solvent is appropriately removed, a conductive metal layer is provided by conductive metal foil and / or plating, and then a circuit is formed using a photoresist or the like, and such a layer is required. Stack several layers to make a laminated board.

(2) Using the prepreg of (1) above as a core material, a layer composed of a resin composition or a solution containing the resin composition (solvent is appropriately removed) and a conductive metal layer are laminated on the core material (one side or both sides) (build). Up method). The layer made of this resin composition may contain an organic and / or inorganic filler.
(3) Without using a core material, only a layer composed of a resin composition or a solution containing the resin composition (solvent is appropriately removed) and a conductive metal layer are alternately laminated to form a laminated board for an electric / electronic circuit.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the present Examples. In the following Examples and Comparative Examples, various physical properties were measured by the following methods.

<Molecular weight>
・ Equipment: GPC HLC-832GPC / HT manufactured by Tosoh Corporation
-Detector: MIRAN 1A infrared spectrophotometer (measurement wavelength, 3.42 μm)
-Column: Showa Denko KK: AD806M / S 3 (Column calibration is 0.5 mg / ml each of Tosoh monodisperse polystyrene (A500, A2500, F1, F2, F4, F10, F20, F40, F288) The solution) was measured, and the logarithmic values of the elution volume and the molecular weight were approximated by a cubic equation.
・ Measurement temperature: 135 ℃
・ Concentration: 20 mg / 10 mL
・ Injection amount: 0.2 ml
-Solvent: o-dichlorobenzene-Flow velocity: 1.0 ml / min

<Ratio of polymer blocks>
[Measurement by carbon NMR]
-Device: Bruker's "AVANCE400 spectrometer"
-Solvent: o-dichlorobenzene-h ₄ / p-dichlorobenzene-d ₄ mixed solvent-Concentration: 0.3 g / 2.5 mL
-Measurement: ¹³ C-NMR
・ Resonance frequency: 400MHz
・ Number of integrations: 3600
・ Flip angle: 45 degrees ・ Data acquisition time: 1.5 seconds ・ Pulse repetition time: 15 seconds ・ Measurement temperature: 100 ° C
・¹ H irradiation: Complete decoupling

<Hydrogenation level of hydrogenated aromatic vinyl polymer block unit, hydrogenation conjugated diene polymer block unit>
[Measurement by proton NMR]
-Device: Bruker's "AVANCE400 spectrometer"
-Solvent: Tetrachloroethane-Concentration: 0.045 g / 1.0 mL
・ Measurement: ^{1 1} H-NMR
・ Resonance frequency: 400MHz
・ Flip angle: 45 degrees ・ Data acquisition time: 4 seconds ・ Pulse repetition time: 10 seconds ・ Number of integrations: 64
-Measurement temperature: 80 ° C
-Hydrogenation level of hydrogenated aromatic vinyl polymer block unit: 6.8 to 7.5 ppm integrated value reduction rate-Hydrogenation-conjugated diene polymer block unit hydrogenation level: 5.7 to 6.4 ppm integrated value reduction rate

<Modification rate of modified cyclic polyolefin>
[Measurement by proton NMR]
-Device: "AVANCE400 spectrometer" manufactured by BRUKER
-Solvent: diorthodichlorobenzene-Concentration: 20 mg / 0.62 mL
・ Measurement: ^{1 1} H-NMR
・ Resonance frequency: 400MHz
・ Flip angle: 45 degrees ・ Data acquisition time: 4 seconds ・ Pulse repetition time: 10 seconds ・ Number of integrations: 64
-Measurement temperature: 120 ° C
-Modification rate of acid-modified cyclic polyolefin: Integral value reduction rate of 3.42 to 3.94 ppm

<Measurement of permittivity and dielectric loss>
The measurement was performed with a transmission attenuation measuring jig with a dielectric lens.
-Device: "Vector Network Analyzer N5227A" manufactured by KEYSIGHT
"Millimeter Wave Module WR10-VNAX" manufactured by VIRGINIA DIODES
"Network analyzer E8631A" manufactured by KEYSIGHT
・ Measurement environment: 26 ° C, humidity 40%
-Measurement frequency: 10 GHz

For the modified cyclic polyolefin, a sheet having a thickness of 1 mm and a size of 10 cm × 10 cm was prepared by hot pressing at 200 ° C., and this was used for measurement.
The cured product was peeled off from the release PET film by the method described in Example 1, cut into a size of 10 cm × 10 cm, and used for measurement.

<Solution state>
The uniformity and fluidity of the liquid were judged by visual observation.
◯: The liquid state is uniform and the liquid level flows rapidly when the container is tilted Δ: The liquid state is not uniform, but the liquid level flows quickly when the container is tilted ×: The liquid state is uniform No, it does not flow when the container is tilted

<Coating film condition>
By visual observation, it was judged by the presence or absence of air bubbles, lumps, unpainted areas, and repelling.
○: Bubbles, lumps, unpainted areas and repelling are pear △: Bubbles, lumps, unpainted areas and repelling are slightly ants ×: Bubbles, lumps, unpainted areas and repelling are many ants

<Hardened film state>
By visual observation, it was judged by the presence or absence of air bubbles, lumps, unpainted areas, and repelling.
○: Bubbles, lumps, unpainted areas and repelling are pear △: Bubbles, lumps, unpainted areas and repelling are slightly ants ×: Bubbles, lumps, unpainted areas and repelling are many ants

<Raw materials>
[Cyclic polyolefin]
・ A-1:
Zelas MC930 manufactured by Mitsubishi Chemical Corporation is used as the cyclic polyolefin, and maleic anhydride and organic peroxide (manufactured by NOF CORPORATION: Perhexa 25B (2.5? Dimethyl? 2.5? Di (t?)) Are used. Butylperoxy) hexane)) is well stirred at a blending ratio of 1.3 parts by mass of maleic anhydride and 0.0065 parts by mass of organic peroxide with respect to 100 parts by mass of cyclic polyolefin, and then biaxially extruded. Using a machine (manufactured by Nippon Steel Co., Ltd., TEX25αIII), melt-kneading is performed at a cylinder temperature of 280 ° C., a screw rotation speed of 400 rpm, and a discharge rate of 10 kg / h. Polyolefin a-1 was obtained. The physical characteristics of the obtained a-1 are shown in Table 1.

[Modified cyclic polyolefin]
・ A-1:
A modified cyclic polyolefin A-1 was obtained in the same manner as in a-1 except that the amount of maleic anhydride was 1.0 part by mass and the amount of organic peroxide was 2 parts by mass. The physical characteristics of A-1 are shown in Table 1.

・ A-2:
After stirring well with 100 parts by mass of a-1 and 1 part by mass of perhexa 25B, a modified cyclic polyolefin A-2 was obtained in the same manner as in a-1. The physical characteristics of A-2 are shown in Table 1.

・ A-2:
As the cyclic polyolefin, Zelas MC930 manufactured by Mitsubishi Chemical Corporation was used as it was without denaturation treatment. The physical characteristics of a-2 are shown in Table 1.

・ A-3:
As a maleic acid-modified styrene-butadiene block copolymer hydride, Tough Tech M1943 manufactured by Asahi Kasei Corporation was used.
Reference numeral a-3 is a modified maleic acid of polyolefin, but the aromatic vinyl polymer block unit of the raw material polyolefin is not hydrogenated. The physical characteristics of a-3 are shown in Table 1.

[Thermosetting resin]
・ B-1:
Made by Mitsubishi Chemical Co., Ltd .: Trade name "jER YX7700" (xylenol skeleton-containing novolac type epoxy resin, epoxy equivalent: 271 g / equivalent, Mn: 660, average number of epoxy groups in one molecule: 2.4); 85 g, scent 2-naphthyl acid (active equivalent: 248 g / equivalent); 38.41 g, 4- (dimethylamino) pyridine; 0.01 g was placed in a reaction vessel equipped with a stirrer and reacted at a reaction temperature of 140 ° C. under a nitrogen gas atmosphere. The reaction was carried out for 6 hours to obtain a solid epoxy resin. The obtained epoxy resin was used.

・ B-2:
Mitsubishi Chemical Corporation: Trade name "jER1007" (bisphenol-A type epoxy resin, epoxy equivalent: 2000 g / equivalent, Mn: 2900) was used.

[Curing agent]
・ C-1:
Made by Sumitomo Chemical Co., Ltd .: The trade name "Unifire W575" (functional group equivalent: 220 g / equivalent, number average molecular weight; 3500) was used.

・ C-2:
Gun Ei Chemical Industry Co., Ltd .: "PSM-4261" (phenol resin) was used.

[catalyst]
Made by Shikoku Kasei Kogyo Co., Ltd .: The trade name "Curesol 2E4MZ" (imidazole-based epoxy resin curing accelerator) was used.

<Example 1>
According to Table 2, 5 g of modified cyclic polyolefin A-1, 9 g of thermosetting resin B-1, 68 mL of toluene as a solvent, and 16.3 g of methyl ethyl ketone (MEK) are placed in a 200 mL separable flask, and the temperature is raised to 60 ° C. with stirring. It was heated to make a solution. Next, the liquid temperature was lowered to 40 ° C., 1.65 g of the curing agent C-2 was added, and when all were dissolved while stirring, 0.05 g of the catalyst was added, and the mixture was further dissolved by stirring for 20 minutes.
The obtained solution was applied onto the release surface of a release PET film (Toray Film Processing Co., Ltd., Therapy PJ271) with a coating thickness of 10 mils, the solvent was removed with a dryer, and then the temperature was 160 ° C. in an oven. The heat treatment was carried out for 2 hours, and the curing treatment was carried out.
The obtained film was peeled off from a release PET film, and the dielectric loss tangent was measured. The results are shown in Table 2.

<Example 2>
The same as in Example 1 except that C-1 was used as the curing agent and only toluene was used as the solvent, but a solution was prepared at the ratio shown in Table 2 and the dielectric loss tangent was measured in the same manner.

<Example 3>
A-2 was used as the modified cyclic polyolefin in the same manner as in Example 2, except that a solution was prepared at the ratio shown in Table 2 and the dielectric loss tangent was measured in the same manner.

<Comparative example 1>
A solution was prepared at the ratio shown in Table 2 without using the modified cyclic polyolefin, and the dielectric loss tangent was measured in the same manner as in Example 1.

<Comparative example 2>
B-2 was used as the thermosetting resin and C-2 was used as the curing agent in the same manner as in Comparative Example 1, except that a solution was prepared at the ratio shown in Table 2 and the dielectric loss tangent was measured in the same manner.

<Comparative example 3>
A solution was prepared in the same manner as in Example 2 except that a-1 was used as the modified cyclic polyolefin, and a cured film was prepared. The obtained cured film was brittle and shattered when peeled from the release PET film, and the dielectric loss tangent could not be measured.

<Comparative example 4>
A solution was prepared in the same manner as in Example 2 except that a-2 was used instead of A-1 as the modified cyclic polyolefin, and a cured film was prepared. The obtained cured film was brittle and shattered when peeled from the release PET film, and the dielectric loss tangent could not be measured.

<Comparative example 5>
A solution was prepared in the same manner as in Example 2 except that a-3 was used instead of A-1 as the modified cyclic polyolefin. I tried to apply it on the release PET film, but the solution gelled and became non-uniform and could not be applied.

<Result>
From these results, block copolymers having aromatic vinyl polymer block units with insufficient hydrogenation (a-3: Comparative Example 5) and cyclic polyolefins with sufficient hydrogenation but not acid-modified ( a-2: Comparative Example 4) and an acid-modified cyclic polyolefin having an excessively large Mw (a-1: Comparative Example 3) are good cured films in the composition with a thermosetting resin. I found that I couldn't get it.

On the other hand, it was found that the thermosetting resin compositions (Examples 1 and 2) using the modified cyclic polyolefin with controlled Mw provide a thermosetting film with significantly improved dielectric loss.

Claims (15)

A resin composition containing a modified cyclic polyolefin, at least one thermosetting resin selected from an epoxy resin, an acrylic resin, a phenol resin, a polyphenylene ether resin, a polyimide resin, and a bismaleimide resin, and a curing agent.
The weight average molecular weight (Mw) of the modified cyclic polyolefin is 60,000 or less, and the modified cyclic polyolefin has a weight average molecular weight (Mw) of 60,000 or less.
The modified cyclic polyolefin is a cyclic polyolefin which is a modified product of unsaturated carboxylic acid and / or its anhydride.
A resin composition comprising a hydrogenated block copolymer in which the cyclic polyolefin is a hydride of a block copolymer containing at least one aromatic vinyl monomer unit and at least one conjugated diene monomer unit. The hydrogenated block copolymer is a hydrogenated product of a hydrogenated aromatic vinyl polymer block unit, which is a hydride of a polymer block composed of the aromatic vinyl monomer unit, and a hydride of a polymer block composed of the conjugated diene monomer unit. Has a conjugated diene polymer block unit,
The resin composition according to claim 1, wherein the hydrogenated block copolymer has at least two hydrogenated aromatic vinyl polymer block units and at least one hydrogenated conjugated diene polymer block unit. The resin composition according to claim 2, wherein the hydrogenated aromatic vinyl polymer block unit has a hydrogenation level of 90% or more, and the hydrogenation-conjugated diene polymer block unit has a hydrogenation level of 95% or more. .. The resin composition according to any one of claims 1 to 3, wherein the modified cyclic polyolefin has a modification rate of 0.1 to 2% by mass with an unsaturated carboxylic acid and / or an anhydride thereof. The resin composition according to any one of claims 1 to 4, wherein the modified cyclic polyolefin has a dielectric loss of less than 0.001 at a measurement frequency of 10 GHz. The content of the modified cyclic polyolefin is 10 to 60% by mass (relative to the entire resin composition), and the total content of the thermosetting resin and the curing agent is 40 to 90% by mass (in the entire resin composition). The resin composition according to any one of claims 1 to 5. A resin composition solution obtained by dissolving the resin composition according to any one of claims 1 to 6 in an organic solvent at a solid content concentration of 10 to 90% by mass. A cured resin composition obtained by curing the resin composition according to any one of claims 1 to 6. A laminated board for an electric / electronic circuit, which comprises the resin composition according to any one of claims 1 to 6. The cured resin composition according to claim 8, wherein the dielectric loss at a measurement frequency of 10 GHz is less than 0.01. The laminate for an electric / electronic circuit according to claim 9, wherein the dielectric loss at a measurement frequency of 10 GHz is less than 0.01. A method for producing a cured resin composition by removing the solvent of the resin composition solution according to claim 7 and then curing the solution. A method for producing a laminate for an electric / electronic circuit by removing the resin composition solvent of the solution according to claim 7 and then curing the solution. The method for producing a cured resin composition according to claim 12, wherein the dielectric loss at a measurement frequency of 10 GHz is less than 0.01. The method for producing a laminate for an electric / electronic circuit according to claim 13, wherein the dielectric loss at a measurement frequency of 10 GHz is less than 0.01.