Modified olefin copolymer, resin composition, laminated sheet, prepreg, cured product, substrate with cured product, and electronic device

Abstract

The invention provides a modified olefin copolymer, a resin composition, a laminated sheet, a prepreg, a cured product, a substrate with the cured product, and an electronic device. The modified olefin copolymer has excellent dielectric properties, heat resistance, and crack resistance. A modified olefin-based copolymer in which the main chain contains a structural unit derived from a conjugated diene compound and / or a structural unit derived from an alicyclic or chain-like non-conjugated olefin compound, and which has a monocyclic structure and / or a polycyclic structure in at least one of the pendant group, the side chain and the molecular chain end, a ring of a monocyclic structure and / or a ring of a polycyclic structure is an alicyclic skeleton containing a carbon atom and / or an alicyclic skeleton containing a carbon atom and a heteroatom, and has a radical-reactive non-conjugated carbon-carbon unsaturated bond.

Description

Technical Field

[0001] The present disclosure relates to a modified olefin-based copolymer, a resin composition, a laminated sheet, and a prepreg. Furthermore, the present disclosure relates to a cured product obtained from the resin composition, a substrate with a cured product formed by curing the resin composition, and an electronic device equipped with the substrate with the cured product. Background Art

[0002] Resin compositions or cured products of resin compositions can be used in various components of electronic parts. For example, resin compositions or cured products thereof can be used as interlayer insulating layers between conductor layers of a multilayer printed wiring board. In addition, prepregs formed by impregnating glass cloth with a resin composition can be used as insulating layers on conductor layers of a printed wiring board. In addition, insulating resin compositions or cured products thereof can be used as sealing resins in semiconductor packaging.

[0003] As such a resin composition, for example, Patent Document 1 discloses a resin composition comprising: a maleimide compound (A) having two or more N-substituted maleimide groups; a polyphenylene ether (B); and a copolymer (C) having structural units derived from a styrene-based compound, structural units derived from maleic anhydride, and structural units derived from an N-substituted maleimide. Furthermore, Patent Document 2 discloses a thermosetting cyclic imide resin composition comprising (A) a styrene-based elastomer, (B) a cyclic imide compound having a specific structure, (C) an epoxy resin, and (D) a reaction accelerator in specific proportions. Furthermore, Patent Document 3 discloses a thermoplastic elastomer comprising side chains containing a hydrogen-bonding crosslinking site having a specific structure, and other side chains containing a covalently bonded crosslinking site. Patent Document 4 discloses a thermoplastic elastomer composition comprising the following substances in specific proportions: at least one elastomeric component selected from the group consisting of an elastomeric polymer (A) having a side chain (a) containing a hydrogen-bonding crosslinking site having a specific structure and a Tg of 25°C or less; and an elastomeric polymer (B) containing a hydrogen-bonding crosslinking site and a covalently bonded crosslinking site in its side chain and a Tg of 25°C or less; clay; and an α-olefin-based resin having no chemically bonded crosslinking site.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2020-169276

[0007] Patent Document 2: Japanese Patent Application Laid-Open No. 2022-111423

[0008] Patent Document 3: Japanese Patent Application Laid-Open No. 2006-131663

[0009] Patent Document 4: International Publication No. 2017 / 047274 Summary of the Invention

[0010] Problems to be solved by the invention

[0011] Along with the high functionalization development of electronic equipment, day by day need the reliability of the electronic components built in the equipment.In resin combination and hardener thereof, also require a kind of material not only with excellent heat resistance but also obtain excellent anti-cracking property after thermal cycle test.And then, need a kind of low dielectric constant, low dielectric loss tangent material, it also can cope with the frequency band of the signal used in the printed wiring board used in electronic equipment, communication equipment etc., i.e., gigahertz band.On the market, need can realize the resin and the resin combination of the raising of the anti-cracking property after thermal cycle test while meeting these two characteristics of dielectric properties and heat resistance.

[0012] The present disclosure has been made in view of the above background, and its purpose is to provide a modified olefin-based copolymer and a resin composition having excellent dielectric properties and heat resistance and further excellent crack resistance after thermal cycle testing, as well as a laminated sheet, a prepreg, a cured product, a substrate with a cured product, and an electronic device formed using the resin composition.

[0013] Technical means to solve the problem

[0014] As a result of diligent research, the present inventors have found that the problems of the present disclosure can be solved by the following aspects, and have completed the present disclosure.

[0015] [1]: A modified olefin-based copolymer, wherein the main chain comprises structural units derived from a conjugated diene compound and / or structural units derived from an alicyclic or chain-like non-conjugated olefin compound, wherein:

[0016] At least any one of the side group, the side chain and the molecular chain terminal has a monocyclic structure and / or a polycyclic structure,

[0017] The ring of the monocyclic structure and / or any ring of the polycyclic structure is at least one of an alicyclic skeleton containing carbon atoms and an alicyclic skeleton containing carbon atoms and heteroatoms, and satisfies at least one of the following (i) and (ii).

[0018] (i) The alicyclic skeleton has a radical-reactive non-conjugated carbon-carbon unsaturated bond.

[0019] (ii) The carbon atoms constituting the alicyclic skeleton and the carbon atoms not constituting the ring bonded to the carbon atoms are bonded via a radically reactive non-conjugated carbon-carbon unsaturated bond.

[0020] [2]: The modified olefin-based copolymer according to [1], wherein the main chain has substantially no unsaturated bonds except at the molecular chain terminals.

[0021] [3]: The modified olefin-based copolymer according to [1] or [2], wherein the main chain contains a structural unit derived from an aromatic vinyl compound.

[0022] [4]: The modified olefin-based copolymer according to any one of [1] to [3], comprising a block comprising a structural unit derived from an aromatic vinyl compound and a block comprising a structural unit derived from a conjugated diene compound.

[0023] [5]: The modified olefin-based copolymer according to [4], wherein the block comprising the structural unit derived from the conjugated diene compound further comprises a structural unit derived from an aromatic vinyl compound.

[0024] [6]: The modified olefin-based copolymer according to any one of [1] to [5] is a modified product of any one of the hydrogenated styrene-based elastomers selected from the group consisting of styrene-ethylene / butylene block copolymer (SEB), styrene-ethylene / propylene block copolymer (SEP), styrene-ethylene / butylene-styrene block copolymer (SEBS), styrene-ethylene / propylene-styrene block copolymer (SEPS), styrene-ethylene / butylene / styrene-styrene block copolymer (SEBSS), styrene-isobutylene-styrene block copolymer (SIBS), and styrene-ethylene-ethylene / propylene styrene block copolymer (SEEPS).

[0025] [7]: A resin composition comprising the modified olefin-based copolymer according to any one of [1] to [6].

[0026] [8]: The resin composition according to [7] further comprises a curable compound, wherein the curable compound comprises at least one selected from the group consisting of an epoxy compound (b1), a cyanate compound (b2), a maleimide compound (b3), an allyl group-containing compound (b4), a vinyl group-containing compound (b5), a (meth)acrylate group-containing compound (b6), and a benzoxazine compound (b7).

[0027] [9]: The resin composition according to [7] or [8], further comprising an inorganic filler.

[0028]

[10] : A laminated sheet comprising a substrate and a resin composition layer formed on the substrate using the resin composition according to any one of [7] to [9].

[0029]

[11] : A prepreg formed by impregnating a base material with the resin composition according to any one of [7] to [9].

[0030]

[12] : A cured product obtained from the resin composition according to any one of [7] to [9].

[0031]

[13] : A substrate with a cured product, comprising a cured product formed by curing the resin composition according to any one of [7] to [9].

[0032]

[14] : An electronic device equipped with the substrate with a cured material according to

[13] .

[0033] Effects of the Invention

[0034] According to the present disclosure, the following excellent effects are achieved: a modified olefin-based copolymer having excellent dielectric properties and heat resistance and further excellent crack resistance after thermal cycle testing, a resin composition, and a laminated sheet, a prepreg, a cured product, a substrate with a cured product, and an electronic device formed using the resin composition can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] [ Figure 1 ] are the IR spectra of resin R-5, Synthesis Example 5 and Comparative Synthesis Example 5. DETAILED DESCRIPTION

[0036] Hereinafter, the present disclosure will be described in detail. In addition, as long as it complies with the purport of the present disclosure, other embodiments are also included in the scope of the present disclosure. In addition, the numerical range determined by using "to" in this specification includes the numerical values ​​recorded before and after "to" as the range of the lower limit and the upper limit. In addition, in this specification, "film" or "sheet" has the same meaning and is not distinguished according to thickness. In addition, the various components appearing in this specification can be used independently and individually as one, or two or more can be used in combination as long as there are no special annotations. The numerical values ​​recorded in this specification refer to the values ​​obtained by the method described in [Examples] described later.

[0037] 1. Modified olefin copolymers

[0038] In the modified olefin copolymer of the present disclosure (hereinafter also referred to as the present copolymer), the main chain comprises structural units derived from conjugated diene compounds and / or structural units derived from alicyclic or chain-like non-conjugated olefin compounds. From the viewpoint of further improving dielectric properties and heat resistance, it is preferred that the main chain, except for the molecular chain ends, does not substantially have unsaturated bonds. In addition, “substantially not comprising” as referred to herein means that it does not have unsaturated bonds except for those inevitably included. At least any one of the side groups, side chains and molecular chain ends of the present copolymer has a monocyclic structure and / or a polycyclic structure. Moreover, the ring of the monocyclic structure and / or any one of the polycyclic structures is at least any one of an alicyclic skeleton comprising carbon atoms and an alicyclic skeleton comprising carbon atoms and heteroatoms, and satisfies at least any one of the following (i) and (ii). In addition, the so-called skeleton refers to a structure formed by atoms that directly form a ring. For example, in the case of a cycloalkenyl group, the atoms that directly form a ring are carbon atoms and do not contain hydrogen. In the case of a maleimide group, the atoms directly forming the ring are a carbon atom and a heteroatom (nitrogen atom).

[0039] (i) The alicyclic skeleton has a radical-reactive non-conjugated carbon-carbon unsaturated bond.

[0040] (ii) The carbon atoms constituting the alicyclic skeleton and the carbon atoms not constituting the ring bonded to the carbon atoms are bonded via a radically reactive non-conjugated carbon-carbon unsaturated bond.

[0041] The so-called "structural unit derived from an alicyclic or chain-like non-conjugated olefin compound" in the main chain refers to a structure in which the main chain is composed of an aliphatic hydrocarbon that does not have aromaticity (i.e., a π-electron conjugated system). The present copolymer having a structural unit derived from an alicyclic non-conjugated olefin compound has a ring structure in the main chain. In addition, the so-called main chain is a linear molecular chain that becomes a trunk in the polymer constituting the resin, and refers to a chain connected by carbon atoms. Carbon atoms constituting an alicyclic structure containing hydrocarbons may also be included in the main chain. From the viewpoint of dielectric properties, it is preferred that a copolymer having a ring containing a heteroatom (e.g., a ring derived from a maleimide group) in the main chain is not included in the present copolymer. In addition, from the viewpoint of crack resistance after thermal cycling test, a chain structure is more preferred in the main chain skeleton of the present copolymer than an alicyclic structure.

[0042] The "alicyclic skeleton" in the monocyclic structure and / or polycyclic structure located at the side chain, side group or molecular chain end refers to a ring structure such as a cyclic aliphatic hydrocarbon group that does not have aromaticity (i.e., π electron conjugated system). The monocyclic structure and / or polycyclic structure may also have functional groups and / or substituents such as maleimide and carbonyl groups. The so-called "monocyclic structure" refers to a structure having a monocyclic ring. It has one or more monocyclic rings. The so-called "polycyclic structure" refers to a bridged structure (bridgehead structure), a condensed ring structure in which two or more monocyclic rings can share (condense) one of the edges of their respective rings, or a structure formed by combining these. As long as it has a ring containing an alicyclic skeleton, an aromatic ring may also be included in a part of the monocyclic structure or a part of the polycyclic structure. It is preferred that no heterocycle is included.

[0043] The "radical-reactive non-conjugated carbon-carbon unsaturated bond" in (i) and (ii) refers to a bond that can form a covalent bond with another modified olefin copolymer and / or a curable compound through a radical reaction. The radical reaction is initiated, for example, by heating, light irradiation, or electron beam irradiation.

[0044] Due to the aforementioned structure, this copolymer exhibits excellent heat resistance. This is believed to be primarily due to the presence of this alicyclic backbone in at least one of the side groups, side chains, and molecular chain ends, allowing for free radical-reactive non-conjugated carbon-carbon unsaturated bonds to form crosslinked structures during curing, thereby enhancing hardenability. In particular, the presence of this alicyclic backbone in the side chains and / or side groups suppresses steric hindrance, improving reactivity and, consequently, enhancing hardenability.

[0045] In addition, the dielectric properties of the cured product of the resin combination comprising this copolymer are excellent. It is believed that its main reason is caused by: by having this alicyclic skeleton at least any one of side group, side chain and molecular chain end, and comprising the structural unit in conjugated diene compound source and / or the structural unit in alicyclic or chain-like non-conjugated olefin compound source, compared with the situation of being cross-linked via oxygen atoms or nitrogen atoms (for example, compared with the situation of being hardened using epoxy compounds), cross-linking site is made into carbon-carbon bond, thus polarization can be reduced, and dielectric relaxation is suppressed. In addition, at least any one of side chain, side group and molecular chain end has this alicyclic skeleton, so steric hindrance is few, is rich in reactivity, therefore can reduce the non-conjugated carbon-carbon unsaturated bond remaining after hardening reaction. As a result, the generation of the hydroxyl caused by oxidation and the reduction of the dielectric properties accompanying this can be suppressed.

[0046] In addition, since the cured product of the resin composition comprising this copolymer has the structure, the crack resistance after the thermal cycle test is excellent. It is believed that the main reason is based on the following structure: by setting the main chain as the structural unit derived from the conjugated diene compound and / or the alicyclic or chain-like non-conjugated olefin-based skeleton, while improving flexibility, the carbon-carbon unsaturated bonds of the alicyclic skeleton of at least any one of the side groups, side chains and molecular chain ends are used to construct a cross-linked structure. From the perspective of more effectively improving flexibility, it is preferred that the structural unit derived from the conjugated diene compound and / or the alicyclic or chain-like non-conjugated olefin-based skeleton in which the main chain does not substantially have unsaturated bonds be set as the main chain skeleton.

[0047] 1-1. Main chain skeleton

[0048] The main chain of this copolymer comprises a structural unit derived from a conjugated diene compound and / or a structural unit derived from an alicyclic or chain-like non-conjugated olefin compound. With respect to further improving dielectric properties and heat resistance, it is preferred that the main chain does not substantially have an unsaturated bond except for the molecular chain end. In the case described, when the main chain skeleton has an unsaturated bond remaining, a copolymer having substantially no unsaturated bonds is obtained by hydrogenation (hydrogenation).

[0049] The monomers (hereinafter also referred to as monomers A) used to obtain the structural units derived from the conjugated diene compound constituting the main chain of the copolymer can be appropriately selected from known monomers. Preferred examples include butadiene, isoprene, 2,3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene, farnesene, chloroprene, and mixtures thereof. Of these, butadiene and isoprene are more preferred.

[0050] The monomers (hereinafter also referred to as monomers B) of the structural units of the alicyclic or chain-like non-conjugated olefin compound source for obtaining the main chain constituting this copolymer can be suitably selected from known monomers. As a preferred example, the heteroatom-substituted olefin compounds such as α-olefins such as ethylene, propylene, 1-pentene, 1-hexene, 1-heptene, 1-octene, N-vinyl pyrrolidone, norbornene, norbornadiene and other dicyclic bodies, tricyclic bodies such as dicyclopentadiene or dihydrodicyclopentadiene, tetracyclododecene and other tetracyclic bodies, pentacyclic bodies such as tricyclopentadiene, tetracyclopentadiene and other heptacyclic bodies, derivatives thereof and the like norbornene monomers can be exemplified. Among these, ethylene and propylene are preferred, and ethylene is particularly preferred.

[0051] From the viewpoint of achieving excellent mechanical strength and heat resistance, the copolymer preferably has a structural unit derived from an aromatic vinyl compound in the main chain. The monomer (hereinafter also referred to as monomer C) for obtaining the structural unit derived from an aromatic vinyl compound constituting the main chain of the copolymer can be appropriately selected from known monomers. Preferred examples include methylstyrenes such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene; 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p-methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl-2,4-dimethylstyrene, o-tert-butylstyrene, m-tert-butylstyrene, p-tert-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, indene, vinylnaphthalene, and N-vinylcarbazole. From the perspective of a balance between production cost and physical properties, styrene, α-methylstyrene, p-methylstyrene, and mixtures thereof are preferred, and styrene is more preferred.

[0052] This copolymer may contain other monomers (hereinafter referred to as monomers D) that are copolymerizable with monomers A and B, without departing from the scope of the present disclosure. From the perspective of maintaining good dielectric properties and crack resistance after thermal cycling, it is preferred that the alicyclic structure forming the main chain skeleton does not contain a heterocycle. Specific examples of monomers D include aromatic vinyl compounds such as N-vinylcarbazole, vinylnaphthalene, and vinylanthracene, β-pinene, 8,9-p-menthene, and dipentene.

[0053] This copolymer can be any one of random copolymer, block copolymer, gradient copolymer (gradientcopolymer), but with respect to the viewpoint of taking into account heat resistance and stress relaxation, preferably block copolymer.As a preferred example, with respect to the viewpoint of taking into account heat resistance and stress relaxation, it is possible to illustrate a block copolymer including a structural unit derived from an aromatic vinyl compound, and a structural unit derived from a conjugated diene compound.With respect to the viewpoint of taking into account heat resistance and stress relaxation, the block copolymer is more preferably a structural unit derived from an aromatic vinyl compound at both ends of a block comprising a structural unit derived from a conjugated diene compound. In addition, the main chain of this copolymer is preferably a block as a structural unit derived from an aromatic vinyl compound, comprising a structural unit derived from styrene, and as a block comprising a structural unit derived from a conjugated diene compound, comprising a structural unit derived from butadiene, isoprene.Preferably ABA type triblock copolymer, AB type diblock copolymer, more preferably ABA type triblock copolymer. Preferred examples of block A include monomers derived from styrene, and preferred examples of block B include monomers derived from butadiene and isoprene.

[0054] Preferred examples of the present copolymer include modified products of any one of the hydrogenated styrene-based elastomers styrene-ethylene / butylene block copolymer (SEB), styrene-ethylene / propylene block copolymer (SEP), styrene-ethylene / butylene-styrene block copolymer (SEBS), styrene-ethylene / propylene-styrene block copolymer (SEPS), styrene-ethylene / butylene / styrene-styrene block copolymer (SEBSS), styrene-isobutylene-styrene block copolymer (SIBS), and styrene-ethylene-ethylene / propylene styrene block copolymer (SEEPS).

[0055] Monomer A~monomer D can be used alone or in combination. Monomer A~monomer D can be used alone or in combination. Monomer A~monomer D can be used alone or in combination. Monomer A~monomer D can be used alone or in combination. Monomer A~monomer D can be used alone or in combination. Monomer A~monomer D can be used alone or in combination. Monomer A~monomer D can be used alone or in combination. Monomer A~monomer D can be used alone or in combination. Monomer A~monomer D can be used alone or in combination. Monomer A~monomer D can be used alone or in combination. Monomer A~monomer D can be used alone or in combination. Monomer A~monomer D can be used alone or in combination. With regard to the viewpoint of stress relaxation, in 100% by mass of this copolymer, the total of the structural unit constituting the monomer A source of this copolymer and the structural unit constituting the monomer B source (including the case of having only one of them) is preferably 30% by mass~90% by mass, more preferably 40% by mass~80% by mass, and further preferably 55% by mass~75% by mass. Monomer A~monomer D can be used alone or in combination ... In addition, the above range is the mass % in the olefin-based copolymer before modification.

[0056] 1-2. Side groups, side chains, and molecular chain ends

[0057] At least one of the side groups, side chains, and molecular chain ends of the present copolymer has a monocyclic structure and / or a polycyclic structure (hereinafter also referred to as a ring containing a non-conjugated C=C bond) containing an alicyclic skeleton that satisfies at least one of (i) and (ii). This imparts crosslinking properties to the present copolymer. By crosslinking the present copolymer, in addition to excellent heat resistance, crack resistance after thermal cycling testing can be improved.

[0058] Examples of the monocyclic structure and polycyclic structure having an alicyclic skeleton satisfying the above-mentioned condition (i) include the following chemical formula (1).

[0059] [Chemistry 1]

[0060]

[0061] R in the formula 1 is a direct bond or a methylene group, R 2is hydrogen or methyl. * in the formula represents the bonding site to the main chain or side chain of the modified olefin copolymer. The hydrogen atom bonded to the carbon of the ring may be substituted by a substituent. Examples of the substituent include: alkyl groups having 1 to 18 carbon atoms (methyl, ethyl, isopropyl, tert-butyl, etc.), alkoxy groups having 1 to 18 carbon atoms (methoxy, ethoxy, propoxy, etc.), aryl groups (phenyl, naphthyl, etc.), heteroaromatic groups (thienyl, etc.), halogenated aryl groups (pentafluorophenyl, 3-fluorophenyl, 3,4,5-trifluorophenyl, etc.), alkenyl groups such as vinylidene, alkynyl groups, amide groups, acyl groups, halogenated alkyl groups (perfluoroalkyl, etc.), hydroxyl groups, nitro groups, cyano groups, carboxyl groups, halogenated groups (fluoro, chloro, bromo, etc.).

[0062] Specific examples of the above-mentioned (ii) include groups represented by the following chemical formula (2).

[0063] [Chemistry 2]

[0064]

[0065] R in the formula 1 、R 2 and * in the formula is as described in Chemical Formula (1). In addition, a hydrogen atom bonded to a carbon atom of the ring may be substituted with a substituent, and preferred examples of the substituent include the substituents exemplified in Chemical Formula (1).

[0066] From the perspective of dielectric properties, it is preferred that the alicyclic skeleton having a non-conjugated carbon-carbon unsaturated bond with free radical reactivity that satisfies at least one of (i) and (ii) does not contain heteroatoms such as maleimide groups. From the perspective of dielectric properties, preferred examples of alicyclic skeletons having non-conjugated carbon-carbon unsaturated bonds include norbornene and terpenes (e.g., α-pinene or limonene). If a norbornene group is present, the alicyclic structure does not contain heteroatoms, thereby improving dielectric properties.

[0067] The molecular chain ends of the present copolymer may be structures that substantially all have the present alicyclic skeleton. In addition, a portion of the molecular chain ends may also contain functional groups other than the present alicyclic skeleton. Furthermore, a portion of the molecular chain ends may be chain-capping ends that do not have functional groups. The molecular chain ends of the present copolymer may not have the present alicyclic skeleton, and the side chains and / or side groups of the present copolymer may have the present alicyclic skeleton. At least any one of the molecular chain ends, side chains, and side groups may have the present alicyclic skeleton.

[0068] 1-3. Copolymerization form, weight average molecular weight, etc.

[0069] From the perspective of heat resistance and crack resistance after thermal cycle testing, the present copolymer is preferably a block copolymer. As a preferred example, a block copolymer comprising a block containing a structural unit derived from an aromatic vinyl compound and a block containing a structural unit derived from a conjugated diene compound can be exemplified. In addition, a modified block copolymer comprising a structural unit derived from a conjugated diene compound and further comprising a structural unit derived from an aromatic vinyl compound is also preferred.

[0070] The weight average molecular weight (hereinafter also referred to as Mw) of the present copolymer is not particularly limited. However, from the perspective of achieving better crack resistance after a thermal cycle test, the Mw is preferably 20,000 or greater, more preferably 50,000 or greater, and even more preferably 70,000 or greater. From the perspective of compatibility between the present copolymer and the curable compound, the Mw of the present copolymer is preferably 400,000 or less, more preferably 300,000 or less, and even more preferably 200,000 or less.

[0071] The position of the ring containing the non-conjugated C=C bond of the copolymer can be any of a side group, a side chain, and a molecular chain end, but from the perspective of the manufacturing process, it is preferably a side group or a side chain. The amount of the free radical reactive non-conjugated carbon-carbon unsaturated bond of the copolymer is not particularly limited, but from the perspective of achieving better heat resistance, the free radical reactive non-conjugated carbon-carbon unsaturated bond value of (i) and (ii) is preferably 1 mgKOH / g to 50 mgKOH / g, more preferably 2 mgKOH / g to 35 mgKOH / g, and even more preferably 5 mgKOH / g to 25 mgKOH / g.

[0072] From the perspective of heat resistance and crack resistance after thermal cycle testing, the content of the block containing structural units derived from the aromatic vinyl compound is preferably 10% to 70% by mass relative to 100% by mass of the copolymer, more preferably 20% to 60% by mass, and even more preferably 25% to 45% by mass.

[0073] 1-4. Manufacturing Method

[0074] An example of the manufacture method of this copolymer is described. As the manufacture method of this copolymer, for example, by making the monomer polymerization of at least a conjugated diene compound and / or an alicyclic or chain-like non-conjugated olefin compound obtain the resin (unmodified copolymer) before modification. The polymerization method can be any one of free radical polymerization, anionic polymerization, cationic polymerization, and living polymerization, and known methods can be applied. Unmodified block copolymer is obtained by successively adding monomers. In the case of not substantially comprising the unsaturated double bond of the main chain of the unmodified block copolymer, after polymerization, hydrogenation is carried out using the known methods such as pressurized hydrogen reaction in the presence of a catalyst.

[0075] The method for introducing (modifying) a non-conjugated C=C bond-containing ring into at least one of a side chain, a pendant group, and a molecular chain terminal is preferably a method of producing the copolymer via a reaction step in which a compound capable of introducing a non-conjugated C=C bond-containing ring reacts with an unmodified copolymer. Alternatively, a copolymer having a C=C bond-containing ring in a pendant group may be obtained by partially using a monomer having the non-conjugated C=C bond-containing ring during polymerization of the olefin-based copolymer.

[0076] The introduction of a ring containing a non-conjugated C=C bond into the molecular chain terminal can be achieved by polymerizing an unmodified olefin copolymer and then, if necessary, performing a hydrogenation reaction to react with a compound containing a ring containing a non-conjugated C=C bond. Alternatively, a compound having a functional group can be introduced into the molecular chain terminal of the unmodified olefin copolymer, and the functional group can be reacted with the compound containing a ring containing a non-conjugated C=C bond. For example, acrylic acid can be introduced into the molecular chain terminal. Subsequently, a compound having a functional group reactive with a carboxyl group (e.g., an amino group, an epoxy group, a hydroxyl group) and a monocyclic and / or polycyclic structure containing an alicyclic skeleton satisfying at least one of (i) and (ii) can be reacted to introduce a ring containing a non-conjugated C=C bond into the molecular chain terminal.

[0077] The introduction of cyclic side chains containing non-conjugated C=C bonds can be achieved, for example, by adding a free radical initiator to an unmodified olefin copolymer under heating and grafting an acid anhydride. Examples of compounds capable of introducing an acid anhydride groups include maleic anhydride, citraconic anhydride, and itaconic anhydride. Commercially available products containing these compounds can also be used.

[0078] After introducing an acid anhydride into an unmodified olefin-based copolymer serving as a precursor of the present copolymer, all or part of the acid anhydride is reacted with a compound containing a monocyclic structure and / or a polycyclic structure having an alicyclic skeleton that satisfies at least either one of (i) and (ii), thereby obtaining the present copolymer having a ring containing a non-conjugated C=C bond in the side chain.

[0079] As a compound containing a monocyclic structure and / or a polycyclic structure having an alicyclic skeleton that satisfies at least one of (i) and (ii), the following compounds having a functional group that reacts with carboxylic acid as a substituent can be exemplified. That is, an indene ring having a functional group that reacts with carboxylic acid (amino group, epoxy group, hydroxyl group, etc.) as a substituent; a cycloolefin ring such as cyclohexene; an alkane ring such as 5-methyl-bicyclo[2.2.1]hept-2-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-hexyl-bicyclo[2.2.1]hept-2-ene, 5-decyl-bicyclo[2.2.1]hept-2-ene, 5-cyclohexyl-bicyclo[2.2.1]hept-2-ene, 5-cyclopentyl-bicyclo[2.2.1]hept-2-ene, etc. Alkenyl substituted forms; 5-ethylidene-bicyclo[2.2.1]hept-2-ene (5-ethylidene-2-norbornene), 5-vinyl-bicyclo[2.2.1]hept-2-ene, 5-propenyl-bicyclo[2.2.1]hept-2-ene, 5-cyclohexenyl-bicyclo[2.2.1]hept-2-ene, 5-cyclopentenyl-bicyclo[2.2.1]hept-2-ene and the like; 5-phenyl-bicyclo[2.2.1]hept-2-ene (5-phenyl-2-norbornene), bicyclo[2.2.1]hept-2-ene, tricyclo[4.3.0.1 2,5 ]Deca-3,7-diene, methyl dicyclopentadiene, dimethyl dicyclopentadiene, tetracyclo[9.2.1.0 2,10 .0 3,8 ]Tetradeca-3,5,7,12-tetraene, tetracyclo[10.2.1.0 2,11 .0 4,9 Pentadecano-4,6,8,13-tetraene and the like contain a norbornene ring. Examples include tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, 8-cyclopentyltetracyclododecene, and other unsubstituted or alkyl-containing tetracyclododecenes; 8-methylenetetracyclododecene, 8-ethylidenetetracyclododecene, 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetracyclododecene, 8-cyclopentenyltetracyclododecene, and other tetracyclododecenes having a double bond outside the ring; and 8-phenyltetracyclododecene and other tetracyclododecenes having an aromatic ring. In addition, tetracyclododecenes having a substituent containing an oxygen atom, such as 8-methoxycarbonyltetracyclododecene, 8-methyl-8-methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, and tetracyclododecene-8,9-dicarboxylic anhydride, which have a functional group reactive with carboxylic acid (amino group, epoxy group, hydroxyl group, etc.) as a substituent, can be exemplified.

[0080] Examples of the compound having an amino group and containing a monocyclic structure and / or a polycyclic structure having an alicyclic skeleton satisfying at least either one of (i) and (ii) include the following compound (3).

[0081] [Chemistry 3]

[0082]

[0083] R in the formula 1 、R 2 As shown in the chemical formula (1). 3 is a direct bond or an alkyl group having 1 to 20 carbon atoms. 3 Preferably, it is a direct bond or an alkyl group having 1 to 6 carbon atoms, R 3 More preferably, it is a direct bond or an alkyl group having 1 to 4 carbon atoms. In addition, a hydrogen atom bonded to a carbon atom of the ring may be substituted with a substituent. Examples of the substituent include the substituents exemplified in the description of Chemical Formula (1). As a particularly preferred compound, 5-norbornene-[2-methylamine] can be exemplified.

[0084] After introducing an acid anhydride into an unmodified olefin-based copolymer, all or part of the acid anhydride is reacted with a compound having an amino group and a monocyclic and / or polycyclic structure having an alicyclic skeleton that satisfies at least one of (i) and (ii) to form an imide bond. This imide bond improves compatibility with the maleimide compound (b3) described later as a curable compound, thereby improving crosslinking properties and the heat resistance of the cured product. In other words, from the perspective of the heat resistance of the cured product, a resin composition in which an imide bond is introduced into any of the side chains, side groups, and molecular chain terminals of the present copolymer and the maleimide compound (b3) is used as the curable compound is preferably used.

[0085] The temperature during the reaction of introducing the acid anhydride into the unmodified olefin-based copolymer is preferably 50°C to 200°C, more preferably 100°C to 180°C. The temperature during the reaction with the compound containing a monocyclic structure and / or a polycyclic structure having an alicyclic skeleton after the introduction of the acid anhydride is preferably 80°C to 250°C, more preferably 100°C to 200°C.

[0086] The reaction time for introducing the acid anhydride into the unmodified olefin copolymer is preferably 1 to 240 minutes, more preferably 10 to 180 minutes. The reaction time after the introduction of the acid anhydride with the compound containing a monocyclic structure and / or a polycyclic structure having an alicyclic skeleton is preferably 30 to 240 minutes, more preferably 60 to 180 minutes.

[0087] It is preferable to add an antioxidant when introducing an acid anhydride and introducing the present alicyclic skeleton into the side chain and / or the side group. As the antioxidant, for example, a known antioxidant can be used. Specific examples of the antioxidant include: phenothiazine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine and 3,7-dioctylphenothiazine; bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl), 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy- Hindered phenol compounds such as 3,5-di-tert-butylanilino)-1,3,5-triazine, and pentaerythritol tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate; phenoxazine compounds such as phenoxazine; nitroso compounds or salts thereof such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine; quinone compounds such as methylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, and 4-benzoquinone; phenolic compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol, and tert-butylcatechol.

[0088] Among them, in terms of achieving more excellent effects of the present disclosure, the antioxidant is preferably at least one selected from the group consisting of phenothiazine compounds, hindered phenol compounds, and phenoxazine compounds.

[0089] Examples of catalysts include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine, picoline, and isoquinoline. Examples of dehydrating agents include aliphatic anhydrides such as acetic anhydride and aromatic anhydrides such as benzoic anhydride. Preferred examples of free radical initiators include the compounds described below.

[0090] Examples of organic solvents used in polymerization include N-methyl-2-pyrrolidone (NMP), 2-butanone, dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N,N-diethylacetamide, hexamethylphosphoramide, N-methylcaprolactam, dimethyl sulfate, cyclohexanone, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and cresol. The solvents may be used alone or in combination of two or more. Aromatic hydrocarbons such as xylene and toluene may also be used in combination.

[0091] 2. Resin composition

[0092] The resin composition of this embodiment (hereinafter also referred to as the present composition) contains at least the present copolymer. With this composition, the inter-molecule rings containing non-conjugated C=C bonds of the present copolymer can be cross-linked using a free radical initiator. Furthermore, the present composition may further contain a curing compound. The inclusion of a curing compound allows cross-linking between the non-conjugated C=C bond rings of the present copolymer and the curing compound. The inclusion of a curing compound facilitates control of the crosslink density of the cured product.

[0093] Because this composition has this structure, its cured product exhibits excellent heat resistance. This is believed to be primarily due to the fact that at least one of the side groups, side chains, and molecular chain ends can form a crosslinked structure starting from a non-conjugated carbon-carbon unsaturated bond of an alicyclic skeleton with relatively stable and moderate reactivity, or a non-conjugated carbon-carbon unsaturated bond directly bonded to the alicyclic skeleton. Furthermore, the relatively flexible and tough chain hydrocarbon backbone in the main chain suppresses the reduction in mobility of the copolymer after curing, improving stress relaxation and dispersibility. Furthermore, it is believed that by combining this copolymer, which has a chain hydrocarbon backbone and relatively low-reactivity "non-conjugated carbon-carbon unsaturated bonds derived from an alicyclic structure and free radical reactivity," with a curing compound, a close contrast is easily achieved with the sparse crosslinked structure, thereby improving heat resistance. To further enhance heat resistance, it is preferable to use a saturated hydrocarbon backbone as the main chain.

[0094] In addition, because this composition has described structure, therefore can provide the resin combination of dielectric properties excellence.By using at least any one of side group, side chain and molecular chain end have this alicyclic skeleton and have this copolymer of chain hydrocarbon skeleton in main chain, have this alicyclic skeleton in side chain and / or side group, therefore steric hindrance is few, be rich in reactivity, therefore can reduce the non-conjugated carbon-carbon unsaturated bond remaining after hardening reaction.As a result, can suppress the generation of hydroxyl group caused by oxidation and the reduction of dielectric properties therewith, therefore dielectric properties excellence.Below, each component and manufacture method of this composition are described in detail.

[0095] 2-1. Hardening compound

[0096] The curable compound is a compound that crosslinks and cures by heating, light irradiation, electron beam irradiation, etc., and its type is not particularly limited. In addition to using one type of curable compound alone, two or more types of the same or different types may be used in combination.

[0097] Preferred examples of the curable compound include epoxy compounds (b1), cyanate compounds (b2), maleimide compounds (b3), allyl group-containing compounds (b4), vinyl group-containing compounds (b5), (meth)acrylate group-containing compounds (b6), and benzoxazine compounds (b7) (hereinafter also referred to as components (b1) to (b7)). The curable compound preferably contains one or more compounds selected from the group consisting of components (b1) to (b7).

[0098] The curable compound is preferably a curable compound (B1) containing a radically reactive non-conjugated carbon-carbon unsaturated bond (hereinafter also referred to as a curable compound (B1)). The radically reactive non-conjugated carbon-carbon unsaturated bond refers to a bond that can react with other curable compounds to form a crosslinked structure and / or react with the radically reactive non-conjugated carbon-carbon unsaturated bond of the present copolymer to form a bond. Preferred examples of the curable compound (B1) that is bonded via a radically reactive non-conjugated carbon-carbon unsaturated bond include a maleimide compound (b3), an allyl group-containing compound (b4), a vinyl group-containing compound (b5), and a (meth)acrylate group-containing compound (b6).

[0099] From the viewpoint of further improving heat resistance, it is preferred to include a maleimide compound (b3) as a curing compound. Maleimide compound (b3) can be used alone, or maleimide compound (b3) can be used in combination with one or more of component (b1), component (b2), component (b4) to component (b7). As a preferred combination, it is preferred to use a combination of a cyanate compound (b2) and a maleimide compound (b3), or a combination of a maleimide compound (b3) and at least one of component (b4) to component (b7). Of these, a combination of a maleimide compound (b3) and an allyl-containing compound (b4) is more preferred. In addition, when maleimide compound (b3) and benzoxazine compound (b7) are subjected to a heating reaction and cross-linked for use, the reactivity of maleimide is improved and the dielectric properties are also excellent, so it is particularly preferred.

[0100] From the viewpoint of forming stronger crosslinks by reaction of carbon-carbon unsaturated bonds, preferred are combinations of a maleimide compound (b3) and an allyl group-containing compound (b4), a maleimide compound (b3) and a vinyl group-containing compound (b5), and a maleimide compound (b3) and a (meth)acrylate group-containing compound (b6).

[0101] From the viewpoint of improving toughness, it is preferred to use a curable compound having a polyphenylene ether structure among (b1) to (b7). More preferred are polyphenylene ether compounds having the following general formula (4) in a portion of the structure among the allyl group-containing compound (b4), the vinyl group-containing compound (b5), the (meth)acrylate group-containing compound (b6), and the benzoxazine compound (b7).

[0102] [Chemistry 4]

[0103]

[0104] R 11 、R 12 、R 13 and R 14 Examples that can be independently exemplified in each repeating unit include: a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group which may have a substituent (a linear or branched compound having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a heptyl group, etc., and an alicyclic compound, such as a cyclohexyl group), an alkoxy group which may have a substituent (an alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, a butoxy group, a propoxy group, etc.), an aryl group which may have a substituent (a phenyl group, a naphthyl group, etc.), an amino group which may have a substituent, a carboxyl group, a nitro group, a cyano group, etc.

[0105] From the viewpoint of heat resistance, particularly long-term heat resistance, the average number of curable functional groups in the polyphenylene ether compound is preferably 1 to 10, more preferably 2 or more.

[0106] The Mw of components (b4) to (b7) having a polyphenylene ether structure is not particularly limited, but from the viewpoint of improving crack resistance after a thermal cycle test, it is preferably 200 or greater, and more preferably 500 or greater. The upper limit of Mw is not particularly limited, but is 10,000 or less in consideration of ease of availability, etc.

[0107] The curable compound is preferably used in an amount of 100% by mass of the components other than the filler and the solvent in the present composition, preferably 10% by mass to 98% by mass, more preferably 30% by mass to 90% by mass, and even more preferably 45% by mass to 85% by mass.

[0108] From the perspective of heat resistance, a preferred embodiment includes a curable compound (B1) having a molecular weight of 100 or more and less than 10,000, wherein the curable compound is bonded via a radically reactive non-conjugated carbon-carbon unsaturated bond. Furthermore, in addition to the above embodiment, the heat resistance is further improved by setting the content of the present copolymer to 5% to 40% by mass relative to the total of 100% by mass of the present copolymer and the curable compound (B1).

[0109] The molecular weight of a curable compound refers to the molecular weight of a low-molecular-weight compound or the number-average molecular weight of a compound obtained by polymerizing monomers. When two or more curable compounds are used, the molecular weight of the curable compound is the sum of the molecular weights of the respective curable compounds multiplied by the content (mass %) of the respective curable compounds.

[0110] The epoxy compound (b1) refers to a curable compound having an epoxy group. The epoxy compound (b1) is preferably used in combination with an active ester compound. The so-called active ester compound refers to a compound having one or more ester groups that react with an epoxy group in one molecule and hardens the epoxy resin. Commercially available products of the active ester compound include "HPC-8000-65T", "EXB9416-70BK" and "EXB8100-65T" manufactured by DIC Corporation.

[0111] By using an active ester compound, ester groups are generated by the reaction between the epoxy compound (b1) and the active ester compound. Therefore, the polarity can be reduced compared to the case of using a phenolic hardener. As a result, the dielectric properties can be more effectively improved.

[0112] Specific examples of the epoxy compound (b1) include: glycidyl ether type epoxy resins; glycidylamine type epoxy resins such as tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, triglycidylmetaaminophenol, or tetraglycidylmeta-xylenediamine, sorbitol polyglycidyl ether; glycidyl ester type epoxy resins such as diglycidyl phthalate, diglycidylhexahydrophthalate, or diglycidyltetrahydrophthalate; cyclic aliphatic (alicyclic) epoxy resins such as epoxycyclohexylmethyl-epoxycyclohexanecarboxylate, or bis(epoxycyclohexyl)adipate; bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AD ​​type epoxy resin. Examples include cresol novolac epoxy resins, phenol novolac epoxy resins, α-naphthol novolac epoxy resins, bisphenol A novolac epoxy resins, dicyclopentadiene epoxy resins, tetrabromobisphenol A epoxy resins, and brominated phenol novolac epoxy resins.

[0113] Cyanate compound (b2) refers to a curable resin having a cyanate group. Examples of the cyanate compound (b2) include bisphenol A type cyanate resin, bisphenol A type cyanate, bisphenol F type cyanate resin, bisphenol E type cyanate resin, bisphenol S type cyanate resin, bisphenol sulfide type cyanate resin, phenyl ether type cyanate resin, naphthalene ether type cyanate resin, biphenyl type cyanate resin, tetramethylbiphenyl type cyanate resin, polyhydroxynaphthalene type cyanate resin, phenol novolac type cyanate resin, cresol novolac type cyanate resin, triphenylmethane type cyanate resin, bisphenol A ... Alkane type cyanate ester resin, tetraphenylethane type cyanate ester resin, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolac type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol co-decanoic acid novolac type cyanate ester resin, naphthol-cresol co-decanoic acid novolac type cyanate ester resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type cyanate ester resin, biphenyl modified phenolic acid novolac type cyanate ester resin, anthracene type cyanate ester resin, etc.

[0114] Commercially available products of the cyanate ester compound (b2) include phenol novolac-type cyanate ester resins ("PT-30" and "PT-60" manufactured by Lonza Japan Co., Ltd.), prepolymers obtained by trimerization of bisphenol-type cyanate ester resins ("BA-230S", "BA-3000S", "BTP-1000S" and "BTP-6020S" manufactured by Lonza Japan Co., Ltd.), and the like.

[0115] From the perspective of improving heat resistance and crack resistance after thermal cycle testing, it is preferred to include a maleimide compound (b3) having a molecular weight of 100 or more and less than 10,000. It is believed that by combining such a relatively low molecular weight, highly reactive maleimide compound (b3) with the present copolymer, which has a relatively high molecular weight, relatively low reactivity, and is bonded using non-conjugated carbon-carbon unsaturated bonds with free radical reactivity derived from an alicyclic structure, it is likely that sparsely and densely cross-linked portions are easily generated, effectively improving heat resistance and crack resistance after thermal cycle testing.

[0116] Examples of the maleimide compound (b3) include polyfunctional maleimides obtained by reacting polyfunctional amines with maleic anhydride. Examples of the polyfunctional amine include isophorone diamine, dicyclohexylmethane-4,4'-diamine, Jeffamine D-230, HK-511, D-400, XTJ-582, D-2000, XTJ-578, XTJ-509, XTJ-510, T-403, and T-5000 manufactured by Huntsman Corporation, XTJ-500, XTJ-501, XTJ-502, XTJ-504, XTJ-511, XTJ-512, and XTJ-590, which have a terminally amino-containing ethylene glycol skeleton, and XTJ-542, XTJ-533, XTJ-536, XTJ-548, and XTJ-559, which have a terminally amino-containing polytetramethylene glycol skeleton.

[0117] Examples of the maleimide compound (b3) 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, N,N'-ethylenebismaleimide, N , N'-hexamethylenebismaleimide, bis(4-maleimide phenyl) ether, bis(4-maleimide phenyl) sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, bisphenol A diphenyl ether bismaleimide, resins with two maleimide groups in the molecule, biphenyl aralkyl maleimide, polyphenylmethane maleimide (Chinese Academy of Sciences Sciences, CAS) number (NO): 67784-74-1, polymer containing formaldehyde and aniline, reaction products with maleic anhydride), N,N'-(toluene-2,6-diyl)bismaleimide, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, N,N'-ethylenebismaleimide, N,N'-trimethylenebismaleimide N,N'-propylene bismaleimide, N,N'-tetramethylene bismaleimide, N,N'-pentamethylene bismaleimide, N,N'-(1,3-pentanediyl)bis(maleimide), N,N'-hexamethylene bismaleimide, N,N'-(1,7-heptanediyl)bismaleimide, N,N'-(1,8-octanediyl)bismaleimide, N,N'-(1,9-nonanediyl)bismaleimide, N,N'-(1,10-decanediyl)bismaleimide )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'-[(methyl amino)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"-[nitrotri(ethylene)]trimaleimide, N,N',N"-[nitrotri(4,1-phenylene)] trimaleimide, 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)] bismaleimide, 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 Maleimide, 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-(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-oxaphenanthren-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'-[cyclohexylenebis(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,N'-(ethylenebis-p-phenylene) bismaleimide, BMI-689, BMI-1500, BMI-1700, BMI-3000, BMI-5000, BMI-9000 manufactured by Designer Molecules, and JFE Chemical (JFE Polyfunctional maleimides such as ODA-BMI and BAFBMI manufactured by CHEMICAL.

[0118] When the maleimide compound (b3) is crosslinked by free radicals, a free radical polymerization initiator may be added. Specifically, azo compounds and organic peroxides can be exemplified. The polymerization initiator may be used alone or in combination of two or more.

[0119] Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane 1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane].

[0120] Examples of the organic peroxide include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionyl peroxide, and diacetyl peroxide.

[0121] The allyl group-containing compound (b4) may be monofunctional or polyfunctional. Examples of monofunctional allyl compounds include (meth)allyl alcohol. Examples of polyfunctional allyl compounds include triallyl isocyanurate, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether, tetraallyloxyethane, polyallylsucrose, di(meth)allyl phthalate, tri(meth)allyl isocyanurate, and tri(meth)allyl cyanurate. In addition, the following compounds may be mentioned.

[0122] [Chemistry 5]

[0123]

[0124] The vinyl-containing compound (b5) may be monofunctional or polyfunctional. Examples of monofunctional vinyl compounds include styrene, vinyltoluene, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, and vinylpyridine. Examples of polyfunctional vinyl compounds include vinyl ethers such as hexanediol dinorbornene carboxylate, vinylbenzyl-modified polyphenylene ether, pentaerythritol tetranorbornene carboxylate, triethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, and cyclohexanediol divinyl ether, and divinylbenzene. Among these, vinyl-containing polyphenylene ethers are particularly preferred.

[0125] The (meth)acrylate group-containing compound (b6) may be monofunctional or polyfunctional, and examples thereof include monofunctional (meth)acrylamide compounds, polyfunctional (meth)acrylamide compounds, monofunctional (meth)acrylates, and polyfunctional (meth)acrylates.

[0126] Examples of the monofunctional (meth)acrylamide compound include diacetone (meth)acrylamide, isobutoxymethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, tert-octyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, (meth)acryloylmorpholine, acrylamide-2-methylpropanesulfonic acid, and N-isopropyl (meth)acrylamide.

[0127] Examples of the polyfunctional (meth)acrylamide compound include N,N'-diacryl-4,7,10-trioxa-1,13-tridecanediamine, N,N',N"-triacryloyldiethylenetriamine, N,N',N",N"'-tetraacryloyltriethylenetetramine, and N,N'-{[2-acrylamide-2-[(3-acrylamidopropoxy)methyl]propane-1,3-diylbis(oxy)]bis(propane-1,3-diyl)}diacrylamide.

[0128] Examples of the monofunctional (meth)acrylate 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, cyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dioctyl (meth)acrylate, and dioctyl (meth)acrylate. Cyclopentenyloxyethyl ester, benzyl (meth)acrylate, (meth)acrylate of phenol alkylene oxide adduct, (meth)acrylate of p-cumylphenol alkylene oxide adduct, (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-dioxolane-4-yl)(methyl)acrylate, (2-isobutyl-2-methyl-1,3-dioxolane-4-yl)(methyl)acrylate, (1,4-dioxaspiro[4,5]decane-2-yl)(methyl)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, (3-ethyloxetane-3-yl)(methyl)acrylate, 2-(meth)acryloyloxyethyl isocyanate, allyl (meth)acrylate, N-(meth)acryloyloxyethyl hexa Hydrophthalimide, N-(meth)acryloyloxyethyltetrahydrophthalimide, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethylsuccinic acid, ω-carboxy-polycaprolactone mono(meth)acrylate, 2-(meth)acryloyloxyethyl acid phosphate, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyldimethoxymethylsilane, 3-(meth)acryloyloxypropyltriethoxysilane, 2-(meth)acryloyloxyethyl acid phosphate.

[0129] In the alkylene oxide adducts, examples of the alkylene oxide include ethylene oxide and propylene oxide.

[0130] Examples of the polyfunctional (meth)acrylate include di(meth)acrylates of aliphatic diols such as methacrylate 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;

[0131] Di(meth)acrylates of alicyclic diols such as cyclohexane dimethylol di(meth)acrylate and tricyclodecane dimethylol di(meth)acrylate;

[0132] Alkylene glycol di(meth)acrylates such as diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tripropylene glycol di(meth)acrylate;

[0133] Esterification product of neopentyl glycol, hydroxypivalic acid and (meth)acrylic acid (hereinafter referred to as "hydroxypivalic acid neopentyl glycol di(meth)acrylate"), caprolactone-modified hydroxypivalic acid neopentyl glycol di(meth)acrylate;

[0134] Di(meth)acrylates of alkylene oxide adducts of bisphenol-based compounds, such as di(meth)acrylates of bisphenol A alkylene oxide adducts;

[0135] Di(meth)acrylates of hydrogenated bisphenol-based compounds, such as di(meth)acrylate of hydrogenated bisphenol A;

[0136] Poly(meth)acrylates of isocyanuric acid alkylene oxide adducts such as di(meth)acrylates of isocyanuric acid alkylene oxide adducts, tri(meth)acrylates of isocyanuric acid alkylene oxide adducts, di(meth)acrylates of caprolactone-modified isocyanuric acid alkylene oxide adducts, and tri(meth)acrylates of caprolactone-modified isocyanuric acid alkylene oxide adducts;

[0137] Polyol poly(meth)acrylates such as trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate or tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate or hexa(meth)acrylate;

[0138] Poly(meth)acrylates of polyol alkylene oxide adducts such as tri(meth)acrylate of trimethylolpropane alkylene oxide adduct, tetra(meth)acrylate of di-trimethylolpropane alkylene oxide adduct, tri(meth)acrylate or tetra(meth)acrylate of pentaerythritol alkylene oxide adduct, penta(meth)acrylate or hexa(meth)acrylate of dipentaerythritol alkylene oxide adduct;

[0139] Urethane (meth)acrylates; epoxy (meth)acrylates; and

[0140] Polyester (meth)acrylate.

[0141] In the alkylene oxide adducts, examples of the alkylene oxide include ethylene oxide and propylene oxide.

[0142] The benzoxazine compound (b7) is a compound having a benzoxazine skeleton, and specifically includes: o-cresol aniline type benzoxazine resin, m-cresol aniline type benzoxazine resin, p-cresol aniline type benzoxazine resin, phenol-aniline type benzoxazine resin, phenol-methylamine type benzoxazine resin, phenol-cyclohexylamine type benzoxazine resin, phenol-m-toluidine type benzoxazine resin, phenol-3,5-dimethylaniline type benzoxazine resin, bisphenol A-aniline type benzoxazine resin, bisphenol A-amine type benzoxazine resin, bisphenol F-aniline type benzoxazine resin, bisphenol S-aniline type benzoxazine resin, dihydroxydiphenyl sulfone-aniline type benzoxazine resin, dihydroxydiphenyl ether-aniline type benzoxazine resin, benzophenone type benzoxazine resin, biphenyl type benzoxazine resin, bisphenol AF-aniline type benzoxazine resin, bisphenol A-methylaniline type benzoxazine resin, phenol-diaminodiphenylmethane type benzoxazine resin, triphenylmethane type benzoxazine resin, and phenolphthalein type benzoxazine resin, etc.

[0143] As curable compounds other than components (b1) to (b7), phenol resins and isocyanate group-containing compounds may also be used.

[0144] 2-2. Other ingredients

[0145] The present composition may further contain other compounds within the scope of the present disclosure. For example, copolymers that do not conform to the present copolymer may also be used. In addition, any thermoplastic resin may also be used. In order to promote the crosslinking reaction of free radical-reactive non-conjugated carbon-carbon unsaturated bonds, a free radical polymerization initiator may be added. In addition, by using a catalyst, the curing process can be efficiently promoted. Preferred examples of such catalysts include imidazole-based, amine-based, and phosphorus-based catalysts.

[0146] As the radical polymerization initiator, a known compound can be used. For example, peroxides such as benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, di-tert-butyl peroxide, tert-butylcumyl peroxide, α,α'-bis(tert-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, dicumyl peroxide, di-tert-butyl peroxyisophthalate, tert-butyl peroxybenzoate, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)octane, di-tert-amyl peroxide, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, bis(trimethylsilyl)peroxide, trimethylsilyltriphenylsilylperoxide, and diisopropylbenzene hydroperoxide can be exemplified. In addition, 2,3-dimethyl-2,3-diphenylbutane is also preferred as the radical polymerization initiator.

[0147] The amount of the radical polymerization initiator is in the range of 0.01 to 10 parts by mass, preferably 0.1 to 8 parts by mass, relative to 100 parts by mass of the copolymer. Within this range, the curing reaction proceeds well without being inhibited.

[0148] Further examples include inorganic fillers, heat stabilizers, dyes, pigments (e.g., carbon black), polymerization inhibitors, defoaming agents, leveling agents, ion trapping agents, moisturizers, viscosity modifiers, preservatives, antibacterial agents, antistatic agents, antiblocking agents, ultraviolet absorbers, infrared absorbers, and electromagnetic wave shielding agents.

[0149] The present composition may be solvent-free or contain a solvent. Examples of the solvent include toluene, xylene, methyl ethyl ketone, N,N-dimethylformamide, methyl isobutyl ketone, N-methyl-pyrrolidone, acetone, methanol, ethanol, butanol, 2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-acetoxy-1-methoxypropane, n-hexane, cyclohexane, cyclohexanone, and mixtures thereof.

[0150] For the viewpoint of giving full play to low dielectric constant more effectively, it is preferred to use fluorine-based filler. As fluorine-based filler, examples include: polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF) (vinylidene fluoride polymer with a linear structure of CF2 and CH2 alternately bonded), neoflon (neoflon) FEP (tetrafluoroethylene-hexafluoropropylene copolymer: tetrafluoroethylene-hexafluoropropylene copolymer resin), PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer: perfluoroalkoxy resin), neoflon (neoflon) ETFE (copolymer of tetrafluoroethylene and ethylene), ECTFE (polychlorotrifluoroethylene: chlorotrifluoroethylene resin), etc.

[0151] The type of inorganic filler is not particularly limited. By using an inorganic filler, crack resistance after a heat cycle test is further improved.

[0152] Specific examples of inorganic fillers include: alumina, aluminum hydroxide, zirconium hydroxide, barium hydroxide, calcium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, magnesium sulfate, titanium oxide, tin oxide, magnesium oxide, zirconium oxide, calcium oxide, zinc oxide, molybdenum oxide, antimony oxide, nickel oxide, calcium silicate, beryllium oxide, calcium titanate, aluminum nitride, boron nitride, titanium dioxide, zinc borate, aluminum borate and other metal compounds; talc; clay; mica; glass fiber, kaolin, hydrotalcite (hy Metal oxides or metal nitrides such as drotalcite, wollastonite, xonotlite, calcium hydrogen phosphate, calcium phosphate, glass flakes, hydrated glass, and sepiolite; hydrated metal compounds; silica-based fillers such as fused crushed silica, fused spherical silica, crystalline silica, amorphous silica, secondary agglomerated silica, micropowdered silica, hollow silica, and porous silica; nitride-based or carbon-based fillers such as silicon carbide, silicon nitride, titanium carbide, and diamond.

[0153] Among these, silica, alumina, aluminum nitride, and boron nitride are more preferred. From the viewpoint of effectively improving crack resistance, silica, alumina, and boron nitride are particularly preferred.

[0154] 2-3. Properties of Resin Composition and Cured Product

[0155] A cured product is obtained by curing the present composition. Here, the so-called cured product refers to a state in which a three-dimensional cross-linked structure is formed by a curing treatment and is cured, and refers to a state in which a curing reaction will not substantially occur even if a further curing treatment is performed. Examples of the curing treatment include: a state in which curable compounds are cross-linked with each other, a state in which a curable compound is cross-linked with the present copolymer, a state in which a curable compound is cross-linked with other components, and a state in which these are arbitrarily combined. The curing treatment is carried out by free radical reactions, etc. Heating may also be performed as needed. In addition, when the present composition is formed into a desired shape such as a sheet, a part of it may undergo a curing reaction, but a state in which a curable product can be cured if a further curing treatment is performed is not included in the cured product described herein. At the stage of the resin composition, it may also be a state in the B stage after a part of the component is semi-cured.

[0156] 3. Method for producing resin composition

[0157] The present composition is obtained by mixing the various ingredients. During mixing, a solvent may be used as appropriate. The solid content concentration is, for example, 20% to 60% by mass. The present composition is, for example, in the form of a powder, a film, a sheet, a plate, a granular, a paste, or a liquid. A liquid or paste-like resin composition can be easily obtained by adjusting the viscosity using a solvent. In addition, a film-like, sheet-like, or plate-like resin composition can be formed, for example, by applying a liquid or paste-like resin composition and drying it. In addition, a powdery or granular resin composition can be obtained, for example, by crushing or breaking the film-like resin composition into the desired size.

[0158] 4. Resin composition layer, laminated sheet and prepreg

[0159] The present composition can be preferably used as a resin composition layer. In addition, the present composition can be preferably used for laminated sheet applications comprising a substrate and a resin composition layer formed by the present composition and arranged on the substrate. The resin composition layer shows excellent adhesion after curing treatment and is therefore preferably used as a bonding application with various materials (resin layer, metal layer, inorganic layer such as indium tin oxide (ITO), composite layer, etc.). For example, it is preferably used as a bonding material for bonding sheets of copper clad laminates (CCL: Copper Clad Laminate), electronic circuit boards, and electronic components.

[0160] For example, a coating liquid (varnish) of the present composition containing a solvent is applied to one side of a release film, and a liquid medium such as an organic solvent is removed at, for example, 40°C to 150°C and dried to obtain a laminated sheet having a resin composition layer (adhesive sheet). By laminating another release film on the surface of the obtained adhesive sheet, a laminated sheet having a release film on both sides can be obtained. By laminating on both sides with a release film, surface contamination of the adhesive sheet can be prevented. The adhesive sheet can be separated by peeling off the release film. The two release films can be of the same or different types. By using release films with different peeling properties, the peeling force can be given different strengths, so that it is easy to peel off in sequence. In addition, a laminated sheet having an adhesive sheet (resin composition layer) can be obtained by applying a coating liquid to a substrate other than a releasable substrate.

[0161] Examples of substrates include resin materials such as polyimide films, polyethylene films, polycarbonate, polyethylene, liquid crystal polymers, phenolic resins, and polyaramid resins; metal materials such as copper, aluminum, and stainless steel; inorganic materials such as ITO, glass, silicon, and silicon carbide; and composite materials comprising any combination thereof. The present composition, by using the present copolymer having the present alicyclic structure and a ring containing a non-conjugated C=C bond in at least one of a side chain, a side group, or a molecular chain terminal, not only exhibits excellent heat resistance on various substrates but also exhibits excellent moldability.

[0162] Coating methods include, for example, notch wheel coating, knife coating, die coating, lip coating, roller coating, curtain coating, bar coating, gravure printing, flexographic printing, screen printing, dip coating, spray coating, and spin coating. To achieve sufficient adhesion and ease of handling, the thickness of the adhesive sheet after drying is preferably 5 μm to 500 μm, more preferably 10 μm to 100 μm.

[0163] The present composition can be preferably used as a material for forming a prepreg obtained by impregnating the present composition in a substrate. The prepreg can be manufactured by, for example, impregnating the present composition in a fiber substrate, then heating and drying the resin composition and semi-hardening (B-stage). With respect to the solid content of the resin composition relative to the fiber substrate, it is preferably relative to the prepreg that the content of the dried resin composition is 20% by mass to 90% by mass. More preferably, it is 30% by mass to 80% by mass, and further preferably 40% by mass to 70% by mass. For example, the present composition can be impregnated or applied to a fiber substrate by making the solid content of the resin composition in the prepreg 20% ​​by mass to 90% by mass, for example, heating and drying for 1 minute to 30 minutes at a temperature of 40°C to 250°C to semi-harden (B-stage) to manufacture.

[0164] As the fiber substrate, known materials can be used without limitation, and examples thereof include organic fibers, inorganic fibers, and glass fibers. Examples of organic fibers include polyimide, polyester, tetrafluoroethylene, wholly aromatic polyamide, and the like. Examples of inorganic fibers include carbon fibers. Examples of glass fibers include E glass cloth, D glass cloth, S glass cloth, Q glass cloth, NE glass cloth, L glass cloth, T glass cloth, spherical glass cloth, and low-dielectric glass cloth. Among these, E glass cloth, T glass cloth, S glass cloth, Q glass cloth, and organic fibers are preferred from the perspective of low thermal expansion coefficient. One fiber substrate may be used alone or two or more may be used in combination.

[0165] The shape of the fiber substrate can be appropriately selected according to the target application and performance. Specific examples include woven fabrics, non-woven fabrics, rovings, chopped strand mats, and surfacing mats. Examples of weaving methods for the woven fabrics include plain weave, mat weave, and twill weave. The shape can be arbitrarily selected and designed according to the desired properties. The thickness of the fiber substrate is, for example, in the range of about 0.01 mm to 1.0 mm. From the perspective of thin film formation, it is preferably 500 μm or less, and more preferably 300 μm or less.

[0166] To achieve the desired properties, the fiber base material may be surface treated with a silane coupling agent or mechanically opened, as needed. Corona treatment or plasma treatment may also be performed. Surface treatments using silane coupling agents include aminosilane coupling, vinylsilane coupling, cationic silane coupling, and epoxysilane coupling.

[0167] The method for impregnating the fiber substrate with the resin composition is not particularly limited. Examples thereof include a method in which a varnish-like resin composition is prepared using an organic solvent such as alcohols, ethers, acetals, ketones, esters, alcohol esters, keto alcohols, ether alcohols, keto ethers, keto esters, or ester ethers, and the fiber substrate is impregnated with the varnish; a method in which the varnish is applied to the fiber substrate or sprayed onto the fiber substrate; and a method in which a film containing the resin composition is laminated on both sides of the fiber substrate.

[0168] Furthermore, the resin composition layer formed from the present composition, its cured layer, etc. are preferably used as an insulating layer, underfill material, adhesive material, etc. for semiconductor chip packaging. In addition, it is also preferably used as a composition for copper-clad laminates, a bonding sheet for wiring board formation, and an outer coating of a flexible substrate.

[0169] 5. Method for manufacturing hardened product

[0170] A cured product is obtained by curing the present composition. In the case of a thermosetting compound, curing is performed by heat curing, and in the case of a light curing compound, curing is performed by light irradiation. For example, a method of forming a resin composition into a desired shape such as a sheet and curing it can be exemplified. A formed body such as a sheet of the resin composition can be simply obtained by applying a resin composition containing a solvent and drying it, and then curing it to form a cured product. The timing of curing can be before, during, or after forming. In addition, the sheet-like portion of the cured product is also referred to as a cured layer.

[0171] The temperature during the heat curing treatment can be appropriately selected according to the type of curable compound. For example, a method of heat treatment at a temperature of 150°C to 300°C for 30 minutes to 180 minutes can be exemplified. In the case of light curing treatment, irradiation with actinic rays at an intensity sufficient for curing can be performed. During curing, pressure can be applied for hot pressing (for example, 2 MPa) as needed. By the curing treatment, a cross-linked structure is formed in the present composition, thereby obtaining a three-dimensional cross-linked cured product.

[0172] 6. Hardened materials and substrates with hardened materials

[0173] The cured product obtained from this composition has excellent heat resistance, excellent crack resistance after thermal cycle testing, and excellent substrate processing suitability during the manufacturing process. Therefore, it is suitable as a cured product for various parts such as metal-clad laminates and printed wiring boards, or as a substrate with a cured product containing such a cured product.

[0174] The metal-clad laminate is obtained, for example, by forming an insulating layer using the present composition and laminating the insulating layer with the metal layer. A sheet or prepreg formed from the present composition can be preferably used in the insulating layer. For example, after laminating the metal layer with the prepreg formed using the present composition, a hardening treatment process is performed by heat pressing to obtain the metal-clad laminate. The heat pressing process can be performed using a known method. For example, it is performed by hot pressing at a temperature of 120°C to 250°C and a pressure of 0.5MPa to 10MPa for 0.5 to 5 hours.

[0175] Examples of the laminate structure of the metal-clad laminate include a two-layer laminate of metal layer / hardened layer, a laminate comprising multiple layers of metal layer / hardened layer / metal layer, or a metal-clad laminate having a multilayer structure of metal layer / hardened layer / metal layer / hardened layer / metal layer alternately stacked. Furthermore, an insulating layer other than the hardened layer formed from the present composition may also be included in the laminate. Furthermore, to adjust the thickness of the hardened layer, multiple prepregs may be stacked and hardened. Furthermore, conductive layers other than the metal layer may also be stacked.

[0176] For example, a circuit substrate having a circuit pattern layer can be obtained by forming a circuit pattern on the metal layer of a metal-clad laminate having a layer structure of metal layer / hardened layer / metal layer. Through holes or through-holes can be formed in the hardened layer by laser or the like. Alternatively, an insulating hardened layer can be superimposed on a core substrate by a build-up process to form through-holes and perform multi-layering. The circuit substrate can be obtained, for example, by forming the metal layer of the metal-clad laminate into the desired circuit pattern using a subtractive method, or by forming the desired circuit pattern on one or both sides of the insulating layer using an additive method.

[0177] As the metal layer, copper foil or the like can be used. In a copper-clad laminate, electrolytic copper plating is performed on the copper foil surface, and after removing the resist layer, etching is performed using an alkaline plating solution or the like. This composition is excellent in substrate processing adaptability such as resistance to plating solutions and is therefore preferred for copper-clad laminate applications. Furthermore, since the cured product has excellent crack resistance and heat resistance after a thermal cycle test, a substrate with a cured product formed by curing this composition can be used for a wide range of applications under various environments.

[0178] Printed wiring boards can be manufactured, for example, by processing the copper foil in a copper-clad laminate by etching, laminating a substrate obtained by forming a signal circuit, etc. with a cover film via a sheet, and undergoing a hardening treatment process. In addition, a flexible printed wiring board can be manufactured, for example, by the following process: a conductor pattern is formed on an insulating flexible film, a protective film is formed thereon via the sheet, and thermal compression bonding is performed. As the flexible film, polyester, polyimide, liquid crystal polymer, PTFE film can be exemplified. The conductor pattern can be exemplified by a method of forming it using a printing technique, a method of forming it by sputtering, and a method of plating.

[0179] It is also possible to form an opening by drilling or laser processing or the like relative to the hardened layer of the present composition formed on one or both sides of a printed wiring board, fill a conductive agent and form a through hole. In addition, a circuit layer can also be formed on the hardened layer of the present composition. The hardened material of the present composition has excellent resistance to plating liquid, and is therefore preferred for manufacturing a multilayer printed wiring board. The printed wiring board formed using the present composition has excellent processing adaptability, excellent heat resistance and crack resistance after thermal cycle test, and is therefore preferred for various electronic devices such as smart phones or tablet terminals.

[0180] The electrical insulation of this copolymer is excellent, so by further using an insulating curable compound in this composition, a cured product with excellent insulating properties can be provided. For example, it can be preferably used as an insulating layer forming material on a circuit substrate (including a cover layer of a printed wiring board, an interlayer insulating layer of a build-up substrate, a bonding sheet, etc.). In addition, by using a conductive material in a filler, for example, it can also be used for a conductive member of an electronic component. Electronic components can exemplify power modules such as power semiconductor devices, light emitting diodes (LEDs), and inverter devices.

[0181] And then, by allocating such as thermal conductive filler as inorganic filler in the hardened material of this composition, it is possible to apply to all purposes requiring heat dissipation.For example, the formability of resin combination can be utilized, preferably as the heat dissipation parts of desired shape.Especially for light and short miniaturization, it is effective as the heat dissipation adhesive material or heat dissipation sheet of the electronic equipment (smart phone, tablet terminal etc.) that fan or radiator cannot be set, battery outer packaging material.In addition, the hardened material of this composition is preferably as the adhesive layer or heat sink (heat spreader) of heating element and radiator.In addition, it can be used as the heat dissipation layer of one or more electronic components coated on substrate.

[0182] The amount of the copolymer blended is optional, but in order to improve the heat resistance of the cured product and further enhance crack resistance after thermal cycling testing, it is preferably present in an amount of 1 to 50% by mass relative to 100% by mass of the non-volatile component (solids) of the composition. This range is more preferably 4 to 44% by mass, and even more preferably 6 to 38% by mass.

[0183] Example

[0184] The present disclosure will be described in more detail below with reference to the following examples. The present disclosure is not limited to the following examples. Unless otherwise specified, "%" and "parts" are based on mass.

[0185] 7. Determination Method

[0186] 7-1. Determination of acid anhydride value

[0187] Accurately measure about 1 g of the sample (resin of each synthesis example) in a co-stopped conical flask and add 100 mL of 1,4-dioxane solvent to dissolve it. Add 10 mL of a mixed solution of octylamine, 1,4-dioxane, and water (the mixing ratio by mass is 1.49 / 800 / 80) that is larger than the amount of anhydride groups in the sample and stir for 15 minutes to react with the anhydride groups. Afterwards, the excess octylamine is titrated with a mixed solution of 0.02 M perchloric acid and 1,4-dioxane. In addition, 10 mL of a mixed solution of octylamine, 1,4-dioxane, and water (the mixing ratio by mass is 1.49 / 800 / 80) to which no sample is added is also measured as a control. The anhydride value is calculated using the following formula (unit: mgKOH / g).

[0188] Acid anhydride value (mgKOH / g) = 0.02 × (BA) × F × 56.11 / S

[0189] B: titration of control (mL)

[0190] A: Titration of sample (mL)

[0191] S: Sample quantity (g)

[0192] F: 0.02 mol / L perchloric acid titer

[0193] 7-2. Determination of amine value

[0194] Accurately measure approximately 1 g of the sample (resin from each synthesis example) in a co-stopped Erlenmeyer flask and dissolve it in 100 mL of cyclohexanone. Separately, add 2 drops and 3 drops of an indicator prepared by mixing 0.20 g of methyl orange dissolved in 50 mL of distilled water and 0.28 g of xylene cyanol FF dissolved in 50 mL of methanol. Hold for 30 seconds. Titrate with 0.1 N alcoholic hydrochloric acid until the solution turns bluish-gray. The amine value is calculated using the following formula.

[0195] Amine value (mgKOH / g) = (5.611×a×F) / S

[0196] in,

[0197] S: Sample quantity (g)

[0198] a: Consumption of 0.1N alcoholic hydrochloric acid solution (mL)

[0199] F: Titer of 0.1N alcoholic hydrochloric acid solution

[0200] 7-3. Determination of weight average molecular weight (Mw)

[0201] The determination of Mw was performed using a gel permeation chromatograph (GPC) "GPC-101" manufactured by Showa Denko. The solvent was tetrahydrofuran (THF), and as the column, two "KF-805L" (manufactured by Showa Denko: GPC column: 8 mm ID × 300 mm size) connected in series were used. The analysis was carried out under the conditions of sample concentration 1 mass%, flow rate 1.0 mL / min, pressure 3.8 MPa, and column temperature 40°C, and Mw was determined by polystyrene conversion. Data analysis was performed using the manufacturer's built-in software to calculate the calibration curve, molecular weight, and peak area, and the retention time range of 17.9 minutes to 30.0 minutes was used as the analysis object to determine Mw.

[0202] 7-4. Radical Reactivity of Non-Conjugated Carbon-Carbon Unsaturated Bonds in (i) and (ii)

[0203] The radical-reactive non-conjugated carbon-carbon unsaturated bond values ​​of (i) and (ii) are calculated based on the designed values ​​of the raw materials used in the polymerization of the copolymer. That is, the values ​​are calculated based on the charge amount of the compound bonded via the radical-reactive non-conjugated carbon-carbon unsaturated bonds of (i) and (ii) relative to the charge amount of the raw materials used in the synthesis of the copolymer.

[0204] 7-5. Calculation of total functional group value

[0205] The total functional group value was defined as the total (mgKOH / g) of the acid anhydride value, the amine value, and the radically reactive non-conjugated carbon-carbon unsaturated bond values ​​(i) to (ii).

[0206] 8. Synthesis of the copolymer

[0207] [Synthesis example 1]

[0208] 48 parts of LICOCENE PP 1602 (polypropylene polyethylene copolymer, (manufactured by Clariant), Mw: 57000, St: 0%) were dissolved in 50 parts of xylene, 20 parts of maleic anhydride as an acid anhydride and 1.7 parts of Luperox DTA (di-tert-amyl peroxide, manufactured by Arkema Yoshitomi) as a free radical initiator were added, and the mixture was stirred at 140° C. for 2 hours while being refluxed. The peak of the carboxyl group origin (1711 cm) was used for FT-IR. -1The end point of the reaction was confirmed by the formation of (near) to obtain a maleic anhydride-modified polyethylene-polypropylene copolymer. Subsequently, 0.5 parts of K-NOX 1010 (pentaerythritol tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, manufactured by KuoChing Chemical Co., Ltd.) was added, the temperature was set to 100°C, 28 parts of 5-norbornene-2-methylamine and 0.08 parts of dimethylbenzylamine as a catalyst were added, and after stirring at 100°C for 2 hours, the mixture was stirred at 170°C for 2 hours while azeotropically co-existing xylene and water produced by the reaction, thereby carrying out imidization. FT-IR was used to identify the peak of the carboxyl group origin (1711cm -1 near the peak originating from the imide group (1704 cm -1 The peak of alkane origin (1397cm -1 The end point of the reaction was confirmed by adding 200 parts of toluene for dilution and 225 parts of methanol to obtain a precipitate. The precipitate was recovered by filtration, 200 parts of toluene were added to the precipitate again and dissolved, and 225 parts of methanol were added to obtain a precipitate. The precipitate was recovered by filtration and dried in a vacuum oven at 100°C for 2 hours to obtain a resin having a non-conjugated carbon-carbon unsaturated bond in the side chain. The free radical reactive carbon-carbon unsaturated bond value was 10 mgKOH / g.

[0209] [Synthesis Examples 2 to 8]

[0210] Synthesis Examples 2 to 8 of copolymers were obtained by the same method as Synthesis Example 1 except that the monomer amounts and blending amounts described in Table 1 were changed.

[0211] [Comparative Synthesis Example 1]

[0212] 48 parts of LICOCENE PP 1602 were dissolved in 50 parts of xylene. 20 parts of maleic anhydride as an acid anhydride and 1.7 parts of Luperox DTA as a free radical initiator were added, and the mixture was stirred at 140°C for 2 hours while refluxed. 200 parts of toluene were then added for dilution, and 225 parts of methanol were added to obtain a precipitate. The precipitate was recovered by filtration, and 200 parts of toluene was added to the precipitate for dissolution, followed by the addition of 225 parts of methanol to obtain a precipitate. The precipitate was recovered by filtration and dried in a vacuum oven at 100°C for 2 hours to obtain a resin having an acid anhydride as a side chain. The acid anhydride value was 10 mgKOH / g.

[0213] [Comparative Synthesis Examples 2 to 7]

[0214] Comparative Synthesis Examples 2 to 7 of copolymers were obtained by the same method as Comparative Synthesis Example 1 except that the monomer amounts and blending amounts described in Table 1 were changed.

[0215] The abbreviations of Table 1 are shown below.

[0216] (resin before modification)

[0217] R-1: Polypropylene (LICOCENE PP 1602, Mw 57,000, St 0%)

[0218] R-2: Hydrogenated styrene-butadiene rubber (Dynaron 2324P, Mw 170,000, St 16%)

[0219] R-3: SEP (G1702, Mw 150,000, St 28%)

[0220] R-4: SEBS (G1652, Mw 72,000, St 30%)

[0221] R-5: SEBSS (A1536, Mw 130,000, St 40%)

[0222] (Compounds containing non-conjugated carbon-carbon unsaturated bonds)

[0223] T-1: 5-Norbornene-2-methylamine

[0224] T-2: N-(4-aminophenyl)maleimide

[0225] Figure 1 IR spectra of the resin R-5 before modification, comparative synthesis example 5 and synthesis example 5 are shown in FIG. As shown in the figure, a peak (1711 cm 2 ) originating from the carboxyl group was confirmed in comparative synthesis example 5. -1 On the other hand, in Synthesis Example 5, a peak (1711 cm) originating from C═O of carboxylic acid was confirmed. -1 The peak (1704 cm) originating from the C=O of the imide group -1 In addition, a peak originating from alkanes (1397 cm -1 nearby).

[0226] [Table 1]

[0227]

[0228] 9. Preparation of resin composition (varnish)

[0229] [Example 1]

[0230] 100 parts of the copolymer (P1) of Synthesis Example 1 and 1 part of (C)-1 as an initiator are placed in a container in terms of solid content, and a mixed solvent (toluene: MEK = 1:1 (mass ratio)) is added so that the non-volatile component concentration becomes 25%. The mixture is stirred for 10 minutes using a disperser to prepare the varnish of Example 1.

[0231] [Examples 2 to 31, Comparative Examples 1 to 22]

[0232] Varnishes of Examples 2 to 31 and Comparative Examples 1 to 22 were prepared by the same method as in Example 1 except that the blending components and blending amounts described in Tables 2 and 3 were changed.

[0233] Materials used in Examples and Comparative Examples are shown below.

[0234] (hardening compound)

[0235] (B)-1: Epoxy compound (b1), XD-1000 (manufactured by Nippon Kayaku Co., Ltd., dicyclopentadiene-type epoxy, multifunctional, functional group equivalent weight 252 g / eq)

[0236] (B)-2: Cyanate compound (b2), BAD (manufactured by Mitsubishi Gas Chemical Co., Ltd., bisphenol A type cyanate, difunctional, functional group equivalent weight 139 g / eq, molecular weight 278)

[0237] (B)-3: Maleimide compound (b3), BMI-4000 (manufactured by Yamato Chemical Industry Co., Ltd., bisphenol A diphenyl ether bismaleimide, difunctional, functional group equivalent weight 285.3 g / eq, molecular weight 570.6)

[0238] (B)-4: Allyl-containing compound (b4), Tmaic (manufactured by Shinryo Corporation, triallyl isocyanurate, trifunctional, molecular weight 249.3)

[0239] (B)-5: Vinyl-containing compound (b5), OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical Co., Ltd., vinylbenzyl-modified polyphenylene ether, difunctional, functional group equivalent weight: 590 g / eq, number average molecular weight: 1180)

[0240] (B)-6: (meth)acrylate-containing compound (b6), Noryl SA9000 (manufactured by SABIC, methacrylate-containing polyphenylene ether, difunctional, functional group equivalent weight: 850 g / eq, number average molecular weight: 1700)

[0241] (B)-7: Benzoxazine compound (b7), 3,3'-(methylene-1,4-diphenylene)bis(3,4-dihydro-2H-1,3-benzoxazine) (manufactured by Shikoku Chemicals Co., Ltd., Pd-type benzoxazine, difunctional, oxazine equivalent weight 217) (Initiator (C))

[0242] (C)-1: Free radical initiator (c1), Percumyl D (manufactured by NOF Corporation, dicumyl peroxide, molecular weight 270.4)

[0243] (C)-2: Epoxy initiator (c2), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd., multifunctional epoxy resin, molecular weight 360.5)

[0244] The epoxy initiator (c2) can be classified as the epoxy compound (b1) in terms of having an epoxy group, but in this embodiment, it is mainly used as an initiator for ring-opening the epoxy based on the amine structure and is therefore classified as the initiator (C).

[0245] (Filler (D))

[0246] (D)-1: SO-C2 (average particle size 0.4 μm to 0.6 μm, manufactured by Admatechs, silica)

[0247] (D)-2: AO-509 (average particle size 7 μm to 13 μm, manufactured by Admatechs, alumina)

[0248] (D)-3: SP-2 (average particle size D50 4 μm, manufactured by Denka Co., Ltd., boron nitride)

[0249] (D)-4: HF-01 (average particle size D50 1.1 μm, manufactured by Tokuyama Co., Ltd., aluminum nitride)

[0250] (Olefin polymer (E) containing a radically reactive carbon-carbon unsaturated bond in a side chain)

[0251] (E)-1: Styrene-butadiene-styrene resin (Tufprene 126S, manufactured by Asahi Kasei Corporation)

[0252] (E)-2: Polybutadiene resin (PB B-3000, manufactured by Nippon Soda Co., Ltd.)

[0253] 10. Preparation of evaluation samples

[0254] 10-1. Preparation of adhesive sheet

[0255] Using a doctor blade, each resin varnish was evenly applied to a 50 μm thick heavy release film (polyethylene terephthalate (PET) film coated with a heavy release agent) to a thickness of 50 μm after drying. The film was then dried at 100°C for 2 minutes. The film was then cooled to room temperature to obtain a single-sided release film adhesive sheet. The adhesive sheet surface of the obtained single-sided release film adhesive sheet was then superimposed on a 50 μm thick light release film (polyethylene terephthalate (PET) film coated with a light release agent), thereby obtaining a double-sided release film adhesive sheet consisting of a heavy release film / adhesive sheet / light release film.

[0256] 10-2. Manufacturing of Copper-Clad Laminates

[0257] The light release film was peeled off from the adhesive sheet with release films on both sides obtained by the above method. The exposed adhesive sheet was then simultaneously bonded to the copper foil side of a single-sided copper-clad laminate composed of a 50 μm polyimide film and a 12 μm copper foil using a vacuum laminator (Nichigo-Morton Co., Ltd., a small pressurized vacuum laminator V-130). The vacuum lamination conditions were a heating temperature of 100°C, a vacuum time of 60 seconds, a vacuum peak pressure of 2 hPa, a pressure of 0.4 MPa, and a pressurizing time of 60 seconds.

[0258] Then, the heavy release film is peeled off, and the polyimide side of the second single-sided copper-clad laminate is temporarily bonded to the exposed bonding sheet surface using a vacuum laminator. The bonding sheet is then thermally cured using vacuum hot pressing at 200°C, 2 hours, and 2 MPa to produce an evaluation sample of the laminated structure of polyimide film / copper foil / hardened bonding sheet / polyimide film / copper foil film.

[0259] 11. Evaluation

[0260] α. Heat resistance

[0261] After the copper-clad laminate made in each example is cut out to width 10mm, length 65mm, keep the test piece under various conditions, afterwards make the copper foil face contact with molten solder and float 1 minute at various temperatures.Afterwards, visual observation test piece's outward appearance, evaluate the subsequent abnormality such as whether foaming, floating, peeling etc. follow after hardening. Said test is the thermal stability of the subsequent layer after hardening when the solder contacts by the appearance evaluation solder.The outward appearance of the person with good heat resistance does not change, produces foaming or peeling after solder treatment relative to this poor heat resistance.These evaluation results are judged according to the following benchmark.

[0262] AA: After being stored at 85°C and 85% relative humidity for 24 hours, the appearance does not change even when it floats in molten solder at 300°C.

[0263] A: Does not meet the requirements of AA. After being stored at 40°C and 90% humidity for 24 hours, the appearance did not change even when it floated in 300°C molten solder.

[0264] B: Does not satisfy A. The test piece stored at 40°C and 90% humidity for 24 hours did not change in appearance when it was floated in molten solder at 280°C.

[0265] C: Does not satisfy A or B. The test piece stored at 23°C and 50% humidity for 24 hours did not change in appearance when it was floated in molten solder at 280°C.

[0266] D: Does not satisfy A to C. The test piece stored at 23°C and 50% humidity for 24 hours did not change in appearance when it was floated in molten solder at 260°C.

[0267] E: Does not satisfy A to D. The test piece stored at 23°C and 50% humidity for 24 hours did not change in appearance when it was floated in molten solder at 240°C.

[0268] F: After being stored at 23°C and 50% humidity for 24 hours, the test piece floated in molten solder at 240°C, and its appearance changed. This is a problem in practical use.

[0269] β. Dielectric properties

[0270] After the adhesive sheet with release film on both sides is stored in an environment of 23°C and a relative humidity of 50% for more than 24 hours, the release film is peeled off. Under the above temperature and humidity environment, the dielectric constant measuring device manufactured by AET is used to calculate the dielectric loss tangent (Df) at a measurement frequency of 10 GHz using the cavity resonator method.

[0271] AA: Df less than 0.0004

[0272] A: Df is 0.0004 or more and less than 0.0005

[0273] B: Df is 0.0005 or more and less than 0.0010

[0274] C: Df is 0.0010 or more and less than 0.0020

[0275] D: Df is 0.0020 or more and less than 0.0030

[0276] E: Df is 0.0030 or more and less than 0.0035

[0277] F: Df is 0.0035 or more, which is problematic in practice.

[0278] γ. Evaluation of stress relaxation (cracking resistance) properties

[0279] A glass cloth-based epoxy copper-clad laminate with a circuit pattern of L / S = 25 μm / 25 μm and copper thicknesses of 25 μm and 50 μm, respectively, was prepared as an inner-layer circuit board. The resin sheets prepared using the above method were vacuum-heat-pressed on both sides at 200°C, 3.0 MPa, and for 2 hours. Finally, copper foil was placed on the outermost layers of both sides to produce printed wiring boards for evaluation.

[0280] Then, the evaluation printed wiring board was placed in a thermal shock device ("TSE-11-A", manufactured by ESPEC) and subjected to a predetermined number of alternating exposures under the following conditions: high temperature exposure: 125°C, 15 minutes, and low temperature exposure: -50°C, 15 minutes. The evaluation printed wiring board was cut, and the exposed cross section was observed for cracks using a scanning electron microscope (SEM) at a magnification of 5000 times. In addition, the so-called crack refers to a crack with a size of 0.1 μm or more. The evaluation criteria are as follows.

[0281] AA: No cracks occurred after 4000 heat cycle tests. This is an extremely good result.

[0282] A: Does not meet AA. No cracks were observed after 3000 heat cycle tests. This is an extremely good result.

[0283] B: Does not satisfy A. No cracks were observed after 1000 heat cycle tests. This is a very good result.

[0284] C: Does not satisfy A and B. No cracks were observed after 200 heat cycle tests. This is a good result.

[0285] D: Does not satisfy A to C. No cracks were observed after 100 heat cycle tests. This presents a practical problem.

[0286] E: Cracks occurred before 100 cycles of testing, which is a problem in practical use.

[0287] [Table 2]

[0288]

[0289]

[0290] This application claims priority based on Japanese Patent Application No. 2023-028746 filed on February 27, 2023, and Japanese Patent Application No. 2023-202239 filed on November 29, 2023, the disclosures of which are incorporated herein in their entirety.

Claims

1. A modified olefin copolymer, wherein the main chain comprises structural units derived from conjugated diene compounds and / or structural units derived from alicyclic or chain non-conjugated olefin compounds, wherein: At least any one of the side group, the side chain and the molecular chain terminal has a monocyclic structure and / or a polycyclic structure, The ring of the monocyclic structure and / or any ring of the polycyclic structure is at least one of an alicyclic skeleton containing carbon atoms and an alicyclic skeleton containing carbon atoms and heteroatoms, and satisfies at least one of the following (i) and (ii); (i) having a free radical-reactive non-conjugated carbon-carbon unsaturated bond in the alicyclic skeleton; (ii) The carbon atoms constituting the alicyclic skeleton and the carbon atoms not constituting the ring bonded to the carbon atoms are bonded via a radically reactive non-conjugated carbon-carbon unsaturated bond. 2 . The modified olefin-based copolymer according to claim 1 , wherein the main chain has substantially no unsaturated bonds except at the molecular chain terminals. 3 . The modified olefin-based copolymer according to claim 1 , wherein the main chain contains a structural unit derived from an aromatic vinyl compound. 4 . The modified olefin-based copolymer according to claim 1 , comprising a block comprising a structural unit derived from an aromatic vinyl compound and a block comprising a structural unit derived from a conjugated diene compound. 5 . The modified olefin-based copolymer according to claim 3 , wherein the block comprising the structural unit derived from the conjugated diene compound further comprises a structural unit derived from an aromatic vinyl compound.

6. The modified olefin copolymer according to claim 1, which is a hydrogenated styrene elastomer A modified product of any one of styrene-ethylene / butylene block copolymer (SEB), styrene-ethylene / propylene block copolymer (SEP), styrene-ethylene / butylene-styrene block copolymer (SEBS), styrene-ethylene / propylene-styrene block copolymer (SEPS), styrene-ethylene / butylene / styrene-styrene block copolymer (SEBSS), styrene-isobutylene-styrene block copolymer (SIBS), and styrene-ethylene-ethylene / propylene styrene block copolymer (SEEPS).

7. A resin composition comprising the modified olefin-based copolymer according to claim 1.

8. The resin composition according to claim 7, further comprising a curable compound, wherein the curable compound comprises at least one selected from the group consisting of an epoxy compound (b1), a cyanate compound (b2), a maleimide compound (b3), an allyl group-containing compound (b4), a vinyl group-containing compound (b5), a (meth)acrylate group-containing compound (b6), and a benzoxazine compound (b7).

9. The resin composition according to claim 7, further comprising an inorganic filler. 10 . A laminated sheet comprising a substrate and a resin composition layer formed on the substrate using the resin composition according to claim 7 . 11 . A prepreg comprising a base material impregnated with the resin composition according to claim 7 .

12. A cured product obtained from the resin composition according to any one of claims 7 to 9. 13 . A substrate with a cured product, comprising a cured product formed by curing the resin composition according to claim 7 . 14 . An electronic device equipped with the substrate with a cured product according to claim 13 .

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