Resin composition, cured product, dry film, film, laminated sheet, prepreg, printed wiring board, and electronic device

Abstract

To provide a resin composition that achieves both low dielectric properties and high-temperature heat resistance, and a cured product, a dry film, a film, a laminate sheet, a prepreg, a printed wiring board, and an electronic device that are formed using the resin composition and achieve both low dielectric properties and high-temperature heat resistance. The problem is solved by a resin composition containing a curable compound (B) and a cyclic olefin resin (A) having a constituent unit derived from at least one selected from alpha-pinene, beta-pinene, alpha-phellandrene, and beta-phellandrene, in which the content of the cyclic olefin resin (A) is 0.5-50 mass% based on the total solids content in the resin composition.

Description

Resin compositions, cured products, dry films, films, laminated sheets, prepregs, printed circuit boards, and electronic equipment.

[0001] This disclosure relates to resin compositions, as well as cured products, dry films, films, laminated sheets, prepregs, printed circuit boards, and electronic devices formed using the resin compositions.

[0002] In recent years, the demand for high-capacity and high-speed communication has led to an increase in the use of electrical signals with higher frequencies than before, such as 10 GHz and above. It is generally known that transmission loss due to dielectric materials around the circuit increases as the frequency increases. To suppress transmission loss, polymer materials used in the semiconductor field, such as printed circuit board materials, interlayer insulating materials, and encapsulating resins used in semiconductor packages, require low dielectric loss tangent. Furthermore, when used in semiconductor material applications, processes such as solder reflow may be required, necessitating high-temperature resistance, for example, above 240°C.

[0003] As a material with excellent low dielectric loss tangent (hereinafter also referred to as low dielectric properties), cyclic olefin resins having an alicyclic skeleton in their molecules are expected to be used as semiconductor materials. For example, Patent Documents 1 and 2 describe the use of norbornene-based polymers as semiconductor materials. Patent Document 3 also describes the use of cyclic olefin resins obtained by polymerizing terpene-based compounds.

[0004] International Publication No. 98 / 56011, Japanese Patent Publication No. 2005-103949, Japanese Patent Publication No. 2008-208349

[0005] However, although norbornene-based polymers described in Patent Documents 1 and 2 have excellent low dielectric properties, they may have insufficient heat resistance. Therefore, polymers generally use functional groups or polar groups as constituent units. However, polymers containing such constituent units have high dielectric constants and dielectric loss tangents, making them unsuitable as materials for applications requiring high-frequency characteristics. Furthermore, there are compatibility issues with curable compounds such as maleimide and epoxy, leading to deterioration of heat resistance due to phase separation. In addition, cyclic olefin resins obtained by polymerizing terpene-based compounds described in Patent Document 3 have excellent dielectric properties, but they may deform or foam in high-temperature processes such as solder reflow, resulting in insufficient high-temperature heat resistance.

[0006] Therefore, the object of this disclosure is to provide a resin composition that achieves both low dielectric properties and high-temperature heat resistance, as well as a cured product, dry film, film, laminated sheet, prepreg, printed circuit board, and electronic device formed using the resin composition that achieve both low dielectric properties and high-temperature heat resistance.

[0007] As a result of diligent research, the present inventors have found that the above problems can be solved by the embodiments shown below, and have completed this disclosure. <1>: A resin composition comprising a cyclic olefin resin (A) having constituent units derived from at least one selected from α-pinene, β-pinene, α-phellandrene, and β-phellandrene, and a curable compound (B), wherein the content of the cyclic olefin resin (A) is 0.5 to 50% by mass based on the total solid content in the resin composition. <2>: The resin composition according to <1>, wherein the cyclic olefin resin (A) has a total of 30 to 100 mol% of constituent units derived from at least one selected from α-pinene, β-pinene, α-phellandrene, and β-phellandrene, based on the total constituent units. <3>: The resin composition according to <1> or <2>, wherein the cyclic olefin resin (A) further has constituent units derived from at least one selected from maleic acid derivatives and maleimide derivatives. <4>: The resin composition according to any one of <1> to <3>, wherein the cyclic olefin resin (A) has constituent units derived from β-pinene. <5>: The resin composition according to any one of <1> to <4>, wherein the cyclic olefin resin (A) has a number average molecular weight of 5,000 to 100,000. <6>: The resin composition according to any one of <1> to <5>, wherein the curable compound (B) includes at least one selected from maleimide resin, epoxy resin, cyanate ester resin, allyl group-containing compound, vinyl group-containing compound, and (meth)acrylate group-containing compound. <7>: A cured product obtained by curing the resin composition according to any one of <1> to <6>. <8>: A dry film made from the resin composition according to any one of <1> to <6>. <9>: A film obtained by curing the dry film according to <8>. <10>: A laminated sheet comprising a resin layer formed on a substrate using the resin composition according to any one of <1> to <6>. <11>: A prepreg obtained by impregnating a fibrous substrate with any of the resin compositions described in <1> to <6>. <12>: A printed wiring board comprising an electrical insulating layer formed from at least one selected from the dry film described in <8>, the film described in <9>, and the prepreg described in <11>, and a conductor layer provided on the electrical insulating layer.<13>: An electronic device equipped with a printed circuit board as described in <12>.

[0008] This disclosure provides excellent advantages, such as a resin composition that achieves both low dielectric properties and high-temperature heat resistance, and a cured product, dry film, film, laminated sheet, prepreg, printed circuit board, and electronic device formed using the resin composition that achieve both low dielectric properties and high-temperature heat resistance.

[0009] <Resin Composition> The resin composition of this disclosure (hereinafter also referred to as "this resin composition") comprises a cyclic olefin resin (A) having a constituent unit derived from at least one selected from α-pinene, β-pinene, α-phellandrene, and β-phellandrene, and a curable compound (B). This resin composition is characterized in that the content of the cyclic olefin resin (A) is 0.5 to 50% by mass based on the total solid content in the resin composition. By including the above-mentioned predetermined range amount of the cyclic olefin resin (A) having the specific constituent unit, the low-polarity structure in this resin composition increases, and as a result, the dielectric loss tangent of the resin composition is sufficiently reduced, exhibiting excellent low dielectric properties. Furthermore, compatibility with the curable compound (B) is maintained, deformation at high temperatures is suppressed, and high-temperature heat resistance is exhibited. Moreover, α-pinene, β-pinene, α-phellandrene, and β-phellandrene are plant-derived biomass raw materials, and the use of cyclic olefin resins using such raw materials is useful from the viewpoint of carbon neutrality and the realization of a circular economy. Embodiments of this disclosure will be described in detail below. This disclosure is not limited to the embodiments described below, and includes embodiments that are implemented in a manner that does not alter the essence of the disclosure.

[0010] <Cyclic Olefin Resin (A)> Cyclic olefin resin (A) has constituent units derived from at least one selected from α-pinene, β-pinene, α-phellandrene, and β-phellandrene. Cyclic olefin resin (A) can be obtained by polymerizing a monomer containing at least one selected from α-pinene, β-pinene, α-phellandrene, and β-phellandrene. The polymerization method for obtaining cyclic olefin resin (A) is not particularly limited and can be appropriately selected from known polymerization methods such as cationic polymerization using Lewis acids and coordination polymerization using metal complexes.

[0011] Examples of the cyclic olefin resin (A) include homopolymers of α-pinene, β-pinene, α-phellandrene, or β-phellandrene, copolymers of any combination thereof, copolymers of at least one monomer selected from α-pinene, β-pinene, α-phellandrene, and β-phellandrene with another monomer, and modified homopolymers or copolymers thereof. Among these, from the viewpoint of low dielectric properties and polymerization stability, it is preferable that the cyclic olefin resin (A) has constituent units derived from β-pinene.

[0012] Examples of monomers copolymerizable with the above-mentioned α-pinene, β-pinene, α-phellandrene, and β-phellandrene include olefin monomers such as ethylene, propylene, butene, hexene, octene, butadiene, and isoprene; vinyl ether monomers such as methyl vinyl ether, methyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether; aromatic vinyl monomers such as styrene and methylstyrene; maleimide monomers such as cyclohexyl maleimide and phenyl maleimide; and maleic anhydride. In particular, from the viewpoint of thermal stability, the cyclic olefin resin (A) preferably contains constituent units derived from at least one selected from maleic acid derivatives and maleimide derivatives, and from the viewpoint of achieving both copolymerizability and low dielectric properties, it is preferable that the total amount of constituent units derived from maleic acid derivatives and maleimide derivatives is 0.1 to 67 mol%, and more preferably 50 to 67 mol%, based on the total constituent units.

[0013] In the cyclic olefin resin (A), the total amount of constituent units derived from at least one selected from the group consisting of α-pinene, β-pinene, α-phellandrene, and β-phellandrene is preferably 30 mol% or more, more preferably 50 mol% or more, and even more preferably 80 mol% or more, based on the total constituent units of the cyclic olefin resin (A), from the viewpoint of low dielectric properties, high temperature heat resistance, and compatibility. For example, it may be 30 to 100 mol%. Including 30 mol% or more of constituent units having a ring structure derived from α-pinene, β-pinene, α-phellandrene, and β-phellandrene provides further advantages in terms of low dielectric properties, high temperature heat resistance, and compatibility with the curable compound (B).

[0014] Modifications of the above-mentioned homopolymer or copolymer include, for example, hydrogenation, epoxidation, silylation, halogenation, and cyclopropanation. Among these, cyclic olefin resin (A) modified by hydrogenation, silylation, or cyclopropanation is preferred from the viewpoint of heat resistance and low dielectric properties. Furthermore, since epoxidation modification of cyclic olefin resin (A) enables crosslinking with curable compound (B), epoxidized cyclic olefin resin (A) is preferred from the viewpoint of compatibility with curable compound (B) and heat resistance.

[0015] The amount of carbon-carbon double bonds in the cyclic olefin resin (A) is preferably 6 mmol / g or less, more preferably 4 mmol / g or less, and even more preferably 2 mmol / g or less, from the viewpoint of thermal stability, and may be, for example, 0 mmol / g or more and 6 mmol / g or less. The amount of carbon-carbon double bonds can be adjusted by the modification described above. For example, when the cyclic olefin resin (A) is polyβ-pinene, which is a homopolymer of β-pinene, the amount of carbon-carbon double bonds is 7.3 mmol / g, and this value can be reduced by modification such as hydrogenation. The amount of carbon-carbon double bonds in the cyclic olefin resin (A) can be determined by iodine value titration, １ This can be determined using the integral value of the signal of hydrogen atoms originating from alkenes in 1H-NMR. In the case of modification such as hydrogenation, １The amount of carbon-carbon double bonds can also be determined from the decrease in the hydrogen atom peak originating from alkenes in 1H-NMR.

[0016] The number-average molecular weight of the cyclic olefin resin (A) is not particularly limited, but from the viewpoint of compatibility with the curable compound (B) and heat resistance, it is preferably 3,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more. Also from the same viewpoint, it is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less, and for example, it may be between 5,000 and 100,000. Having a number-average molecular weight of 3,000 to 100,000 allows for suppression of the resin's own mobility while maintaining compatibility with the curable compound (B), thereby suppressing deformation at high temperatures.

[0017] <Curable Compound (B)> The resin composition of this disclosure comprises a curable compound (B) having one or more reactive functional groups in its molecule. The reactive functional group may be a functional group capable of radical polymerization, anionic polymerization, or cationic polymerization, such as a maleimide group, epoxy group, allyl group, vinyl group, or (meth)acryloyl group, or it may be a functional group capable of condensation, such as a cyanate group. That is, as curable compound (B), for example, maleimide resin, epoxy resin, cyanate ester resin, allyl group-containing compound, vinyl group-containing compound, and (meth)acryloyl group-containing compound can be used. From the viewpoint of low dielectric properties, it is preferable that the curable compound (B) contains a vinyl group.

[0018] [Maleimide resins] Maleimide resins include, for example, 4,4'-diphenylmethanebismaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane, 4-methyl-1,3-phenylenebismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, bisphenol A diphenyl ether bismaleimide, and polyphenylmethanemaleimide (CA SNO: 67784-74-1, reaction product of a polymer consisting of formaldehyde and aniline and maleic anhydride), N,N'-(toluene-2,6-diyl)bismaleimide), 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl sulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, N,N'-ethylene bismaleimide, N,N'-trimethylene bismaleimide, N,N'-propylene bismaleimide, N,N'-tetramethylene Bismaleimide, N,N'-pentamethylenebismaleimide, N,N'-(1,3-pentanediyl)bis(maleimide), N,N'-hexamethylenebismaleimide, N,N'-(1,7-heptanediyl)bismaleimide, N,N'-(1,8-octandiyl)bismaleimide, N,N'-(1,9-notanediyl)bismaleimide, N,N'-(1,10-decanediyl)bismaleimide, N,N'-(1,11-undecanediyl)bismaleimide, N,N'-(1,12-dodecanediyl)bismaleimide, N, N'-[(1,4-phenylene)bismethylene]bismaleimide, N,N'-[(1,2-phenylene)bismethylene]bismaleimide, N,N'-[(1,3-phenylene)bismethylene]bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, N,N'-[(methylimino)bis(4,1-phenylene)]bismaleimide, N,N'-(2-hydroxypropane-1,3-diylbisiminobiscarbonylbisethylene)bismaleimide, N,N'-(dithiobisethylene)bismaleimide, N,N'-[hexamethylenebis(iminocarbonylmethylene)]bismaleimide, N,N'-carbonylbis(1,4-phenylene)bismaleimide, N,N',N''-[nitrilotris(ethylene)]trismaleimide, N,N',N''-[nitrilotris(4,1-phenylene)]trismaleimide, N,N'-[p-phenylenebis(oxy-p-phenylene)]bismaleimide, N,N'-[methylenebis(oxy)bis(2-methyl-1,4-phenylene)]bismaleimide, N,N'-[methylenebis(oxy-p-phenylene )]bis(maleimide)N,N'-[dimethylsilylenebis[(4,1-phenylene)(1,3,4-oxadiazole-5,2-diyl)(4,1-phenylene)]]bismaleimide, N,N'-[(1,3-phenylene)bisoxybis(3,1-phenylene)]bismaleimide, 1,1'-[3'-oxospiro[9H-xanthene-9,1'(3'H)-isobenzofuran]-3,6-diyl]bis(1H-pyrrole-2,5-dione), N,N'-(3,3'-dichlorobiphenyl-4,4'-diyl)bismaleimide, N,N '-(3,3'-dimethylbiphenyl-4,4'-diyl)bismaleimide, N,N'-(3,3'-dimethoxybiphenyl-4,4'-diyl)bismaleimide, N,N'-[methylenebis(2-ethyl-4,1-phenylene)]bismaleimide, N,N'-[methylenebis(2,6-diethyl-4,1-phenylene)]bismaleimide, N,N'-[methylenebis(2-bromo-6-ethyl-4,1-phenylene)]bismaleimide, N,N'-[methylenebis(2-methyl-4,1-phenylene)]bismaleimide, N,N'-[ethyl [Nbis(oxyethylene)]bismaleimide, N,N'-[sulfonylbis(4,1-phenylene)bis(oxy)bis(4,1-phenylene)]bismaleimide, N,N'-[naphthalene-2,7-diylbis(oxy)bis(4,1-phenylene)]bismaleimide, N,N'-[p-phenylenebis(oxy-p-phenylene)]bismaleimide, N,N'-[(1,3-phenylene)bisoxybis(3,1-phenylene)]bismaleimide, N,N'-(3,6,9-trioxaundecane-1,11-diyl)bismaleimide, N,N'-[isopropylidenebis[p-phenyleneoxycarbonyl(m-phenylene)]]bismaleimide, N,N'-[isopropylidenebis[p-phenyleneoxycarbonyl(p-phenylene)]]bismaleimide, N,N'-[isopropylidenebis[(2,6-dichlorobenzene-4,1-diyl)oxycarbonyl(p-phenylene)]]bismaleimide, N,N'-[(phenylimino)bis(4,1-phenylene)]bismaleimide, N,N'-[azobis(4,1-phenylene)] Smaleimide, N,N'-[1,3,4-oxadiazole-2,5-diylbis(4,1-phenylene)]bismaleimide, 2,6-bis[4-(maleimido-N-yl)phenoxy]benzonitrile, N,N'-[1,3,4-oxadiazole-2,5-diylbis(3,1-phenylene)]bismaleimide, N,N'-[bis[9-oxo-9H-9-phospha(V)-10-oxaphenanthrene-9-yl]methylenebis(p-phenylene)]bismaleimide, N,N'-[Hexaful Oroisopropylidenebis[p-phenyleneoxycarbonyl(m-phenylene)]]bismaleimide, N,N'-[carbonylbis[(4,1-phenylene)thio(4,1-phenylene)]]bismaleimide, N,N'-carbonylbis(p-phenyleneoxyp-phenylene)bismaleimide, N,N'-[5-tert-butyl-1,3-phenylenebis[(1,3,4-oxadiazole-5,2-diyl)(4,1-phenylene)]]bismaleimide, N,N'-[cyclohexylidenebis( 4,1-phenylene) bismaleimide, N,N'-[methylenebis(oxy)bis(2-methyl-1,4-phenylene)] bismaleimide, N,N'-[5-[2-[5-(dimethylamino)-1-naphthylsulfonylamino]ethylcarbamoyl]-1,3-phenylene] bismaleimide, N,N'-(oxybisethylene) bismaleimide, N,N'-[dithiobis(m-phenylene)] bismaleimide, N,N'-(3,6,9-trioxaundecane-1,11-diyl) bismaleimide, N,Examples of polyfunctional maleimides include N'-(ethylenebis-p-phenylene)bismaleimide, BMI-689, BMI-1500, BMI-1700, BMI-3000, BMI-5000, BMI-9000 from Designermolecules, and ODA-BMI and BAFBMI from JFE Chemical.

[0019] [Epoxy Resins] Examples of epoxy resins include tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, triglycidylmethaminophenol, tetraglycidylmetaxylylenediamine, sorbitol polyglycidyl ether, diglycidyl phthalate, diglycidylhexahydrophthalate, diglycidyltetrahydrophthalate, epoxycyclohexylmethyl-epoxycyclohexanecarboxylate, bis(epoxycyclohexyl)adipate, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD ​​type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, α-naphthol novolac type epoxy resin, bisphenol A type novolac type epoxy resin, dicyclopentadiene type epoxy resin, tetrabrombisphenol A type epoxy resin, and brominated phenol novolac type epoxy resin.

[0020] [Cyanate ester resins] Examples of cyanate ester resins include 1,3- or 1,4-dicyanatebenzene, 1,3,5-tricyanatebenzene, 1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatenaphthalene, 1,3,6-tricyanatenaphthalene, 4,4-dicyanatebiphenyl, bis(4-cyanatephenyl)methane, bis(3,5-dimethyl-4-cyanatephenyl)methane, 2,2-bis(4-cyanatephenyl)propane, 2,2-bis(3,5-dibromo-4-cyanatephenyl)propane, 2,2-bis(3,5-dimethyl-4-cyanatephenyl)propane, bis Examples include cyanate ester compounds obtained by the reaction of (4-cyanatephenyl) ether, bis(4-cyanatephenyl) thioether, bis(4-cyanatephenyl) sulfone, tris(4-cyanatephenyl) phosphite, tris(4-cyanatephenyl) phosphate, oligomers (novolac, hydroxyl group-containing thermoplastic resins (hydroxypolyphenylene ether, hydroxypolystyrene, hydroxypolycarbonate, etc.)) with cyanide halides, and cyanate ester compounds obtained by the reaction of polyfunctional phenols, in which phenol is linked with dicyclopentadiene, with cyanide halides. These may be used individually or in combination of two or more.

[0021] [Allyl group-containing compounds] Examples of allyl group-containing compounds include (meth)allyl alcohol, triallyl isocyanurate, trimethylolpropanediallyl ether, trimethylolpropanetrialyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether, tetraallyloxyethane, polyallyl saccharose, di(meth)allyl phthalate, tri(meth)allyl isocyanurate, and tri(meth)allyl cyanurate.

[0022] [Vinyl group-containing compounds] Examples of vinyl group-containing compounds include styrene, vinyltoluene, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinylpyridine, hexanediol dinorbornene carboxylate, vinylbenzyl-modified polyphenylene ether, pentaerythritol tetranorbornene carboxylate, triethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexanediol divinyl ether, and divinylbenzene.

[0023] Examples of vinyl group-containing compounds other than those mentioned above include homopolymers of divinylbenzene, diisopropenylbenzene, butadiene, and isoprene, as well as vinyl group-containing polymers obtained by copolymerizing these with other monomers.

[0024] [(meth)acryloyl group-containing compounds] Examples of (meth)acryloyl group-containing compounds include monofunctional (meth)acrylamide, polyfunctional (meth)acrylamide, monofunctional (meth)acrylate, and polyfunctional (meth)acrylate. (Meth)acryloyl group-containing compounds having monofunctional (meth)acrylate and / or polyfunctional (meth)acrylate are also called (meth)acrylate group-containing compounds.

[0025] Examples of monofunctional (meth)acrylamide compounds include diacetone (meth)acrylamide, isobutoxymethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, t-octyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, (meth)acryloylmorpholine, acrylamide-2-methylpropanesulfonic acid, and N-isopropyl (meth)acrylamide. Examples of polyfunctional (meth)acrylamide compounds include N,N'-diacryloyl-4,7,10-trioxa-1,13-tridecanediamine, N,N',N''-triacryloyldiethylenetriamine, N,N',N'',N'''-tetraacryloyltriethylenetetramine, and N,N'-{[2-acrylamide-2-[(3-acrylamidepropoxy)methyl]propane-1,3-diyl)bis(oxy)]bis(propane-1,3-diyl)}diacrylamide.

[0026] Examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, cyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, benzyl (meth)acrylate, phenol alkylene oxide adducts (meth)acrylates, and p-cumylphenol alkylene oxide adducts. (meth)acrylate of substances, (meth)acrylate of o-phenylphenol alkylene oxide adducts, (meth)acrylate of nonylphenol alkylene oxide adducts, 2-methoxyethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, (meth)acrylate of alkylene oxide adduct of 2-ethylhexyl alcohol, tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, (2-ethyl-2-methyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (2-isobutyl-2-methyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (1,4-dioxaspiro[4,5]decane-2-yl)methyl (meth)acrylate, glycidyl (meth)acrylate, 3,Examples include 4-epoxycyclohexylmethyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, 2-(meth)acryloyloxyethyl isocyanate, allyl (meth)acrylate, N-(meth)acryloyloxyethyl hexahydrophthalimide, N-(meth)acryloyloxyethyl tetrahydrophthalimide, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl succinic acid, ω-carboxy-polycaprolactone mono(meth)acrylate, 2-(meth)acryloyloxyethyl acid phosphate, 3-(meth)acryloyloxypropyl trimethoxysilane, 3-(meth)acryloyloxypropyl dimethoxymethylsilane, 3-(meth)acryloyloxypropyl triethoxysilane, and 2-(meth)acryloyloxyethyl acid phosphate.

[0027] Examples of polyfunctional (meth)acrylates include (meth)acryloyl group-containing polyphenylene ether, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, and 1,9-nonanediol di( Meth)acrylate, cyclohexanedimethylol di(meth)acrylate and tricyclodecanedimethylol di(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate and tripropylene glycol di(meth)acrylate, esterification reaction product of neopentyl glycol, hydroxypivalic acid and (meth)acrylic acid (hereinafter referred to as "hydroxypivalic acid neopentyl glycol di(meth)acrylate").), neopentyl glycol di(meth)acrylate of caprolactone-modified hydroxypivalate, di(meth)acrylate of bisphenol compounds such as di(meth)acrylate of bisphenol A alkylene oxide adduct, di(meth)acrylate of hydrogenated bisphenol compounds such as di(meth)acrylate of hydrogenated bisphenol A, di(meth)acrylate of isocyanurate alkylene oxide adduct, tri(meth)acrylate of isocyanurate alkylene oxide adduct, di(meth)acrylate of caprolactone-modified isocyanurate alkylene oxide adduct, poly(meth)acrylate of isocyanurate alkylene oxide adduct such as tri(meth)acrylate of caprolactone-modified isocyanurate alkylene oxide adduct, trimethylolpropane Examples include polyol poly(meth)acrylates such as tri(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, pentaerythritol tri or tetra(meth)acrylate, dipentaerythritol penta or hexa(meth)acrylate, tri(meth)acrylate of trimethylolpropanealkylene oxide adducts, tetra(meth)acrylate of ditrimethylolpropanealkylene oxide adducts, tri or tetra(meth)acrylate of pentaerythritol alkylene oxide adducts, and penta or hexa(meth)acrylate of dipentaerythritol alkylene oxide adducts: urethane(meth)acrylate, epoxy(meth)acrylate, and polyester(meth)acrylate.

[0028] From the viewpoint of low dielectric properties and high-temperature heat resistance, it is important that the content of the cyclic olefin resin (A) in the resin composition of this disclosure is 0.5 to 50% by mass, based on the total solid content in the resin composition. By having the content of the cyclic olefin resin (A) within the above range, the dielectric loss tangent of the resin composition is sufficiently reduced, and low dielectric properties can be achieved. Furthermore, compatibility with the curable compound (B) is maintained, deformation at high temperatures is suppressed, and high-temperature heat resistance can be achieved. From the viewpoint of low dielectric properties, the content of the cyclic olefin resin (A) is preferably 5% by mass or more, more preferably 10% by mass or more. Furthermore, from the viewpoint of high-temperature heat resistance, it is preferably 30% by mass or less, more preferably 20% by mass or less.

[0029] From the viewpoint of low dielectric properties and high-temperature heat resistance, the resin composition of this disclosure has a curable compound (B) content of preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the total solid content in the resin composition. Furthermore, it is preferably 99.5% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 80% by mass or less.

[0030] [Solvent] The resin composition of the present disclosure may contain a solvent. Examples of solvents include hexane, cyclohexane, methylcyclohexane, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-pyrrolidone, N,N-dimethylformamide, butanol, 2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, and 2-acetoxy-1-methoxypropane. From the viewpoint of solubility of the cyclic olefin resin, aliphatic hydrocarbon compounds or alicyclic hydrocarbon compounds are preferred, and among these, hexane, cyclohexane, and methylcyclohexane can be preferably used.

[0031] [Other Components] The resin compositions of this disclosure may contain other components such as non-curable polymers, curing initiators or catalysts. Examples of non-curable polymers include polybutadiene, polyisoprene, butadiene styrene copolymers and their hydrogenated products, and polyphenylene ethers. Examples of curing initiators include maleimide resins, allyl group-containing compounds, and radical polymerization initiators for accelerating the curing of vinyl group-containing compounds. Examples of radical polymerization initiators include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, di-t-butyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, t-butyl peroxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, di-t-amyl peroxide, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-hexyl peroxypivalate, and lauroyl peroxide. Examples of catalysts that promote curing include maleimide resins and imidazole-based catalysts that promote the curing of epoxy resins. Examples of imidazole-based catalysts include 2-methylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole.

[0032] <Use of Resin Composition> [Cured product, dry film, film, resin sheet, prepreg] The resin composition of this disclosure exhibits excellent low dielectric properties and high-temperature heat resistance, and can be used, for example, for adhesive layer formation, and for insulating layer formation of electronic elements such as various memories and printed circuit boards. When the resin composition is used for the above applications, it may be in the form of a cured product obtained by curing the resin composition, or in the form of a dry film made of the resin composition and a film obtained by curing the dry film (i.e., a cured film), or in the form of a resin sheet having a resin layer formed by the resin composition on a substrate, or it may be a prepreg obtained by impregnating a fibrous substrate with the resin composition. Curing may be carried out under known conditions, for example, under conditions such as 200°C for 2 hours. A dry film can be obtained, for example, by applying a resin composition containing a solvent to a release film, drying the solvent, and then peeling off the release film. A resin sheet can also be obtained by laminating the dry film made by the above method with a substrate. The resin sheet may be pressed and / or heat-cured as needed. An electrical insulating layer containing the cured product may also be laminated to a substrate having a conductive layer on its surface.

[0033] Examples of substrates include polymer films such as polyimide, polyethylene terephthalate, polyethylene, and polypropylene; metal foils such as gold, silver, copper, aluminum, nickel, and stainless steel; and inorganic materials such as ITO, glass, silicon, and silicon carbide. From the viewpoint of electrical conductivity and cost, copper used as CCL (copper clad laminate) is preferred for the metal foil, and the thickness may be in the range of 1 to 50 μm.

[0034] The thickness of the cured product, dry film, film, or resin layer made using the resin composition can be appropriately selected according to the application and required performance, but for example, it may be in the range of 50 to 200 μm.

[0035] Prepregs can be obtained by impregnating a fiber substrate with a resin composition as a fiber reinforcing material. Examples of fiber substrates include glass fibers, carbon fibers, aramid fibers, and polyester fibers.

[0036] <Electronic device> A printed wiring board can be obtained by providing a conductor layer on an electrical insulation layer formed of at least one selected from the group consisting of a dry film, a film, and a prepreg of the present disclosure. The printed wiring board can be manufactured, for example, by forming an electronic circuit on a metal foil layer of a resin sheet provided with a cured product of a resin formed of a resin composition on a metal foil. Further, by mounting electronic components such as semiconductor elements on the printed wiring board, it can be used as an electronic device. Examples of the electronic device include a server, a router, a GPS antenna, an antenna for a wireless base station, a millimeter wave antenna, an RFID antenna, a mobile phone, a smartphone, a PHS, a PDA, a tablet terminal, a personal computer, a television, a digital camera, a digital video camera, a POS terminal, a wearable terminal, a digital media player, an electronic control system device, an in-vehicle communication device, a car navigation device, a millimeter wave radar, an in-vehicle camera module, a semiconductor test device, and a high-frequency measurement device.

[0037] Hereinafter, the present disclosure will be described more specifically with reference to examples. However, the following examples do not limit the scope of rights of the present disclosure in any way. In the examples and comparative examples, "parts" and "%" represent "parts by mass" and "mass%" unless otherwise specified. Mol represents the amount of substance, and mol% represents the ratio of the amount of substance in all monomers.

[0038] <Method for measuring number average molecular weight (Mn) and mass average molecular weight (Mw)> The number average molecular weight of the cyclic olefin resin (A) and the mass average molecular weight (Mw) of the vinyl group-containing compound V1 were measured values in terms of standard polystyrene by gel permeation chromatography (GPC). The following conditions were used as the measuring apparatus and measuring conditions. For other matters, it was based on JIS K7252-1 to 4:2008. (Conditions) Column: A combination of TOSOH TSKgel SuperHZM-H, TOSOH TSKgel SuperHZ4000, and TOSOH TSKgel SuperHZ2000 Carrier: Tetrahydrofuran Measurement temperature: 40 ° C Carrier flow rate: 1.0 mL / min Sample concentration: 0.1 mass% Detector: RI (refractive index) detector Injection volume: 0.1 mL

[0039] <Method for Measuring the Amount of Carbon-Carbon Double Bonds> Using tetralin as a standard substance, １ From the comparison of the area of the peak derived from the aromatic ring protons of tetralin (about 7 ppm) and the area of the peak derived from the double bond protons of the cyclic olefin resin (A) (about 5 ppm) in the H-NMR spectrum, the amount of carbon-carbon double bonds in the cyclic olefin resin (A) was measured. Tetralin and the cyclic olefin resin (A) were accurately weighed and dissolved in deuterated chloroform, １ and the H-NMR measurement was performed. At this time, the value of the amount of carbon-carbon double bonds can be obtained by the following formula 1.

[0040] <Production of Cyclic Olefin Resin (A)> [Production Example 1] Cyclic Olefin Resin (A1) A reaction vessel equipped with a stirrer and a nitrogen inlet tube was dried by heating under a nitrogen stream. 40 mL (40 mmol) of an n-hexane solution of ethylaluminum dichloride and 260 mL of methylene chloride (in this example, a reagent manufactured by Fuji Film Wako Pure Chemical Corporation dehydrated with molecular sieve 3A was used.) were charged, stirring was started, and it was cooled to -30 °C in a cooling bath. Next, 64 mL (450 mmol) of β-pinene (in this example, a reagent manufactured by Merck KGaA purified by simple distillation was used.) was added, and stirring was continued for another 30 minutes.p>Next, 100 mL of methanol was added, the reaction vessel was taken out of the cooling bath, and stirred until it reached room temperature. Next, the reaction solution was separated and washed once each with an aqueous hydrochloric acid solution and an aqueous sodium hydroxide solution. The obtained organic layer was added to 3000 mL of methanol, and the precipitate was filtered and dried to obtain a cyclic olefin resin (A1). The number average molecular weight of the obtained resin was [5,200].

[0041] [Production Example 2] Cyclic Olefin Resin (A2) A cyclic olefin resin (A2) was obtained in the same manner as in Production Example 1, except that 260 mL of methylene chloride was changed to 150 mL of methylene chloride and 110 mL of methylcyclohexane (in this example, a reagent manufactured by Fuji Film Wako Pure Chemical Corporation dehydrated with molecular sieve 3A was used.), and the cooling temperature of the cooling bath was changed from -30 °C to -78 °C. The number average molecular weight Mn of the obtained resin was [11,200].

[0042] [Production Example 3] Cyclic Olefin Resin (A3) A cyclic olefin resin (A3) was obtained in the same manner as in Production Example 1, except that 40 mL (40 mmol) of n-hexane solution of ethylaluminum dichloride was replaced with 5.4 g (40 mmol) of aluminum chloride, 260 mL of methylene chloride was replaced with 150 mL of methylcyclohexane and 150 mL of methylene chloride, and the cooling temperature of the cooling tank was changed from -30°C to -78°C. The number average molecular weight of the obtained resin was 29,600.

[0043] [Production Example 4] Cyclic Olefin Resin (A4) A reaction vessel equipped with a stirrer and a nitrogen inlet tube was dried by heating under a nitrogen stream. 7 mL of a hexane solution containing 0.22 mmol of 1,3-Bis(1-chloro-1-methylethyl)benzene (in this example, the benzene synthesized by the method described in Polym. Chem., 2014, 5, 3222) was added, along with 0.7 mL (6.7 mmol) of diethyl ether, 9 mL (9 mmol) of an n-hexane solution of ethylaluminum dichloride, 270 mL of methylcyclohexane, and 300 mL of methylene chloride. Stirring was started, and the mixture was cooled to -78°C in a condenser. Next, 64 mL (450 mmol) of β-pinene was added over 4 hours using a syringe pump, and the mixture was stirred for a further 30 minutes. Then, 200 mL of methanol was added, the reaction vessel was removed from the condenser, and the mixture was stirred until it reached room temperature. Next, the reaction mixture was separated and washed once each with hydrochloric acid aqueous solution and sodium hydroxide aqueous solution. The resulting organic layer was added to 3000 mL of methanol, and the precipitate was filtered and dried to obtain a cyclic olefin resin (A4). The number-average molecular weight of the obtained resin was 49,300.

[0044] [Production Example 5] Cyclic Olefin Resin (A5) A cyclic olefin resin (A5) was obtained in the same manner as in Production Example 4, except that 7 mL of a hexane solution containing 0.22 mmol of 1,3-Bis(1-chloro-1-methylethyl)benzene was replaced with 7 mL of a hexane solution containing 0.22 mmol of (1-Chloro-1-methylethyl)benzene (in this example, the compound synthesized by the method described in Polym. Chem., 2014, 5, 3222 was used), 270 mL of methylcyclohexane and 300 mL of methylene chloride were replaced with 135 mL of methylcyclohexane and 150 mL of methylene chloride, and the addition time using a syringe pump was changed from 4 hours to 1 hour. The number average molecular weight of the obtained resin was 10,100.

[0045] [Production Example 6] Hydrogenated Cyclic Olefin Resin (A6) 10 g of the cyclic olefin resin (A2) obtained in Production Example 2, 7.2 g of palladium-alumina, and 120 mL of heptane were added to an autoclave and pressurized to 0.9 MPa with hydrogen gas. Next, the temperature was raised to 140°C and the mixture was stirred for 5 hours to carry out the hydrogenation reaction. After cooling, the palladium-alumina was filtered, and the solvent was removed by vacuum drying to obtain the hydrogenated cyclic olefin resin (A6). The hydrogenation rate of the obtained resin was: １ The decrease in double bond protons (approximately 5 ppm) of the β-pinene polymer, as determined by 1H-NMR spectroscopy, was found to be 50%. The number-average molecular weight of the obtained resin was 10,700.

[0046] [Production Example 7] Hydrogenated Cyclic Olefin Resin (A7) A hydrogenated cyclic olefin resin (A7) was obtained in the same manner as in Production Example 6, except that the reaction time for the hydrogenation reaction was changed to 13 hours. The hydrogenation rate of the obtained resin was 74%, and the number average molecular weight was 10,200.

[0047] [Production Example 8] Hydrogenated Cyclic Olefin Resin (A8) A hydrogenated cyclic olefin resin (A8) was obtained in the same manner as in Production Example 6, except that the reaction time for the hydrogenation reaction was changed to 40 hours. １No double-bonded proton peaks (approximately 5 ppm) were observed in the 1H-NMR spectrum, indicating that the hydrogenation rate of the obtained resin was 100%. The number-average molecular weight of the obtained resin was 10,200.

[0048] [Production Example 9] Hydrogenated Cyclic Olefin Resin (A9) A hydrogenated cyclic olefin resin (A9) was obtained in the same manner as in Production Example 6, except that the cyclic olefin resin (A3) from Production Example 3 was used as the raw material. The hydrogenation rate of the obtained resin was 53%, and the number average molecular weight was 28,600.

[0049] [Production Example 10] Hydrogenated Cyclic Olefin Resin (A10) A hydrogenated cyclic olefin resin (A10) was obtained in the same manner as in Production Example 7, except that the cyclic olefin resin (A3) from Production Example 3 was used as the raw material. The hydrogenation rate of the obtained resin was 73%, and the number average molecular weight was 28,200.

[0050] [Production Example 11] Hydrogenated Cyclic Olefin Resin (A11) A hydrogenated cyclic olefin resin (A11) was obtained in the same manner as in Production Example 8, except that the cyclic olefin resin (A3) from Production Example 3 was used as the raw material. The hydrogenation rate of the obtained resin was 100%, and the number average molecular weight was 27,800.

[0051] [Production Example 12] Hydrogenated Cyclic Olefin Resin (A12) A hydrogenated cyclic olefin resin (A12) was obtained in the same manner as in Production Example 6, except that the cyclic olefin resin (A4) from Production Example 4 was used as the raw material. The hydrogenation rate of the obtained resin was 55%, and the number average molecular weight was 48,900.

[0052] [Production Example 13] Hydrogenated Cyclic Olefin Resin (A13) A hydrogenated cyclic olefin resin (A13) was obtained in the same manner as in Production Example 7, except that the cyclic olefin resin (A4) from Production Example 4 was used as the raw material. The hydrogenation rate of the obtained resin was 75%, and the number average molecular weight was 49,000.

[0053] [Production Example 14] Hydrogenated Cyclic Olefin Resin (A14) A hydrogenated cyclic olefin resin (A14) was obtained in the same manner as in Production Example 8, except that the cyclic olefin resin (A4) from Production Example 4 was used as the raw material. The hydrogenation rate of the obtained resin was 100%, and the number average molecular weight was 46,000.

[0054] [Production Example 15] A cyclic olefin resin (A15) was obtained in the same manner as in Production Example 3, except that 64 mL (450 mmol) of β-pinene was replaced with a mixture of 57.6 mL (405 mmol) of β-pinene and 5.9 mL (45 mmol) of 4-vinyl-1-cyclohexene. The number-average molecular weight of the obtained resin was 22,000.

[0055] [Production Example 16] A cyclic olefin resin (A16) was obtained in the same manner as in Production Example 3, except that 64 mL (450 mmol) of β-pinene was replaced with a mixture of 44.7 mL (315 mmol) of β-pinene and 17.6 mL (135 mmol) of 4-vinyl-1-cyclohexene. The number-average molecular weight of the obtained resin was 18,300.

[0056] [Production Example 17] Cyclic Olefin Resin (A17) 10 g of the cyclic olefin resin (A16) obtained in Production Example 16, 7.2 g of palladium-alumina, and 120 mL of heptane were added to an autoclave and pressurized to 0.9 MPa with hydrogen gas. Next, the temperature was raised to 140°C and the mixture was stirred for 40 hours to carry out the hydrogenation reaction. After cooling, the palladium-alumina was filtered out and the solvent was removed by vacuum drying to obtain hydrogenated cyclic olefin resin (A17). １ No double-bonded proton peaks (approximately 5 ppm) were observed in the 1H-NMR spectrum, indicating that the hydrogenation rate of the obtained resin was 100%. The number-average molecular weight of the obtained resin was 17,900.

[0057] [Production Example 18] Cyclic Olefin Resin (A18) A reaction vessel equipped with a stirrer and a nitrogen inlet tube was dried by heating under a nitrogen atmosphere. 10.0 g (57.8 mmol) of phenylmaleimide, 4.4 g (28.9 mmol) of β-pinene, 0.4 g (2.4 mmol) of azobisisobutyronitrile, and 67.5 mL of 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanol were charged into the vessel, and the temperature was raised to 80°C, where stirring was continued for 50 hours. After cooling to room temperature, the reaction mixture was added to 500 mL of methanol, and the precipitate was filtered and dried to obtain cyclic olefin resin (A18). The number-average molecular weight of the obtained resin was 11,900.

[0058] [Production Example 19] Cyclic Olefin Resin (A19) A cyclic olefin resin (A19) was obtained in the same manner as in Production Example 18, except that the amount of azobisisobutyronitrile was changed to 0.2 g (1.2 mmol) and the amount of 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanol was changed to 40.0 mL. The number average molecular weight of the obtained resin was 24,500.

[0059] [Production Example 20] Hydrogenated Cyclic Olefin Resin (A20) 10 g of cyclic olefin resin (A) obtained in Production Example 19, 7.2 g of palladium-alumina, and 120 mL of heptane were added to an autoclave and pressurized to 0.9 MPa with hydrogen gas. The temperature was then raised to 140°C and stirred for 40 hours. After cooling, the palladium-alumina was filtered out and the solvent was removed by vacuum drying to obtain hydrogenated cyclic olefin resin (A20). １ No double-bonded proton peaks (approximately 5 ppm) were observed in the 1H-NMR spectrum, indicating that the hydrogenation rate of the obtained resin was 100%. The number-average molecular weight of the obtained resin was 24,200.

[0060] [Production Example 21] Epoxidized Cyclic Olefin Resin (A21) 5 g of the β-pinene polymer obtained in Production Example 2 was added to a reaction vessel equipped with a stirrer and dissolved in 340 mL of dichloromethane. 340 mL of a 0.125 M aqueous sodium hydrogen carbonate solution was added thereto, and the mixture was stirred at 0°C. 3.0 g of 30% aqueous meta-chloroperbenzoic acid was added thereto in 4 portions at 5-minute intervals. Thereafter, the mixture was returned to room temperature and stirred for 1 hour, 350 mL of saturated sodium thiosulfate was added, and the mixture was further stirred for 30 minutes. The organic layer of the reaction solution was recovered, washed by liquid separation with water, and the solvent was removed by drying under reduced pressure to obtain an epoxidized cyclic olefin resin (A21). The epoxidation rate of the obtained resin was １ From the decrease in the double bond protons (about 5 ppm) of the β-pinene polymer by 1H-NMR spectrum, it was found to be 27%. The number average molecular weight of the obtained resin was 12,200.

[0061] [Production Example 22] Epoxidized Cyclic Olefin Resin (A22) An epoxidized cyclic olefin resin (A22) was obtained in the same manner as Production Example 21, except that the amount of 30% aqueous meta-chloroperbenzoic acid to be added was changed to 4.8 g. The epoxidation rate of the obtained resin was 55%, and the number average molecular weight was 11,900.

[0062] [Production Example 23] Epoxidized Cyclic Olefin Resin (A23) An epoxidized cyclic olefin resin (A23) was obtained in the same manner as Production Example 21, except that the amount of 30% aqueous meta-chloroperbenzoic acid to be added was changed to 11.0 g. １ The peak of the double bond protons (about 5 ppm) could not be confirmed from the 1H-NMR spectrum, and the epoxidation rate of the obtained resin was 100%. The number average molecular weight of the obtained resin was 12,200.

[0063] [Production Example 24] Epoxidized Cyclic Olefin Resin (A24) An epoxidized cyclic olefin resin (A24) was obtained in the same manner as Production Example 23, except that the β-pinene polymer to be used was changed to the β-pinene polymer obtained in Production Example 10. １The 1H-NMR spectrum did not show any peaks for double-bonded protons (approximately 5 ppm), indicating that all of the alkenes that were not hydrogenated in Production Example 10 were epoxidized. The number-average molecular weight of the obtained resin was 10,100.

[0064] [Production Example 25] Silane-modified cyclic olefin resin (A25) A reaction vessel equipped with a stirrer and a nitrogen inlet tube was dried by heating under a nitrogen stream. 5 g of the β-pinene polymer obtained in Production Example 3, 1.1 g (8.0 mmol) of aluminum chloride, and 35 mL of methylene chloride were charged into it, and stirring was started. The mixture was then cooled to 0°C. 5.5 g (47.5 mmol) of triethylsilane was added dropwise over 1 hour, and the mixture was stirred for a further 3 hours. After returning to room temperature, 100 mL of saturated aqueous solution of sodium bicarbonate was added, and the mixture was stirred for a further 1 hour. The organic layer was removed, and the solvent was removed using a vacuum dryer to obtain silane-modified cyclic olefin resin (A25). １ No double-bonded proton peaks (approximately 5 ppm) were detected from the 1H-NMR spectrum, indicating a silanation rate of 100% in the obtained resin. The number-average molecular weight of the obtained resin was 15,200.

[0065] [Production Example 26] Brominated Cyclic Olefin Resin (A26) A reaction vessel equipped with a stirrer and a nitrogen inlet tube was dried by heating under a nitrogen stream. 5 g of the β-pinene polymer obtained in Production Example 3 and 8 mL of carbon tetrachloride were added, and stirring was started, followed by cooling to 0°C. 1.6 g (19.8 mmol) of bromine diluted in 2 mL of carbon tetrachloride was added dropwise over 30 minutes, and stirring was continued for 3 hours. After returning to room temperature, the organic layer was washed three times with water and once with a 5% sodium carbonate aqueous solution. The organic layer was removed, and the solvent was removed using a vacuum dryer to obtain brominated cyclic olefin resin (A26). The bromination rate of the obtained resin was １ The decrease in double bond protons (approximately 5 ppm) of the β-pinene polymer, as determined by 1H-NMR spectroscopy, was 41%. The number-average molecular weight of the obtained resin was 27,200.

[0066] [Production Example 27] Cyclopropanated Cyclic Olefin Resin (A27) A reaction vessel equipped with a stirrer and a nitrogen inlet tube was dried by heating under a nitrogen stream. 5 g of the β-pinene polymer obtained in Production Example 3, 57.8 mL (57.8 mmol) of n-hexane solution of diethylzinc, and 51.5 mL of dichloromethane were charged into it, and stirring was started. The mixture was then cooled to 0°C. 4.8 mL (59.43 mmol) of diiodomethane was added dropwise over 1 hour, the temperature was raised, and reflux was carried out for 8 hours. After returning to room temperature, 2.5 mL of saturated ammonium chloride aqueous solution was added dropwise over 30 minutes. The organic layer was washed twice with saturated brine, the organic layer was removed, and the solvent was removed using a vacuum dryer to obtain cyclopropanated cyclic olefin resin (A27). The cyclopropanation rate of the obtained resin was １ The decrease in double bond protons (approximately 5 ppm) of the β-pinene polymer, as determined by 1H-NMR spectroscopy, was 72%. The number-average molecular weight of the obtained resin was 30,200.

[0067] [Production Example 28] Cyclic Olefin Resin (A28) A cyclic olefin resin (A28) was obtained in the same manner as in Production Example 3, except that β-pinene purified by simple distillation was replaced with α-pinene purified by simple distillation. The number-average molecular weight of the obtained resin was 6,200.

[0068] [Production Example 29] Cyclic Olefin Resin (A29) A cyclic olefin resin (A29) was obtained in the same manner as in Production Example 3, except that β-pinene purified by simple distillation was replaced with α-phellandrene purified by simple distillation. The number-average molecular weight of the obtained resin was 7,100.

[0069] [Production Example 30] Cyclic Olefin Resin (A30) A cyclic olefin resin (A30) was obtained by reacting in the same manner as in Production Example 1, except that β-pinene was replaced with β-phellandrene. The number-average molecular weight of the obtained resin was 12,000.

[0070]

[0071] <Preparation of Vinyl Group-Containing Compounds> [Preparation Example 31] Vinyl Group-Containing Compound V1 Vinyl group-containing compound V1 was synthesized according to the description of Example 3 in International Publication No. 2024 / 135180. Specifically, 0.47 moles (67.0 mL) of divinylbenzene, 0.28 moles (39.3 mL) of ethylvinylbenzene, 1.60 moles (184.4 mL) of styrene, and 3.51 moles (403.3 mL) of n-propyl acetate were placed in a 1.0 L reactor and heated. When the temperature rose to 90°C, 48 mmol of boron trifluoride diethyl ether complex was added and the mixture was reacted for 1.5 hours. 171 ml of 7% sodium bicarbonate aqueous solution was added to the polymerization solution to stop the reaction, and the aqueous phase was removed by liquid-liquid extraction. Another 171 ml of 7% sodium bicarbonate aqueous solution was added thereto and the mixture was stirred for 30 minutes. The oil layer was then extracted and washed three times with pure water. The reaction solution was poured into a large amount of methanol, and the resulting white precipitate was collected to obtain a vinyl group-containing compound V1, a vinyl aromatic copolymer with a Mw of 13,000 and a vinyl equivalent of 390 g / eq.

[0072] <Preparation of Resin Composition> [Example 1] Resin Composition C1 30 parts of cyclic olefin resin (A1), 69 parts of curable resin (B) BMI-TMH (manufactured by Yamato Chemical Industries), 1 part of perhexin 25B (manufactured by NOF Corporation) and 200 parts of tetrahydrofuran were mixed to obtain resin composition C1.

[0073] [Examples 2-90, Comparative Examples 1-3] Resin compositions C2-C90, C ratio 1-C ratio 3 Resin compositions C2-C90, C ratio 1-C ratio 3 Resin compositions C2-C90, C ratio 1-C ratio 3 were obtained in the same manner as in Example 1, except that the compound composition was changed to that shown in Tables 2-5.

[0074] <Evaluation of Resin Composition> Using the obtained resin composition, laminated sheets and copper-clad laminates were obtained as follows. [Preparation of Laminated Sheet] The obtained resin composition was coated onto a polyethylene terephthalate (PET) substrate so that the thickness after drying was 100 μm, and dried in an oven at 80°C for 30 minutes. A release film (Diafoil MRX-50 (thickness 50 μm)) was placed on the resin composition surface of the obtained laminated sheet, and it was pressed at 20 MPa for 2 hours under reduced pressure at 100°C. After cooling, the release film was peeled off, and a laminated sheet having a resin layer formed by the resin composition on the PET substrate was obtained.

[0075] [Preparation of copper-clad laminate] The obtained resin composition was coated onto a release film so that its thickness after drying would be 50 μm, and dried in an oven at 80°C for 30 minutes. The release film was peeled off the obtained laminate, and the obtained resin composition film was sandwiched between the roughened surfaces of two copper foils (F2-WS (thickness 18 μm)), and pressed at 20 MPa for 2 hours under reduced pressure at 200°C to obtain a copper-clad laminate having a resin layer formed by the resin composition.

[0076] (Evaluation of Low Dielectric Properties) For the obtained laminated sheets, the dielectric loss tangent at a measurement frequency of 10 GHz was determined by the cavity resonator method using a dielectric constant measuring device (manufactured by AET Co., Ltd.) under an atmosphere of 23°C and 50% relative humidity, and was evaluated according to the following criteria: S: Dielectric loss tangent is less than 0.001. A: Dielectric loss tangent is 0.001 or more and less than 0.002. B: Dielectric loss tangent is 0.002 or more and less than 0.003. C: Dielectric loss tangent is 0.003 or more and less than 0.004. D: Dielectric loss tangent is 0.004 or more and less than 0.005. E: Dielectric loss tangent is 0.005 or more: There are practical problems.

[0077] (High Temperature Heat Resistance) The obtained copper-clad laminate was cut to a width of 10 mm and a length of 65 mm, and the copper foil surface was brought into contact with molten solder at various temperatures from 240 to 300°C and floated for 1 minute. After that, the appearance of the test piece was visually observed to check for any adhesion abnormalities such as foaming, lifting, or peeling of the adhesive layer after curing. These evaluation results were evaluated according to the following criteria: A: No change in appearance even when floated in molten solder at 290°C. B: Does not satisfy A above. No change in appearance even when floated in molten solder at 280°C. C: Does not satisfy A and B above. No change in appearance even when floated in molten solder at 260°C. D: Does not satisfy A to C above. No change in appearance even when floated in molten solder at 240°C. E: Change in appearance when floated in molten solder at 240°C: Target not met.

[0078]

[0079]

[0080]

[0081]

[0082] The abbreviations in Tables 2-5 are shown below. <Resins> Resin 1: Norbornene copolymer (TOPAS 5013l-10, manufactured by Mitsui Chemicals, Inc.) Resin 2: Polypropylene (IsoTactic polypropylene Mn5000, manufactured by Merck KGaA)

[0083] <Curable Compounds> BMI-TMH: 1,6'-bismaleimide-(2,2,4-trimethyl)hexane (manufactured by Yamato Chemical Industries, Ltd.) SA9000: End-terminated methacrylic polyphenylene ether (manufactured by Saudi Basic Industries Corporation) OPE-2st: End-terminated vinyl polyphenylene ether (manufactured by Mitsubishi Gas Chemical Company, Inc.) BVBz: Divinylbenzene (manufactured by Merck KGaA) TAIC: Triaryl isocyanurate (manufactured by Merck KGaA) TAC: 2,4,6-Traryloxy-1,3,5-triazine (manufactured by Merck KGaA) BADCY: Bisphenol A dicyanate (manufactured by Mitsubishi Gas Chemical Company, Inc.) BMI-2300: Formaldehyde, polymer with benzenamine, maleated, cyclized (manufactured by Yamato Chemical Industries, Ltd.) EPICLON HP-6000: Naphthalene-type epoxy resin (manufactured by DIC Corporation) NC-7000L: Naphthalene skeleton-containing novolac-type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) B-3000: Polybutadiene (manufactured by Nippon Soda Co., Ltd.)

[0084] <Other ingredients> SA90: Polyphenylene ether (manufactured by Saudi Basic Industries Corporation) Perhexyn 25B: 2,5-dimethyl-2,5-di(t-butylperoxy)hexyn-3 (manufactured by NOF Corporation) 2PZ: 2-phenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0085] As shown in Tables 2 to 5, the resin compositions of this disclosure were confirmed to achieve both excellent low dielectric properties and high-temperature heat resistance. This is presumed to be due to the inclusion of a predetermined amount of cyclic olefin resin (A) having predetermined structural units. On the other hand, when olefin resins that do not have the predetermined structural units, such as norbornene copolymer or polypropylene, were used, it was confirmed that the high-temperature heat resistance was inferior, as shown in Comparative Examples 1 and 2. This is thought to be due to compatibility problems with the curable compound (B) caused by differences in the resin structure. Furthermore, Comparative Example 3 lacked proper control of resin polarity and exhibited inferior low dielectric properties.

[0086] As shown in the comparison between Example 2 and Examples 6-8, Example 3 and Examples 9-11 and 25-27, Example 4 and Examples 12-14, and Examples 2, 3, and 15 and Examples 16 and 17, it was confirmed that high-temperature heat resistance is improved when the amount of carbon-carbon double bonds is 6 mmol / g or less. As shown in the comparison between Examples 2 and 3 and Examples 18-20, it was confirmed that high-temperature heat resistance is improved when the cyclic olefin resin (A) has a constituent unit derived from at least one selected from maleic acid derivatives and maleimide derivatives.

[0087] As shown in the comparison between Example 2 and Examples 21-23, it was confirmed that the high-temperature heat resistance of the cyclic olefin resin (A) was improved by having a curable epoxy structure. This is presumed to be due to an improved degree of crosslinking.

[0088] As shown in the comparison between Examples 2 and 3 and Examples 31 and 32, it was confirmed that the high-temperature heat resistance improved as the proportion of curable compound (B) increased. This is presumed to be due to an increase in the crosslinking density in the resin composition.

[0089] This application claims priority based on Japanese Patent Application No. 2024-158052, filed on 12 September 2024, and incorporates all of its disclosures herein.

Claims

1. A resin composition comprising a cyclic olefin resin (A) having constituent units derived from at least one selected from α-pinene, β-pinene, α-phellandrene, and β-phellandrene, and a curable compound (B), wherein the content of the cyclic olefin resin (A) is 0.5 to 50% by mass based on the total solid content in the resin composition.

2. The resin composition according to claim 1, wherein the cyclic olefin resin (A) has a total of 30 to 100 mol% of constituent units derived from at least one selected from α-pinene, β-pinene, α-phellandrene, and β-phellandrene, based on the total constituent units.

3. The resin composition according to claim 1, wherein the cyclic olefin resin (A) further comprises a constituent unit derived from at least one selected from maleic acid derivatives and maleimide derivatives.

4. The resin composition according to claim 1, wherein the cyclic olefin resin (A) has constituent units derived from β-pinene.

5. The resin composition according to claim 1, wherein the cyclic olefin resin (A) has a number average molecular weight of 5,000 to 100,000.

6. The resin composition according to claim 1, wherein the curable compound (B) comprises at least one selected from maleimide resin, epoxy resin, cyanate ester resin, allyl group-containing compound, vinyl group-containing compound, and (meth)acrylate group-containing compound.

7. A cured product obtained by curing the resin composition described in claim 1.

8. A dry film comprising the resin composition described in claim 1.

9. A film obtained by curing the dry film described in claim 8.

10. A laminated sheet comprising a resin layer formed on a substrate using the resin composition described in claim 1.

11. A prepreg comprising a fibrous substrate impregnated with the resin composition described in claim 1.

12. A printed circuit board comprising an electrical insulating layer formed from at least one selected from the dry film described in claim 8, the film described in claim 9, and the prepreg described in claim 11, and a conductor layer provided on the electrical insulating layer.

13. An electronic device comprising a printed circuit board as described in claim 12.

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