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

Abstract

To provide 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 wiring board, and electronic device formed using the resin composition that achieve both low dielectric properties and high-temperature heat resistance. [Solution] The above problem is solved by 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.

Description

[Technical Field]

[0001] This disclosure relates to a resin composition that achieves both low dielectric properties and high-temperature heat resistance, and to a cured product, dry film, film, laminated sheet, prepreg, printed circuit board, and electronic equipment formed using the resin composition that achieve both low dielectric properties and high-temperature heat resistance. [Background technology]

[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 material 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 (hereinafter also referred to as low dielectric property). Furthermore, when used in semiconductor material applications, processes such as solder reflow may be required, and high-temperature resistance, for example, of 240°C or higher, is necessary.

[0003] As materials with excellent low dielectric properties, cyclic olefin resins having an alicyclic skeleton within the molecule 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. Furthermore, Patent Document 3 describes the use of cyclic olefin resins obtained by polymerizing terpene-based compounds. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 98 / 56011 [Patent Document 2] Japanese Patent Publication No. 2005-103949 [Patent Document 3] Japanese Patent Publication No. 2008-208349 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, norbornene-based polymers described in Patent Documents 1 and 2, while exhibiting excellent low dielectric properties, may have insufficient heat resistance. Therefore, polymers generally use those containing 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. Furthermore, while the cyclic olefin resin obtained by polymerizing the terpene compound described in Patent Document 3 has excellent dielectric properties, it may deform or foam during high-temperature processes such as solder reflow, and suffers from insufficient high-temperature heat resistance. Therefore, the object of the present invention 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 wiring board, and electronic device formed using the resin composition that achieve both low dielectric properties and high-temperature heat resistance. [Means for solving the problem]

[0006] <1> The present invention relates to a resin composition comprising 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), 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 present invention relates to a cyclic olefin resin (A) having 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. <1> This relates to the resin composition described above. <3> The present invention relates to a cyclic olefin resin (A) further comprising a constituent unit derived from at least one selected from maleic acid derivatives and maleimide derivatives. <1> or <2> This relates to the resin composition described above. <4> The present invention relates to a cyclic olefin resin (A) having constituent units derived from β-pinene. <1> ~ <3> This relates to the resin composition described in any one of the items. <5> The present invention relates to a cyclic olefin resin (A) having a number average molecular weight of 5,000 to 100,000. <1> ~ <4> This relates to the resin composition described in any one of the items. <6> The present invention relates to a curable compound (B) comprising 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. <1> ~ <5> This relates to the resin composition described in any one of the items. <7> The present invention <1> ~ <6> This relates to a cured product obtained by curing a resin composition described in any one of the items. <8> The present invention <1> ~ <6> This relates to a dry film comprising the resin composition described in any one of the items. <9> The present invention <8> This relates to a film obtained by curing the dry film described above. <10> On the substrate, <1> ~ <6> The present invention relates to a laminated sheet comprising a resin layer formed from the resin composition described in any one of the items. <11> This invention relates to a fibrous substrate, <1> ~ <6> This relates to a prepreg impregnated with any one of the resin compositions described in item 1. <12> The present invention <8> The dry film described above, <9> The film described above, and <11> The present invention relates to a printed wiring board comprising an electrical insulating layer formed from at least one prepreg selected from those described above, and a conductor layer provided on the electrical insulating layer. <13> The present invention relates to an electronic device including a printed wiring board described in <12>.

Effects of the Invention

[0007] According to the present invention, it is possible to provide a resin composition that achieves both low dielectric properties and high heat resistance at high temperatures, as well as a cured product, dry film, film, laminated sheet, prepreg, printed wiring board, and electronic device that are formed using the resin composition and achieve both low dielectric properties and high heat resistance at high temperatures.

Embodiments for Carrying Out the Invention

[0008] <Resin Composition> The resin composition of the present invention contains a cyclic olefin resin (A) having a structural unit derived from at least one selected from α-pinene, β-pinene, α-felandrene, and β-felandrene, and a curable compound (B), and 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 containing a cyclic olefin resin (A) having the above specific structural unit in a predetermined range, the low-polarity structure in the present resin composition increases, the dielectric tangent of the present resin composition sufficiently decreases, and excellent low dielectric properties are exhibited. In addition, the compatibility with the curable compound (B) is maintained, deformation at high temperatures is suppressed, and high heat resistance is exhibited. Furthermore, α-pinene, β-pinene, α-felandrene, and β-felandrene are biomass raw materials derived from plants, and the use of a cyclic olefin resin using such raw materials is also useful from the viewpoints of achieving carbon neutrality and a recycling-based society. Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and embodiments implemented within a range not changing the gist of the present invention are also included.

[0009] <Cyclic Olefin Resin (A)> The cyclic olefin resin (A) has a structural unit derived from at least one selected from α-pinene, β-pinene, α-felandrene, and β-felandrene. The cyclic olefin resin (A) can be obtained by polymerizing a monomer containing at least one selected from α-pinene, β-pinene, α-felandrene, and β-felandrene. The polymerization method for obtaining the cyclic olefin resin (A) is not particularly limited, and it can be appropriately selected from known polymerization methods such as cationic polymerization using a Lewis acid and coordination polymerization using a metal complex.

[0010] Examples of the cyclic olefin resin (A) include, for example, a homopolymer of α-pinene, β-pinene, α-felandrene, or β-felandrene, or a copolymer obtained by arbitrarily combining these, or a copolymer of at least one monomer selected from α-pinene, β-pinene, α-felandrene, and β-felandrene and another monomer, and a modified product of these homopolymers or copolymers. Among them, from the viewpoints of low dielectric properties and polymerization stability, the cyclic olefin resin (A) preferably has a structural unit derived from β-pinene.

[0011] Examples of the monomer copolymerizable with the above α-pinene, β-pinene, α-felandrene, and β-felandrene include, for example, 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 methyl styrene; maleimide monomers such as cyclohexyl maleimide and phenyl maleimide; and maleic anhydride. Among them, from the viewpoint of thermal stability, the cyclic olefin resin (A) preferably contains a structural unit derived from at least one selected from maleic acid derivatives and maleimide derivatives. From the viewpoint of achieving both copolymerizability and low dielectric properties, the total content of the structural units derived from maleic acid derivatives and maleimide derivatives is preferably 0.1 to 67 mol% based on all the structural units, more preferably 50 to 67 mol%.

[0012] 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 further improves low dielectric properties, high temperature heat resistance, and compatibility with the curable compound (B).

[0013] 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.

[0014] From the viewpoint of thermal stability, 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. For example, it may be 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, in the case of 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 cyclic olefin resin (A) can be determined by iodine titration or, 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 denaturation 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.

[0015] 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. By having a number-average molecular weight within the above range, the mobility of the resin itself can be suppressed while maintaining compatibility with the curable compound (B), thereby suppressing deformation at high temperatures.

[0016] <Curable compound (B)> The resin composition of the present invention 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.

[0017] [Maleimide resin] Examples of maleimide resins include 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 (CASNO: 67784- 74-1, Reaction product of a polymer consisting of formaldehyde and aniline with 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'-pentamethylene 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 '-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'-[ethylenebis(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)]bismaleimide, N,N'-[1,3,4-oxadiazole-2,5-diylbis(4,1-phenylene)]bismaleimide, 2,6-bis[4-(maleimino [do-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'-[hexafluoroisopropylidenebis[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'-[cyclohexyllidenebis(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-f Examples of polyfunctional maleimides include [phenylene]bismaleimide, N,N'-(oxybisethylene)bismaleimide, N,N'-[dithiobis(m-phenylene)]bismaleimide, N,N'-(3,6,9-trioxaundecane-1,11-diyl)bismaleimide, N,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 Corporation.

[0018] [Epoxy resin] 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.

[0019] [Cyanate ester resin] 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.

[0020] [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.

[0021] [Vinyl group-containing compound] 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.

[0022] 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.

[0023] [(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.

[0024] 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.

[0025] 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 adduct, (meth)acrylate of nonylphenol alkylene oxide adduct, 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.

[0026] 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.

[0027] 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 the present invention is 0.5 to 50% by mass, based on the total solid content in the resin composition. By keeping 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. The content of the cyclic olefin resin (A) is preferably 5% by mass or more, more preferably 10% by mass or more, from the viewpoint of low dielectric properties. Furthermore, from the viewpoint of high-temperature heat resistance, it is preferably 30% by mass or less, more preferably 20% by mass or less.

[0028] From the viewpoint of low dielectric properties and high-temperature heat resistance, the resin composition of the present invention preferably contains 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.

[0029] [solvent] The resin composition of the present invention 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. Examples include aliphatic hydrocarbon compounds or alicyclic hydrocarbon compounds, and among these, hexane, cyclohexane, and methylcyclohexane can be suitably used, from the viewpoint of solubility of cyclic olefin resins.

[0030] [Other ingredients] The resin composition of the present invention may also contain other components such as a non-curable polymer, a curing initiator or catalyst, etc. Examples of non-curing polymers include polybutadiene, polyisoprene, butadiene styrene copolymers and their hydrogenated derivatives, and polyphenylene ethers. Examples of initiators that promote curing include radical polymerization initiators for promoting the curing of maleimide resins, allyl group-containing compounds, and vinyl group-containing compounds. Examples of such radical polymerization initiators include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-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 imidazole-based catalysts that promote the curing of maleimide resins and epoxy resins. Examples of such imidazole-based catalysts include 2-methylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole.

[0031] <Use of resin composition> [Cured products, dry films, films, resin sheets, prepregs] The resin composition of the present invention exhibits excellent low dielectric properties and high-temperature heat resistance, and can be used, for example, for adhesive layer formation, and for forming insulating layers on 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 (i.e., a cured film) obtained by curing the dry 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, at 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 produced by the above method with a substrate. The resin sheet may be pressed and / or heat-cured as needed. Furthermore, an electrical insulating layer containing the cured product may be laminated to a substrate having a conductive layer on its surface.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] <Electronic equipment> A printed wiring board can be obtained by providing a conductive layer on an electrical insulating layer formed from at least one selected from the group consisting of dry film, film, and prepreg of the present invention. A printed wiring board can be manufactured, for example, by forming an electronic circuit on a metal foil layer of a resin sheet comprising a cured resin product formed from a resin composition on metal foil. Furthermore, by mounting electronic components such as semiconductor elements on a printed circuit board, it can be used as an electronic device. Examples of such electronic devices include servers, routers, GPS antennas, antennas for wireless base stations, millimeter-wave antennas, RFID antennas, mobile phones, smartphones, PHS devices, PDAs, tablet devices, personal computers, televisions, digital cameras, digital video cameras, POS terminals, wearable devices, digital media players, electronic control systems, in-vehicle communication equipment, car navigation equipment, millimeter-wave radar, in-vehicle camera modules, semiconductor testing equipment, and high-frequency measuring equipment. [Examples]

[0036] The present invention will be described in more detail below with reference to examples, but these examples do not limit the scope of the present invention in any way. In the examples and comparative examples, "parts" and "%" refer to "parts by mass" and "mass%" respectively, unless otherwise specified. A mole represents the amount of substance, and mol% represents the proportion of the amount of substance in the total monomer.

[0037] <Method for measuring number-average molecular weight (Mn) and mass-average molecular weight (Mw)> The number-average molecular weight of cyclic olefin resin (A) and the mass-average molecular weight (Mw) of vinyl group-containing compound V1 were measured using gel permeation chromatography (GPC) on a standard polystyrene basis. The following conditions were used for the measurement equipment and conditions. Other matters were based on JIS K7252-1~4:2008. (conditions) Column: A combination of TOSOH TSKgelSuperHZM-H, TOSOH TSKgelSuperHZ4000, and TOSOH TSKgelSuperHZ2000. Carrier: Tetrahydrofuran Measurement temperature: 40℃ Carrier flow rate: 1.0 mL / min Sample concentration: 0.1% by mass Detector: RI (refractive index) detector Injection volume: 0.1mL <Method for measuring the amount of carbon-carbon double bonds> Using tetralin as the standard substance, 1 The amount of carbon-carbon double bonds in cyclic olefin resin (A) was determined by comparing the area of ​​the peak derived from the aromatic ring proton of tetralin (approximately 7 ppm) and the area of ​​the peak derived from the double bond proton of cyclic olefin resin (A) (approximately 5 ppm) in the 1H-NMR spectrum. The tetralin and cyclic olefin resin (A) were accurately weighed and dissolved in deuterated chloroform. 1 ¹H-NMR measurements were performed. The value of the carbon-carbon double bond can be determined using Equation 1 below.

number

[0038] <Manufacturing of cyclic olefin resin (A)> [Manufacturing 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 atmosphere. 40 mL (40 mmol) of n-hexane solution of ethylaluminum dichloride and 260 mL of methylene chloride (in this example, a reagent from Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated with molecular sieve 3A, was used) were added, stirring was started, and the mixture was cooled to -30°C in a condenser. Next, 64 mL (450 mmol) of β-pinene (in this example, a reagent from Merck KGaA, purified by simple distillation, was used) was added, and the mixture was stirred for another 30 minutes. Then, 100 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 aqueous hydrochloric acid solution and aqueous sodium hydroxide solution. The resulting organic layer was added to 3000 mL of methanol, and the precipitate was filtered and dried to obtain cyclic olefin resin (A1). The number-average molecular weight of the obtained resin was 5,200.

[0039] [Manufacturing 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 replaced with 110 mL of methylcyclohexane (in this example, a reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. and dehydrated with molecular sieve 3A was used) and 150 mL of methylene chloride, and the cooling temperature of the condenser was changed from -30°C to -78°C. The number-average molecular weight Mn of the obtained resin was 11,200.

[0040] [Manufacturing 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 an 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 condenser was changed from -30°C to -78°C. The number-average molecular weight of the obtained resin was 29,600.

[0041] [Manufacturing 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 atmosphere. 7 mL of 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 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. Finally, the reaction mixture was separated and washed once each with aqueous hydrochloric acid solution and aqueous sodium hydroxide 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.

[0042] [Manufacturing 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.

[0043] [Manufacturing 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 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, revealed that the hydrogenation rate of the obtained resin was 50%. The number-average molecular weight of the obtained resin was 10,700.

[0044] [Manufacturing 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.

[0045] [Manufacturing 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. 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 10,200.

[0046] [Manufacturing Example 9] Hydrogenated Cycloolefin 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.

[0047] [Manufacturing 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.

[0048] [Manufacturing 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.

[0049] [Manufacturing 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.

[0050] [Manufacturing 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.

[0051] [Manufacturing 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.

[0052] [Manufacturing Example 15] Cyclic Olefin Resin (A15) 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.

[0053] [Manufacturing Example 16] Cyclic Olefin Resin (A16) 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.

[0054] [Manufacturing 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, and the solvent was removed by vacuum drying to obtain the hydrogenated cyclic olefin resin (A17). 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 17,900.

[0055] [Manufacturing 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, with stirring 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 a cyclic olefin resin (A18). The number-average molecular weight of the obtained resin was 11,900.

[0056] [Manufacturing 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.

[0057] [Manufacturing Example 20] Hydrogenated Cyclic Olefin Resin (A20) 10 g of the 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 a 100% hydrogenation rate of the obtained resin. The number-average molecular weight of the obtained resin was 24,200.

[0058] [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 intervals of 5 minutes. 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 27% as determined from the decrease in the double bond protons (at about 5 ppm) of the β-pinene polymer by H-NMR spectrum. The number average molecular weight of the obtained resin was 12,200.

[0059] [Production Example 22] Epoxidized Cyclic Olefin Resin (A22) An epoxidized cyclic olefin resin (A22) was obtained in the same manner as in 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.

[0060] [Production Example 23] Epoxidized Cyclic Olefin Resin (A23) An epoxidized cyclic olefin resin (A23) was obtained in the same manner as in 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 (at about 5 ppm) could not be confirmed from the H-NMR spectrum, and the epoxidation rate of the obtained resin was 100%. The number average molecular weight of the obtained resin was 12,200.

[0061] [Production Example 24] Epoxidized Cyclic Olefin Resin (A24) An epoxidized cyclic olefin resin (A24) was obtained in the same manner as in 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.

[0062] [Manufacturing 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 atmosphere. 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 the vessel, 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 a silane-treated cyclic olefin resin (A25). 1 No double-bonded proton peaks (approximately 5 ppm) were observed in 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.

[0063] [Manufacturing Example 26] Brominated Cycloolefin 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. The mixture was then cooled 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 the mixture was stirred for a further 3 hours. Afterward, the mixture was returned to room temperature, and 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 a 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.

[0064] [Manufacturing 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 the vessel, 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. Afterward, the mixture was returned to room temperature, and 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 a cyclopropanetized cyclic olefin resin (A27). The cyclopropane content 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.

[0065] [Manufacturing 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.

[0066] [Manufacturing 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.

[0067] [Manufacturing Example 30] Cyclic Olefin Resin (A30) The reaction was carried out in the same manner as in Production Example 1, except that β-pinene was replaced with β-phellandrene, to obtain a cyclic olefin resin (A30). The number-average molecular weight of the obtained resin was 12,000.

[0068] [Table 1]

[0069] <Manufacturing of vinyl group-containing compounds> [Production Example 31] Vinyl group-containing compound V1 Vinyl group-containing compound V1 was synthesized according to the description in Example 3 of 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 reaction was allowed to proceed for 1.5 hours. After stopping the reaction by adding 171 ml of 7% sodium bicarbonate aqueous solution to the polymerization solution, the aqueous phase was removed by liquid-liquid extraction, and another 171 ml of 7% sodium bicarbonate aqueous solution was added 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.

[0070] <Manufacturing of resin compositions> [Example 1] Resin composition C1 A resin composition C1 was obtained by mixing 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 as other components.

[0071] [Examples 2-90, Comparative Examples 1-3] Resin compositions C2-C90, C ratio 1-C ratio 3 Resin compositions C2 to C90 and C ratios 1 to C3 were obtained in the same manner as in Example 1, except that the compounding compositions were changed as shown in Tables 2 to 5.

[0072] <Evaluation of resin compositions> Using the obtained resin composition, laminated sheets and copper-clad laminates were obtained as follows. [Fabrication of laminated sheets] The obtained resin composition was coated onto a polyethylene terephthalate (PET) substrate to a thickness of 100 μm after drying, 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 100°C under reduced pressure at 20 MPa for 2 hours. 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.

[0073] [Fabrication of copper-clad laminates] The obtained resin composition was coated onto a release film to a thickness of 50 μm after drying, and dried in an oven at 80°C for 30 minutes. The release film was peeled off the resulting laminate, and the obtained resin composition film was sandwiched between the roughened surfaces of two copper foils (F2-WS (thickness 18 μm)), pressed at 20 MPa under reduced pressure at 200°C for 2 hours to obtain a copper-clad laminate having a resin layer formed by the resin composition.

[0074] (Evaluation of low dielectric properties) The obtained laminated sheets were evaluated using the cavity resonator method with a dielectric constant measuring device (manufactured by AET Co., Ltd.) under conditions of 23°C and 50% relative humidity, to determine the dielectric loss tangent at a measurement frequency of 10 GHz, and were evaluated according to the following criteria. S: Dielectric loss tangent is less than 0.001 A: Dielectric loss tangent is 0.001 or greater, and less than 0.002. B: Dielectric loss tangent is 0.002 or greater, and less than 0.003. C: Dielectric loss tangent is 0.003 or greater, and less than 0.004. D: Dielectric loss tangent is 0.004 or greater, and less than 0.005. E: Dielectric loss tangent is 0.005 or higher: Target not met

[0075] (High temperature heat resistance) The obtained copper-clad laminates were 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 pieces was visually observed to check for any adhesion abnormalities such as foaming, lifting, or peeling of the hardened adhesive layer. 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 condition A above. No change in appearance even when suspended in molten solder at 280°C. C: Does not satisfy conditions A and B above. No change in appearance even when suspended in molten solder at 260°C. D: Does not satisfy the above conditions A-C. No change in appearance even when suspended in molten solder at 240°C. E: Appearance changes when suspended in molten solder at 240℃: Target not met

[0076] [Table 2]

[0077] [Table 3]

[0078] [Table 4]

[0079] [Table 5]

[0080] The abbreviations used in Tables 2-5 are shown below. <Resin> Resin 1: Norbornene copolymer (TOPAS 5013l-10, manufactured by Mitsui Chemicals, Inc.) Resin 2: Polypropylene (Isotactic polypropylene Mn5000, manufactured by Merck KGaA)

[0081] <Curable compound> BMI-TMH: 1,6'-bismaleimide-(2,2,4-trimethyl)hexane (manufactured by Yamato Chemical Industries, Ltd.) SA9000: End-terminated methacrylate polyphenylene ether (manufactured by Saudi Basic Industries Corporation) OPE-2st: Vinyl polyphenylene ether at both ends (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.)

[0082] <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.)

[0083] According to Tables 2-5, the resin composition of the present invention achieves 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, Comparative Examples 1 and 2, which used olefin resins that do not have the specified structural units, such as norbornene copolymer or polypropylene, exhibited poor high-temperature heat resistance. This is thought to be due to compatibility issues with the curable compound (B) caused by differences in the resin structure. Furthermore, Comparative Example 3 lacked proper control of resin polarity and exhibited poor dielectric properties.

[0084] Comparisons between Example 2 and Examples 6-8, between Example 3 and Examples 9-11 and 25-27, between Example 4 and Examples 12-14, and between Examples 2, 3, and 15 and Examples 16 and 17 demonstrate that high-temperature heat resistance is improved when the carbon-carbon double bond content is 6 mmol / g or less. A comparison of Examples 2 and 3 with Examples 18 to 20 shows that the high-temperature heat resistance of the cyclic olefin resin (A) is improved by having a constituent unit derived from at least one selected from maleic acid derivatives and maleimide derivatives.

[0085] A comparison of Example 2 with Examples 21-23 showed that the cyclic olefin resin (A) exhibits improved high-temperature heat resistance due to its curable epoxy structure. This is presumed to be due to an improved degree of crosslinking.

[0086] A comparison of Examples 2 and 3 with Examples 31 and 32 showed that increasing the proportion of curable compound (B) improved high-temperature heat resistance. This is presumed to be due to an increase in the crosslinking density in the resin composition.

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 wiring 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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