Resin composition, and prepreg, film with resin, metal foil with resin, metal foil-clad laminate, and wiring board using same

Abstract

One aspect of the present invention relates to a resin composition containing: a hydrocarbon compound (A) represented by formula (1) (in formula (1), X represents a hydrocarbon group having 6 or more carbon atoms and contains at least one group selected from an aromatic ring group and an aliphatic ring group, and n represents an integer of 1-10; a polyphenylene ether compound (B) having a reactive carbon-carbon unsaturated double bond; and at least one of a polyfunctional vinyl aromatic copolymer (C) and an acenaphthylene compound (D) # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a resin composition, a prepreg using the same, a resin-coated film, a resin-coated metal foil, a metal-clad laminate, and a wiring board. Background Art

[0002] In recent years, with the remarkable increase in the information communication speed in various electronic devices such as switches, routers, and servers, in order to utilize high frequency bands, printed wiring boards are increasingly required to have low transmission loss. Since polyphenylene ether resin has excellent dielectric properties such as a dielectric constant and a dielectric loss factor, it is being studied as a material for coping with high frequencies.

[0003] For example, Patent Document 1 and Patent Document 2 disclose that a resin composition containing a modified polyphenylene ether can provide excellent low dielectric properties.

[0004] On the other hand, with the high performance of chips, the package substrates mounted on the printed wiring boards used in the above-described electronic devices have gradually become larger, and in order to suppress warping of the substrates, substrates having a small coefficient of thermal expansion in the plane direction are adopted. As a result, the difference in the coefficient of thermal expansion between the package substrate and the printed wiring board has become larger, and thus a problem of reduced reliability during mounting has occurred. Therefore, printed wiring boards are required not only to have low dielectric properties but also to have a low coefficient of thermal expansion.

[0005] In view of the above circumstances, the present invention has been made, and an object thereof is to provide a resin composition whose cured product has not only low dielectric properties but also a low coefficient of thermal expansion. In addition, an object of the present invention is to provide a prepreg, a resin-coated film, a resin-coated metal foil, a metal-clad laminate, and a wiring board using the resin composition.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: International Patent Publication No. 2014 / 034103

[0009] Patent Document 2: International Patent Publication No. 2014 / 203511 Summary of the Invention

[0010] A resin composition according to one aspect of the present invention contains: a hydrocarbon compound (A) represented by the following formula (1),

[0011]

[0012] In formula (1), X represents a hydrocarbon group having 6 or more carbon atoms and containing at least one selected from an aromatic ring group and an aliphatic ring group, and n represents an integer of 1 to 10;

[0013] A polyphenylene ether compound (B) having a reactive carbon-carbon unsaturated double bond; and

[0014] At least one of a polyfunctional vinyl aromatic copolymer (C) and an acenaphthene compound (D). BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 is a schematic cross-sectional view showing the structure of a prepreg according to an embodiment of the present invention.

[0016] Figure 2 is a schematic cross-sectional view showing the structure of a metal foil-clad laminate according to an embodiment of the present invention.

[0017] Figure 3 is a schematic cross-sectional view showing the structure of a wiring board according to an embodiment of the present invention.

[0018] Figure 4 is a schematic cross-sectional view showing the structure of a resin-coated metal foil according to an embodiment of the present invention.

[0019] Figure 5 is a schematic cross-sectional view showing the structure of a resin-coated film according to an embodiment of the present invention.

[0020] Figure 6 shows the GPC chromatogram of the compound obtained in Synthesis Example 1.

[0021] Figure 7 shows the 1 1H-NMR chromatogram of the compound obtained in Synthesis Example 1.

[0022] Figure 8 shows the GPC chromatogram of the compound obtained in Synthesis Example 2.

[0023] Figure 9 shows the 1 1H-NMR chromatogram of the compound obtained in Synthesis Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0024] The resin composition according to an embodiment of the present invention (hereinafter, also simply referred to as the resin composition) contains: the hydrocarbon compound (A) represented by the above formula (1); a polyphenylene ether compound (B) having a reactive carbon-carbon unsaturated double bond; and at least one of a polyfunctional vinyl aromatic copolymer (C) and an acenaphthene compound (D).

[0025] By containing at least one of a polyfunctional vinyl aromatic copolymer (C) and an acenaphthylene compound (D) in addition to a hydrocarbon compound (A) and a polyphenylene ether compound (B) having a reactive carbon-carbon unsaturated double bond, the cured product of the resin composition has low dielectric properties and can achieve low thermal expansion. That is, according to the present invention, a resin composition can be provided, the cured product of which has low dielectric properties and low thermal expansion. Further, by using the resin composition, a prepreg, a resin-coated film, a resin-coated metal foil, a metal-clad laminate, and a wiring board having excellent such properties can be provided.

[0026] In addition, in order to maintain high reliability as an electronic material property, adhesiveness and heat resistance are also required. It is considered that the resin composition of the present embodiment, by the above configuration, has excellent adhesiveness and heat resistance in addition to low dielectric properties and low thermal expansion.

[0027] In addition, a material having a high Tg of the cured product is one of the factors for further improving heat resistance (solder heat resistance, reflow heat resistance, etc.). Further, for the cured product, if a material having a high Tg is used, it also has the advantage that the thermal expansion coefficient of the material becomes a smaller value in the temperature range from room temperature to the reflow or solder temperature. Generally, this is because the thermal expansion increases rapidly at a temperature exceeding the glass transition temperature. That is, if the glass transition temperature is low, the thermal expansion coefficient increases in the high-temperature region exceeding the glass transition temperature. In the case of a wiring board, if the glass transition temperature is low, the thermal expansion coefficient in the vertical direction increases in the high-temperature region, and thus problems such as disconnection of vias and / or laser vias may occur, and there is a risk of reducing the connection reliability. It is considered that, according to the configuration of the present embodiment as described above, a resin composition having a cured product with a high Tg can be provided.

[0028] Hereinafter, each component of the resin composition according to the present embodiment will be specifically described.

[0029] <Hydrocarbon compound (A)>

[0030] The hydrocarbon compound (A) contained in the resin composition of the present embodiment is a compound represented by the following formula (1).

[0031]

[0032] In formula (1), X represents a hydrocarbon group having at least one selected from an aromatic ring group and an aliphatic ring group and having 6 or more carbon atoms. Further, n represents an integer of 1 to 10.

[0033] It is considered that by containing the hydrocarbon compound (A), the cured product of the resin composition of the present embodiment can achieve low dielectric properties and can suppress the thermal expansion coefficient to a low level.

[0034] The aromatic ring group is not particularly limited, and examples thereof include a phenylene group, a xylylene group, a naphthylene group, a tolylene group, a biphenylene group, etc.

[0035] The aliphatic ring group is not particularly limited, and examples thereof include a group containing an indane structure represented by the following formula (3) and a group containing a cycloolefin structure.

[0036]

[0037] In formula (3), each Rb is independent. That is, Rb may be the same group or different groups respectively. For example, when r is 2 or 3, the two or three Rb bonded to the same benzene ring may be the same group or different groups respectively. Rb represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group (alkoxy group) having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group (thiol group). In addition, r represents an integer of 0 to 3.

[0038] The number of carbon atoms in the formula (1) is not particularly limited as long as it is 6 or more. From the viewpoint of maintaining a high Tg, it is more preferably 6 or more and 20 or less.

[0039] In a preferred embodiment, the hydrocarbon compound of the present embodiment contains a hydrocarbon compound (A1) represented by the following formula (2).

[0040]

[0041] In formula (2), n represents an integer of 1 to 10.

[0042] It is considered that by containing the hydrocarbon compound (A1), the above-described effects can be obtained more reliably.

[0043] <Polyphenylene ether compound (B)>

[0044] As the polyphenylene ether compound (B), a polyphenylene ether compound having a reactive carbon-carbon unsaturated double bond is used. Since it is preferable to use, for example, a terminally modified polyphenylene ether compound that exhibits excellent low dielectric characteristics after curing, it is preferable to use a modified polyphenylene ether compound in which the terminal is modified with a substituent having a carbon-carbon unsaturated double bond as the polyphenylene ether compound (B).

[0045] As a substituent having a carbon-carbon unsaturated double bond, groups representing a styrene structure or a (meth)acrylate structure represented by the following formula (4) or (5) can be exemplified.

[0046]

[0047] In formula (5), R 1 represents a hydrogen atom or an alkyl group. The alkyl group is not particularly limited, and is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms. Specifically, for example, methyl, ethyl, propyl, hexyl, decyl, etc. can be exemplified.

[0048] More specifically, as the substituent, vinylbenzyl (vinylbenzyl) such as p-vinylbenzyl and m-vinylbenzyl, vinylphenyl, acrylate group, methacrylate group, etc. can be exemplified.

[0049] It is considered that by using this modified polyphenylene ether compound, low dielectric properties such as low dielectric constant and low dielectric loss factor and excellent heat resistance can be maintained, and high Tg and adhesion can also be improved.

[0050] It should be noted that the modified polyphenylene ether compound can be used alone - one kind, or two or more kinds can be used in combination.

[0051] In the present embodiment, the weight average molecular weight (Mw) of the modified polyphenylene ether compound used as the thermosetting resin is not particularly limited, and is preferably 1000 to 5000, more preferably 1000 to 4000. It should be noted that here, the weight average molecular weight is only a value obtained by measuring by a usual molecular weight measurement method, and specifically, a value measured by gel permeation chromatography (GPC) etc. can be exemplified. In addition, when the modified polyphenylene ether compound has repeating units (s, m, n) in the molecule, these repeating units are preferably values that make the weight average molecular weight of the modified polyphenylene ether compound fall within this range.

[0052] If the weight-average molecular weight of the modified polyphenylene ether compound is within the above range, the modified polyphenylene ether compound not only has excellent low dielectric properties possessed by the polyphenylene ether backbone, but also has more excellent heat resistance of the cured product and excellent moldability. It is considered that this is based on the following reasons. When compared with ordinary polyphenylene ether, if the weight-average molecular weight is within the above-mentioned range, the molecular weight is lower, so there is a tendency for the heat resistance of the cured product to decrease. Regarding this point, it is considered that: the modified polyphenylene ether compound of the present embodiment has a styrene structure or a (meth)acrylate structure at the end, so it has high reactivity, and the cured product can obtain sufficiently high heat resistance. In addition, it is considered that: if the weight-average molecular weight of the modified polyphenylene ether compound is within the above-mentioned range, although the molecular weight is higher than that of styrene or divinylbenzene, it is lower than that of general polyphenylene ether, so the moldability is also excellent. Therefore, it is considered that the modified polyphenylene ether compound can obtain the effects of not only more excellent heat resistance of the cured product but also excellent moldability.

[0053] In addition, regarding the average number (terminal functional group number) of the substituents possessed by each molecule of the modified polyphenylene ether in the modified polyphenylene ether compound used as the thermosetting resin in the present embodiment at the molecular end, there is no particular limitation. Specifically, it is preferably 1 to 5, more preferably 1 to 3. If the number of terminal functional groups is too small, there is a tendency that it is difficult to obtain a cured product with sufficient heat resistance. In addition, if the number of terminal functional groups is too large, the reactivity becomes too high, and for example, there may be adverse conditions such as a decrease in the storage stability of the resin composition or a decrease in the fluidity of the resin composition. That is, if this modified polyphenylene ether is used, there is a risk of forming problems such as moldability problems due to insufficient fluidity, for example, forming defects such as voids during multi-layer forming, and it is difficult to obtain a printed wiring board with high reliability.

[0054] It should be noted that the number of terminal functional groups of the modified polyphenylene ether compound may include: a numerical value representing the average value of the substituents of each molecule of all the modified polyphenylene ether compounds present in 1 mole of the modified polyphenylene ether compound, etc. The number of terminal functional groups can be measured, for example, by measuring the number of remaining hydroxyl groups in the obtained modified polyphenylene ether compound and calculating the reduction amount compared with the number of hydroxyl groups of the polyphenylene ether before modification. The reduction amount compared with the number of hydroxyl groups of the polyphenylene ether before modification is the number of terminal functional groups. And, the method for measuring the number of remaining hydroxyl groups in the modified polyphenylene ether compound can be obtained by adding a quaternary ammonium salt (tetraethylammonium hydroxide) associated with hydroxyl groups to a solution of the modified polyphenylene ether compound and measuring the UV absorbance of the mixed solution.

[0055] In addition, the intrinsic viscosity of the modified polyphenylene ether compound used in the present embodiment is not particularly limited. Specifically, it may be 0.03 to 0.12 dl / g, preferably 0.04 to 0.11 dl / g, and more preferably 0.06 to 0.095 dl / g. If the intrinsic viscosity is too low, there is a tendency for the molecular weight to be low, and it is difficult to obtain low dielectric properties such as a low dielectric constant and a low dielectric loss factor. In addition, if the intrinsic viscosity is too high, the viscosity is high, it is difficult to obtain sufficient fluidity, and there is a tendency for the formability of the cured product to decrease. Therefore, as long as the intrinsic viscosity of the modified polyphenylene ether compound is within the above range, excellent heat resistance and formability of the cured product can be achieved.

[0056] It should be noted that the intrinsic viscosity here refers to the intrinsic viscosity measured in dichloromethane at 25°C. More specifically, for example, it is a value obtained by measuring a 0.18 g / 45 ml dichloromethane solution (liquid temperature 25°C) with a viscometer. As such a viscometer, for example, AVS500 Visco System manufactured by Schott can be cited.

[0057] It should be noted that the polyphenylene ether compound used in the resin composition of the present embodiment can be synthesized by a known method or a commercially available product can be used. As commercially available products, for example, "OPE-2st 1200" and "OPE-2st 2200" manufactured by Mitsubishi Gas Chemical Company, Inc., and "SA9000" manufactured by SABIC Innovative Plastics can be cited.

[0058] <Polyfunctional vinyl aromatic polymer (C)>

[0059] The resin composition of the present embodiment contains, in addition to the above components (A) and (B), at least one selected from polyfunctional vinyl aromatic polymer (C) and acenaphthylene compound (D) described later. By containing at least one selected from polyfunctional vinyl aromatic polymer (C) and acenaphthylene compound (D), the resin composition of the present embodiment can more reliably obtain the effects of low dielectric properties and low thermal expansion properties as described above.

[0060] In particular, by containing polyfunctional vinyl aromatic polymer (C), it has more excellent dielectric properties. In addition, by containing acenaphthylene compound (D) described later, it has the advantages of more excellent low thermal expansion property, heat resistance, and a higher glass transition temperature. Moreover, it is considered that the adhesion is more excellent.

[0061] In addition, the resin composition of the present embodiment may contain both polyfunctional vinyl aromatic polymer (C) and acenaphthylene compound (D). In this case, a cured product that equally has the above-described effects (low dielectric properties, low thermal expansion property, high Tg, and heat resistance) can be obtained.

[0062] The polyfunctional vinyl aromatic copolymer (B) contains a repeating unit (a) derived from a divinyl aromatic compound and a repeating unit (b) derived from a monovinyl aromatic compound, and also contains a repeating unit (a1) represented by the following formula (a1) as a part of the repeating unit (a) derived from the divinyl aromatic compound.

[0063]

[0064] In formula (a1), R 2 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0065] In the polyfunctional vinyl aromatic copolymer (B), when the total of the repeating unit (a) and the repeating unit (b) is set to 100 mol%, it contains 2 mol% or more and less than 95 mol% of the repeating unit (a), and contains 5 mol% or more and less than 98 mol% of the repeating unit (b). And, when the total of the repeating unit (a) and (b) is set to 100 mol%, it contains 2 to 80 mol% of the repeating unit (a1).

[0066] The number-average molecular weight Mn of the polyfunctional vinyl aromatic copolymer (B) is 300 to 100,000, and the molecular weight distribution represented by the ratio of the weight-average molecular weight Mw to the number-average molecular weight is preferably 100.0 or less. Further, it is preferably soluble in toluene, xylene, tetrahydrofuran, dichloroethane, or chloroform.

[0067] The polyfunctional vinyl aromatic copolymer (B) is not particularly limited, and examples thereof include copolymers containing structural units derived from the repeating unit (a) and the repeating unit (b), etc. The repeating unit (a) is derived from a divinyl aromatic compound represented by the following formula (6), and the repeating unit (b) is derived from a monovinyl aromatic compound, etc. These structural units may be regularly arranged or randomly arranged.

[0068]

[0069] In formula (6), R 3 is an aromatic hydrocarbon group having 6 to 30 carbon atoms derived from a monovinyl aromatic compound, and R 4 is an aromatic hydrocarbon group having 6 to 30 carbon atoms derived from a divinyl aromatic compound, and h to k are each independently an integer of 0 to 200 on the condition that their sum is 2 to 20,000.

[0070] Preferably, the polyfunctional vinyl aromatic copolymer (B) is one in which R 3 and R 4A copolymer formed from repeating units of an aromatic hydrocarbon group selected from the group consisting of a phenyl group which may have a substituent, a biphenyl group which may have a substituent, a naphthyl group which may have a substituent, and a terphenyl group which may have a substituent, and the like.

[0071] The polyfunctional vinyl aromatic copolymer (B) is preferably soluble in a solvent. In addition, the repeating units described in the present specification are derived from monomers and include units present in the main chain of the copolymer and repeating units, and units or end groups present in the terminal or side chain. The repeating units are also referred to as structural units.

[0072] Relative to the total of the divinyl aromatic compound and the structural unit (b) derived from the monovinyl aromatic compound, the structural unit (a) derived from the divinyl aromatic compound preferably contains 2 mol% or more and less than 95 mol%. The structural unit (a) derived from the divinyl aromatic compound may have multiple structures such as a structure in which only one of the two vinyl groups reacts and a structure in which both react. Among them, relative to the above total, it preferably contains 2 to 80 mol% of the repeating unit in which only one vinyl group represented by the above formula (a1) reacts, more preferably 5 to 70 mol%, still more preferably 10 to 60%, and particularly preferably 15 to 50%. It is considered that by setting it to 2 to 80 mol%, the dielectric loss factor is low, the heat resistance is excellent, and the compatibility with other resins is excellent. If it is less than 2 mol%, the heat resistance tends to decrease, and if it exceeds 80 mol%, the adhesion strength tends to decrease.

[0073] Relative to the above total, the polyfunctional vinyl aromatic copolymer (B) preferably contains 5 mol% or more and less than 98 mol% of the structural unit (b) derived from the monovinyl aromatic compound. More preferably, it contains 10 mol% or more and less than 90 mol%. Still more preferably 15 mol% or more and less than 85 mol%. If it is less than 5 mol%, the formability may be insufficient, and if it exceeds 98 mol%, the heat resistance of the cured product may be insufficient.

[0074] The vinyl group present in the above formula (a1) acts as a crosslinking component and contributes to the heat resistance of the polyfunctional vinyl aromatic copolymer (B). On the other hand, it is considered that the structural unit (b) derived from the monovinyl aromatic compound is usually polymerized by the 1,2-addition reaction of the vinyl group and thus does not have a vinyl group. That is, the structural unit (b) derived from the monovinyl aromatic compound does not act as a crosslinking component but contributes to the formability.

[0075] As the monovinyl aromatic compound, styrene is preferably cited. In addition, a monovinyl aromatic compound other than styrene may also be used together with styrene. In this case, when the total content of the structural unit (b1) derived from styrene and the structural unit (b2) derived from a monovinyl aromatic compound other than styrene is set to 100 mol%, the content of the structural unit (b1) derived from styrene is preferably 99 to 20 mol%. More preferably, it is 98 to 30 mol%. If the content of (b1) is within the above range, heat-resistant oxidative deterioration resistance and moldability are both achieved, so it is preferred. When the structural unit (b1) is more than 99 mol%, there is a tendency for the heat resistance to decrease, and when the structural unit (b2) is more than 80 mol%, there is a tendency for the moldability to decrease.

[0076] The number average molecular weight of the polyfunctional vinyl aromatic copolymer (B) (number average molecular weight in terms of standard polystyrene measured by GPC) is preferably 300 to 100,000, more preferably 400 to 50,000, and further preferably 500 to 10,000. If Mn is less than 300, the amount of the monofunctional copolymer component contained in the polyfunctional vinyl aromatic copolymer (B) increases, so there is a tendency for the heat resistance of the cured product to decrease. In addition, if Mn exceeds 100,000, gels are likely to be formed and the viscosity increases, so there is a tendency for the molding processability to decrease. In addition, the value of the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (weight average molecular weight in terms of standard polystyrene measured by GPC) to Mn is 100.0 or less, preferably 50.0 or less, more preferably 1.5 to 30.0, and most preferably 2.0 to 20.0. If Mw / Mn exceeds 100.0, there is a tendency for the processing characteristics of the polyfunctional vinyl aromatic copolymer (B) to deteriorate and gels are likely to occur.

[0077] The divinyl aromatic compound functions to form a branched structure to make the copolymer polyfunctional, and when the obtained polyfunctional vinyl aromatic copolymer (B) is thermally cured, it functions as a crosslinking component for developing heat resistance. As an example of the divinyl aromatic compound, there is no limitation as long as it is an aromatic having two vinyl groups. Divinylbenzene (including positional isomers or a mixture thereof), divinylnaphthalene (including positional isomers or a mixture thereof), and divinylbiphenyl (including positional isomers or a mixture thereof) are preferably used. In addition, these can be used alone or in combination of two or more. From the viewpoint of molding processability, divinylbenzene (meta-isomer, para-isomer or a mixture of their positional isomers) is more preferred.

[0078] Examples of the monovinyl aromatic compound include styrene and a monovinyl aromatic compound other than styrene. However, styrene is preferably an essential component, and a monovinyl aromatic compound other than styrene is used simultaneously.

[0079] Styrene, as a monomer component, serves to impart low dielectric properties and heat-oxidative degradation resistance to the polyfunctional vinyl aromatic copolymer (B), and also serves as a chain transfer agent to control the molecular weight of the polyfunctional vinyl aromatic copolymer (B). In addition, monovinyl aromatic compounds other than styrene improve the solvent solubility and processability of the polyfunctional vinyl aromatic copolymer (B).

[0080] Examples of the monovinyl aromatic compounds other than styrene are not limited as long as they are aromatics other than styrene having one vinyl group, and include vinyl aromatic compounds such as vinylnaphthalene and vinylbiphenyl; nucleus-alkyl-substituted vinyl aromatic compounds such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, and p-ethylvinylbenzene. Since the effect of preventing gelation of the polyfunctional vinyl aromatic copolymer (B), improving solvent solubility and processability is high, the cost is low and it is easily available, ethyl vinylbenzene (including each positional isomer or a mixture thereof), ethyl vinylbiphenyl (including each positional isomer or a mixture thereof), or ethyl vinylnaphthalene (including each positional isomer or a mixture thereof) is preferably used. From the viewpoints of dielectric properties and cost, ethyl vinylbenzene (meta-isomer, para-isomer or a mixture of their positional isomers) is more preferably used.

[0081] In addition, within the range that does not impair the effects of the present invention, other monomer components such as trivinyl aromatic compounds, trivinyl aliphatic compounds, divinyl aliphatic compounds, and monovinyl aliphatic compounds can be used singly or in combination of two or more, and structural units (c) derived from them are introduced into the polyfunctional vinyl aromatic copolymer (B).

[0082] Examples of the above other monomer components include, for example, 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, 1,2,4-trivinylcyclohexane, ethylene glycol diacrylate, butadiene, 1,4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, triallyl isocyanurate, etc. These can be used alone or in combination of two or more.

[0083] The mole fraction of the other monomer components is preferably less than 30 mol% relative to the total of all monomer components. That is, the mole fraction of the repeating unit (c) derived from the other monomer components relative to the total of the structural units (a), (b), and (c) derived from all monomer components constituting the copolymer is preferably less than 30 mol%.

[0084] <Acenaphthylene compound (D)>

[0085] As long as the acenaphthylene compound (D) is a compound having an acenaphthylene structure in the molecule, it can be used without particular limitation. Examples of the acenaphthylene compound (D) include acenaphthylene, alkyl acenaphthylenes, halogenated acenaphthylenes, phenyl acenaphthylenes, and the like.

[0086] Examples of the alkyl acenaphthylenes include 1-methylacenaphthylene, 3-methylacenaphthylene, 4-methylacenaphthylene, 5-methylacenaphthylene, 1-ethylacenaphthylene, 3-ethylacenaphthylene, 4-ethylacenaphthylene, 5-ethylacenaphthylene, and the like. Examples of the halogenated acenaphthylenes include 1-chloroacenaphthylene, 3-chloroacenaphthylene, 4-chloroacenaphthylene, 5-chloroacenaphthylene, 1-bromoacenaphthylene, 3-bromoacenaphthylene, 4-bromoacenaphthylene, 5-bromoacenaphthylene, and the like. Examples of the phenyl acenaphthylenes include 1-phenylacenaphthylene, 3-phenylacenaphthylene, 4-phenylacenaphthylene, 5-phenylacenaphthylene, and the like. The acenaphthylene compound may be a monofunctional acenaphthylene compound having one acenaphthylene structure in the molecule as described above, or a polyfunctional acenaphthylene compound having two or more acenaphthylene structures in the molecule.

[0087] (Content)

[0088] In the resin composition of the present embodiment, with respect to a total of 100 parts by mass of the hydrocarbon compound (A), the polyphenylene ether compound (B), the polyfunctional vinyl aromatic copolymer (C), and the acenaphthylene compound (D), the content of the hydrocarbon compound (A) is preferably 5 to 50 parts by mass. It is considered that if it is within this range, the effects of the present invention as described above can be obtained more reliably. The more preferred range is 15 parts by mass or more and 50 parts by mass or less.

[0089] In addition, with respect to a total of 100 parts by mass of the hydrocarbon compound (A), the polyphenylene ether compound (B), the polyfunctional vinyl aromatic copolymer (C), and the acenaphthylene compound (D), the content of the polyphenylene ether compound (B) in the resin composition of the present embodiment is preferably 5 to 50 parts by mass. It is considered that if it is within this range, the effects of the present invention as described above can be obtained more reliably. The more preferred range is 15 parts by mass or more and 35 parts by mass or less.

[0090] In addition, with respect to a total of 100 parts by mass of the hydrocarbon compound (A), the polyphenylene ether compound (B), the polyfunctional vinyl aromatic copolymer (C), and the acenaphthylene compound (D), the content of the polyfunctional vinyl aromatic copolymer (C) in the resin composition of the present embodiment is preferably 0 to 50 parts by mass. It is considered that if it is within this range, the effects of the present invention as described above can be obtained more reliably. The more preferred range is 10 parts by mass or more and 40 parts by mass or less.

[0091] In addition, with respect to a total of 100 parts by mass of the hydrocarbon compound (A), the polyphenylene ether compound (B), the polyfunctional vinyl aromatic copolymer (C), and the acenaphthylene compound (D), the content of the acenaphthylene compound (D) in the resin composition of the present embodiment is preferably 0 to 30 parts by mass. It is considered that if it is within this range, the effects of the present invention as described above can be obtained more reliably. The more preferable range is 10 parts by mass or more and 25 parts by mass or less.

[0092] (Inorganic filler)

[0093] The resin composition according to the present embodiment may further contain an inorganic filler. Examples of the inorganic filler include substances added to improve the heat resistance and flame retardancy of the cured product of the resin composition, and there is no particular limitation. It is considered that by containing an inorganic filler, the heat resistance and flame retardancy can be further improved, and the coefficient of thermal expansion can be suppressed to a lower level (lower thermal expansibility) can be achieved.

[0094] Specific examples of the inorganic filler that can be used in the present embodiment include, for example, metal oxides such as silica, alumina, titanium oxide, magnesium oxide, and mica; metal hydroxides such as magnesium hydroxide and aluminum hydroxide; talc; aluminum borate, barium sulfate, aluminum nitride, and boron nitride; barium titanate, strontium titanate, calcium titanate, aluminum titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate; magnesium carbonate such as anhydrous magnesium carbonate and calcium carbonate; and their boehmite-treated products. Among them, metal hydroxides such as silica, magnesium hydroxide, and aluminum hydroxide, alumina, boron nitride, and barium titanate, strontium titanate, etc. are preferred, and silica is more preferred. The silica is not particularly limited, and examples thereof include pulverized silica, spherical silica, and silica particles.

[0095] These inorganic fillers can be used alone or in combination of two or more. In addition, the inorganic filler as described above can be used directly, or an inorganic filler surface-treated with a silane coupling agent of epoxy silane type, vinyl silane type, methacryloyl silane type, phenylamino silane type, or amino silane type can be used. As the silane coupling agent, a method of adding by bulk blending can be adopted instead of the method of pre-surface-treating the filler material.

[0096] When the resin composition of the present embodiment contains an inorganic filler, with respect to a total of 100 parts by mass of the hydrocarbon compound (A), the polyphenylene ether compound (B), the polyfunctional vinyl aromatic copolymer (C), and the acenaphthylene compound (D), the content of the inorganic filler is preferably 10 to 300 parts by mass, more preferably 40 to 250 parts by mass.

[0097] (Flame retardant)

[0098] The resin composition according to this embodiment may further contain a flame retardant. By containing the flame retardant, the flame retardancy of the cured product of the resin composition can be further improved.

[0099] The flame retardant that can be used in this embodiment is not particularly limited. Specifically, in the field of using halogen-based flame retardants such as bromine-based flame retardants, preferably, for example: ethylenedipentabromobenzene with a melting point of 300 °C or higher, ethylenebistetrabromoimide, decabromodiphenyl ether, and tetradecabromodiphenoxybenzene. It is considered that by using halogen-based flame retardants, the detachment of halogens at high temperatures can be suppressed, and the reduction of heat resistance can be suppressed. In addition, in fields where halogen-free is required, a phosphorus-containing flame retardant (phosphorus-based flame retardant) is sometimes used. The phosphorus-based flame retardant is not particularly limited, and examples thereof include: HCA-based flame retardants, phosphate ester-based flame retardants, phosphazene-based flame retardants, bisdiphenylphosphine-based flame retardants, and phosphinate-based flame retardants. Specific examples of the HCA-based flame retardant include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, or a compound obtained by previously reacting them. Specific examples of the phosphate ester-based flame retardant include a polycondensed phosphate ester of bisxylenyl phosphate. Specific examples of the phosphazene-based flame retardant include phenoxyphosphazene. Specific examples of the bisdiphenylphosphine-based flame retardant include xylylene bis(diphenylphosphine). Specific examples of the phosphinate-based flame retardant include a metal phosphinate of dialkylaluminum phosphinate. As the flame retardant, each of the exemplified flame retardants can be used alone, or two or more of them can be used in combination.

[0100] When the resin composition of this embodiment contains a flame retardant, the content of the flame retardant is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, based on 100 parts by mass of the total mass of the resin composition excluding the inorganic filler.

[0101] <Other components>

[0102] The resin composition according to this embodiment may also contain components other than the above components (other components) as needed within the range that does not impair the effects of the present invention. As other components contained in the resin composition according to this embodiment, for example, radical polymerizable compounds, styrene-based elastomers, catalysts such as reaction initiators and reaction promoters, silane coupling agents, polymerization retarders, polymerization inhibitors, flame retardant aids, defoaming agents, homogenizers, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes or pigments, dispersants, and lubricants and other additives may also be contained.

[0103] (Radical polymerizable compound)

[0104] The radical polymerizable compound that can be used in this embodiment is not particularly limited as long as it is a radical polymerizable compound that reacts with at least one of the above components (A) to (D). Examples thereof include vinyl compounds, allyl compounds, acrylate compounds, methacrylate compounds, and maleimide compounds.

[0105] The vinyl compound that can be used in this embodiment is a compound having a vinyl group in the molecule, and examples thereof include polyfunctional vinyl compounds having two or more vinyl groups in the molecule. As the polyfunctional vinyl compound, for example, divinylbenzene, curable polybutadiene having a carbon-carbon unsaturated double bond in the molecule, and curable butadiene-styrene copolymer having a carbon-carbon unsaturated double bond in the molecule can be cited.

[0106] The allyl compound that can be used in this embodiment is a polyfunctional allyl compound having two or more allyl groups in the molecule, and examples thereof include triallyl isocyanurate (TAIC) and other triallyl isocyanurate compounds, diallyl bisphenol compounds, and diallyl phthalate (DAP).

[0107] The acrylate compound that can be used in this embodiment is a compound having an acryloyl group in the molecule, and examples thereof include polyfunctional acrylate compounds having two or more acryloyl groups in the molecule. As the polyfunctional acrylate compound, for example, dacrylate compounds such as tricyclodecane dimethanol diacrylate can be cited.

[0108] The methacrylate compound that can be used in this embodiment is a compound having a methacryloyl group in the molecule, and examples thereof include polyfunctional methacrylate compounds having two or more methacryloyl groups in the molecule. As the polyfunctional methacrylate compound, for example, dimethacrylate compounds such as tricyclodecane dimethanol dimethacrylate (DCP) can be cited.

[0109] As the maleimide compound that can be used in the present embodiment, any compound having a maleimide group in the molecule can be used without particular limitation. Specifically, examples of the maleimide compound include: monofunctional maleimide compounds having one maleimide group in the molecule, polyfunctional maleimide compounds having two or more maleimide groups in the molecule, and modified maleimide compounds. Examples of the polyfunctional maleimide compounds include: aromatic maleimide compounds containing an aromatic group in the molecule, maleimide compounds containing an imide group having an imide group in the molecule, aliphatic maleimide compounds containing a long-chain alkyl group in the molecule, maleimide compounds containing an indane structure in the molecule, and maleimide compounds having an arylene structure bonded in a meta-orientation in the molecule. Examples of the modified maleimide compounds include, for example: modified maleimide compounds in which a part of the molecule is modified with an amine compound, modified maleimide compounds in which a part of the molecule is modified with a silicone compound, and modified maleimide compounds in which a part of the molecule is modified with an amine compound and a silicone compound.

[0110] (Styrene-based elastomer)

[0111] The styrene-based elastomer that can be used in the present embodiment is a polymer obtained by polymerizing monomers containing styrene-based monomers and can be a styrene-based copolymer. In addition, examples of the styrene-based copolymer include copolymers obtained by copolymerizing one or more of the above-mentioned styrene-based monomers and one or more other monomers copolymerizable with the styrene-based monomers. As long as the styrene-based copolymer has a structure derived from the styrene-based monomer in the molecule, it can be a random copolymer or a block copolymer. Examples of the block copolymer include binary copolymers of a structure (repeating unit) derived from the styrene-based monomer and the other copolymerizable monomer (repeating unit), and ternary copolymers of a structure (repeating unit) derived from the styrene-based monomer, the other copolymerizable monomer (repeating unit), and a structure (repeating unit) derived from the styrene-based monomer.

[0112] The styrene-based elastomer can also be a hydrogenated styrene-based copolymer obtained by hydrogenating the styrene-based copolymer.

[0113] The styrene-based elastomer can be used alone as one kind of styrene-based polymer or two or more kinds can be used in combination.

[0114] As the styrenic elastomer, commercially available products can also be used, such as "SEPTON (registered trademark) V9827", "SEPTON (registered trademark) 2063", etc. manufactured by Kuraray Co., Ltd.; "FTR (registered trademark) 2140", "FTR (registered trademark) 6125", etc. manufactured by Mitsui Chemicals, Inc.; "Tuftec (registered trademark) H1517" manufactured by Asahi Kasei Corporation; and "Dynaron (registered trademark) 9901P" manufactured by JSR Corporation.

[0115] The resin composition according to the present embodiment may contain a reaction initiator (catalyst) and a reaction accelerator as described above. The reaction initiator and the reaction accelerator are not particularly limited as long as they can promote the curing reaction of the resin composition. Specifically, for example, metal oxides, azo compounds, peroxides, imidazole compounds, phosphorus-based curing accelerators, amine-based curing accelerators, etc. can be cited.

[0116] (Prepreg, resin-coated film, metal-clad laminate, wiring board, and resin-coated metal foil)

[0117] Next, the prepreg, metal-clad laminate, wiring board, and resin-coated metal foil for wiring boards using the resin composition of the present embodiment will be described.

[0118] Figure 1 It is a schematic cross-sectional view showing an example of the prepreg 1 according to the embodiment of the present invention. In addition, each symbol in the figure represents the following: 1 prepreg, 2 resin composition or semi-cured product of the resin composition, 3 fibrous substrate, 11 metal-clad laminate, 12 insulating layer, 13 metal foil, 14 wiring, 21 wiring board, 31 resin-coated metal foil, 32, 42 resin layer, 41 resin-coated film, 43 support film.

[0119] As Figure 1 shown, the prepreg 1 according to the present embodiment includes: the resin composition or the semi-cured product of the resin composition 2; and a fibrous substrate 3. As the prepreg 1, a prepreg in which the fibrous substrate 3 is present in the resin composition or its semi-cured product 2 can be cited. That is, the prepreg 1 includes: the resin composition or its semi-cured product; and the fibrous substrate 3 present in the resin composition or its semi-cured product 2.

[0120] It should be noted that in this embodiment, the "semi-cured product" is a substance in a state where the resin composition is cured halfway to a degree where it can still be further cured. That is, the semi-cured product is a substance in a state where the resin composition is semi-cured (B-stage). For example, if the resin composition is heated, the viscosity initially decreases slowly and then starts to cure, and the viscosity slowly increases. In this case, examples of semi-curing include the state during the period from when the viscosity starts to increase until just before complete curing.

[0121] As the prepreg obtained by using the resin composition according to this embodiment, as described above, it can be a prepreg having a semi-cured product of the resin composition, or it can also be a prepreg having the uncured resin composition. That is, it can be a prepreg having a semi-cured product (B-stage resin composition) of the resin composition and a fibrous substrate, or it can be a prepreg having the resin composition before curing (A-stage resin composition) and a fibrous substrate. Specifically, for example, a prepreg in which a fibrous substrate is present in the resin composition can be cited. It should be noted that the resin composition or its semi-cured product can be a substance obtained by heating and drying the resin composition.

[0122] When manufacturing the prepreg, the resin-coated metal foil, the metal-clad laminate described later, etc., the resin composition according to this embodiment is mostly prepared in the form of a varnish and used in the form of a resin varnish. This resin varnish can be prepared, for example, as follows.

[0123] First, each component that can be dissolved in an organic solvent, such as a resin component and a reaction initiator, is put into an organic solvent and dissolved. At this time, heating can be performed as needed. Then, an inorganic filler or the like, which is a component insoluble in the organic solvent, is added and dispersed to a specified dispersed state using a ball mill, a bead mill, a planetary mixer, a roll mill, etc., thereby preparing a resin composition in the form of a varnish. As the organic solvent used here, as long as it can dissolve the hydrocarbon compound (A), the polyphenylene ether compound (B), the polyfunctional vinyl aromatic copolymer (C), the acenaphthylene compound (D), etc. and does not hinder the curing reaction, there is no particular limitation. Specifically, for example, toluene, methyl ethyl ketone, cyclohexanone, cyclopentanone, methylcyclohexane, dimethylformamide, and propylene glycol monomethyl ether acetate can be cited. These can be used alone or in combination of two or more.

[0124] As a method for manufacturing the prepreg 1 of this embodiment using the resin composition in the form of a varnish of this embodiment, for example, a method of impregnating the resin composition 2 in the form of a resin varnish into the fibrous substrate 3 and then drying it can be cited.

[0125] As the fibrous substrate used in manufacturing prepregs, specific examples include, for example: glass cloth, aramid cloth, polyester cloth, LCP (liquid crystal polymer) non-woven fabric, glass non-woven fabric, aramid non-woven fabric, polyester non-woven fabric, pulp paper, and cotton linter paper, etc. It should be noted that when using glass cloth, a laminate with excellent mechanical strength can be obtained, and in particular, glass cloth processed by flattening treatment is preferably used. As the glass cloth used in this embodiment, there is no particular limitation, and examples include glass cloth such as E glass, S glass, NE glass, Q glass, and L glass, etc. As the flattening treatment, specifically, for example, it can be carried out by continuously pressing the glass cloth with a pressure roller at an appropriate pressure to compress the yarns into a flat shape. It should be noted that as the thickness of the fibrous substrate, a fibrous substrate with a thickness of, for example, 0.01 to 0.3 mm is usually used.

[0126] The impregnation of the resin varnish (resin composition 2) into the fibrous substrate 3 is carried out by impregnation and coating, etc. This impregnation can also be repeated multiple times as needed. In addition, at this time, multiple resin varnishes with different compositions and concentrations can also be used to repeat the impregnation, so as to finally adjust to the desired composition (content ratio) and resin amount.

[0127] The fibrous substrate 3 impregnated with the resin varnish (resin composition 2) is heated under desired heating conditions, for example, heated at 80°C or higher and 180°C or lower for 1 minute or more and 10 minutes or less. By heating, the solvent is volatilized from the varnish to reduce or remove the solvent, and a prepreg 1 in a pre-cured (A-stage) or semi-cured state (B-stage) is obtained.

[0128] In addition, as Figure 4 shown, the resin-coated metal foil 31 of this embodiment has the following structure: a structure in which a resin layer 32 containing the above-mentioned resin composition or a semi-cured product of the resin composition and a metal foil 13 are laminated. That is, the resin-coated metal foil of this embodiment can be a resin-coated metal foil having: a resin layer containing the resin composition before curing (the resin composition in the A-stage); and a metal foil, or can be a resin-coated metal foil having: a resin layer containing a semi-cured product of the resin composition (the resin composition in the B-stage); and a metal foil.

[0129] As a method for manufacturing the resin-coated metal foil 31, the following methods can be listed as examples: a method of coating the resin composition in the form of a resin varnish as described above on the surface of a metal foil 13 such as a copper foil, and then drying it. As the coating method, a bar coater, comma coater, die coater, roll coater, gravure coater, etc. can be cited.

[0130] As the metal foil 13, the metal foil used for metal-clad laminates, wiring boards, etc. can be used without limitation, and examples include copper foil and aluminum foil, etc.

[0131] In addition, as Figure 5 shown, the resin-containing film 41 of the present embodiment has the following structure: a structure in which a resin layer 42 containing the resin composition or a semi-cured product of the resin composition and a film support substrate 43 are laminated. That is, the resin-containing film of the present embodiment may be a resin-containing film having: the resin composition before curing (the resin composition in the A-stage); and a film support substrate, or may be a resin-containing film having: a semi-cured product of the resin composition (the resin composition in the B-stage); and a film support substrate.

[0132] As a method for manufacturing the resin-containing film 41, for example, after coating the resin composition in the form of a resin varnish as described above on the surface of the film support substrate 43, the solvent is volatilized from the varnish to reduce or remove the solvent, whereby a resin-containing film in a pre-cured state (A-stage) or a semi-cured state (B-stage) can be obtained.

[0133] Examples of the film support substrate include electrically insulating films such as polyimide films, PET (polyethylene terephthalate) films, polyethylene naphthalate films, polyester films, polyisophthalic acid films, polyether ether ketone films, polyphenylene sulfide films, aramid films, polycarbonate films, and polyarylate films.

[0134] It should be noted that for the resin-containing film and the resin-containing metal foil of the present embodiment, similar to the above-described prepreg, the resin composition or its semi-cured product may be a resin composition or its semi-cured product obtained by drying or heat-drying the resin composition.

[0135] The thicknesses of the above-mentioned metal foil 13 and film support substrate 43 can be appropriately set according to the desired purpose. For example, as the metal foil 13, a metal foil of about 0.2 to 70 μm can be used. In the case where the thickness of the metal foil is, for example, 10 μm or less, in order to improve the operability, a copper foil with a release layer and a carrier can be used. By applying the resin varnish to the metal foil 13 and the film support substrate 43 by coating or the like, if necessary, this operation can be repeated multiple times. In addition, at this time, multiple resin varnishes having different compositions and concentrations can also be used to repeatedly perform coating, so as to finally adjust to the desired composition (content ratio) and resin amount.

[0136] Regarding the drying or heat-drying conditions in the methods for manufacturing the resin-containing metal foil 31 and the resin-containing film 41, there are no particular limitations. After coating the resin composition in the form of a resin varnish on the above-mentioned metal foil 13 and film support substrate 43, it is heated under desired heating conditions, for example, at 50 to 180 °C for about 0.1 to 10 minutes, so that the solvent is volatilized from the varnish to reduce or remove the solvent, thereby obtaining the resin-containing metal foil 31 and the resin-containing film 41 in a pre-cured state (A-stage) or a semi-cured state (B-stage).

[0137] The metal foil 31 with resin and the film 41 with resin may be provided with a covering film or the like as needed. By providing a covering film, the intrusion of foreign substances and the like can be prevented. As the covering film, there is no particular limitation as long as it can be peeled off without damaging the form of the resin composition, and for example, a polyolefin film, a polyester film, a TPX film, a film formed by providing a release agent layer on these films, and paper obtained by laminating these films on a paper substrate can be used.

[0138] As Figure 2 shown, the metal-clad laminate 11 of the present embodiment includes: an insulating layer 12 containing a cured product of the above-described resin composition or a cured product of the above-described prepreg; and a metal foil 13. It should be noted that, as the metal foil 13 for the metal-clad laminate 11, the same metal foil as the above-described metal foil 13 can be used.

[0139] In addition, the metal-clad laminate 11 of the present embodiment can also be produced using the above-described metal foil 31 with resin or the film 41 with resin.

[0140] Regarding the method of producing a metal-clad laminate using the prepreg 1, the metal foil 31 with resin, and the film 41 with resin obtained through the above operations, by taking one piece or overlapping multiple pieces of the prepreg 1, the metal foil 31 with resin, and the film 41 with resin, and further overlapping a metal foil 13 such as a copper foil on the upper and lower two surfaces or one surface thereof, and subjecting it to hot pressing and forming for lamination and integration, a laminate with metal foils on both surfaces or one surface is produced. The hot pressing conditions can be appropriately set according to the thickness of the laminate to be manufactured, the type of the resin composition, etc. For example, the temperature can be set to 170 to 230 °C, the pressure can be set to 1.5 to 5.0 MPa, and the time can be set to 60 to 150 minutes.

[0141] In addition, the metal-clad laminate 11 can also be produced without using the prepreg 1 or the like by forming a film-like resin composition on the metal foil 13 and performing hot pressing.

[0142] In addition, as Figure 3 shown, the wiring board 21 of the present embodiment includes: an insulating layer 12 containing a cured product of the above-described resin composition or a cured product of the above-described prepreg; and a wiring 14.

[0143] The resin composition of the present embodiment is suitable for use as a material for an insulating layer of a wiring board. As a method for manufacturing the wiring board 21, for example, an etching process or the like is performed on the metal foil 13 on the surface of the obtained metal foil-clad laminate 11 to form a circuit (wiring), whereby a wiring board 21 having a conductor pattern (wiring 14) as a circuit provided on the surface of the laminate can be obtained. As a method for forming a circuit, in addition to the method described above, for example, a method for forming a circuit by a semi-additive process (SAP: Semi Additive Process) or a modified semi-additive process (MSAP: Modified Semi Additive Process) can be cited.

[0144] The prepreg, resin film, and resin metal foil obtained using the resin composition of the present embodiment are very useful in industrial applications because their cured products have excellent low dielectric properties and low thermal expansion properties. In addition, the metal foil-clad laminate and wiring board obtained by curing it also have low dielectric properties and low thermal expansion properties.

[0145] This specification has disclosed the technologies of various embodiments as described above, and the main technologies are summarized as follows.

[0146] The resin composition according to the first aspect of the present invention contains: a hydrocarbon compound (A) represented by the above formula (1); a polyphenylene ether compound (B) having a reactive carbon-carbon unsaturated double bond; and at least one of a polyfunctional vinyl aromatic copolymer (C) and an acenaphthylene compound (D).

[0147] The resin composition according to the second aspect of the present invention is: in the resin composition of the first aspect, the hydrocarbon compound (A) contains the hydrocarbon compound (A1) represented by the above formula (2).

[0148] The resin composition according to the third aspect of the present invention is: in the resin composition of the first or second aspect, with respect to a total of 100 parts by mass of the hydrocarbon compound (A), the polyphenylene ether compound (B), the polyfunctional vinyl aromatic copolymer (C), and the acenaphthylene compound (D), the content of the hydrocarbon compound (A) is 5 to 50 parts by mass.

[0149] The resin composition according to the fourth aspect of the present invention is: in the resin composition of any one of the first to third aspects, with respect to a total of 100 parts by mass of the hydrocarbon compound (A), the polyphenylene ether compound (B), the polyfunctional vinyl aromatic copolymer (C), and the acenaphthylene compound (D), the content of the polyphenylene ether compound (B) is 5 to 50 parts by mass.

[0150] The resin composition according to the fifth aspect of the present invention is as follows: in the resin composition according to any one of the first to fourth aspects, the content of the polyfunctional vinyl aromatic copolymer (C) is 0 to 50 parts by mass with respect to a total of 100 parts by mass of the hydrocarbon compound (A), the polyphenylene ether compound (B), the polyfunctional vinyl aromatic copolymer (C), and the acenaphthylene compound (D).

[0151] The resin composition according to the sixth aspect of the present invention is as follows: in the resin composition according to any one of the first to fifth aspects, the content of the acenaphthylene compound is 0 to 30 parts by mass with respect to a total of 100 parts by mass of the hydrocarbon compound (A), the polyphenylene ether compound (B), the polyfunctional vinyl aromatic copolymer (C), and the acenaphthylene compound (D).

[0152] The resin composition according to the seventh aspect of the present invention is as follows: in the resin composition according to any one of the first to sixth aspects, a phosphorus-based flame retardant is contained.

[0153] The resin composition according to the eighth aspect of the present invention is as follows: in the resin composition according to any one of the first to seventh aspects, an inorganic filler is contained.

[0154] The ninth aspect of the present invention relates to a prepreg, which includes: the resin composition according to any one of the first to eighth aspects or a semi-cured product of the resin composition; and a fibrous substrate.

[0155] The tenth aspect of the present invention relates to a resin-containing film, which includes: a resin layer containing the resin composition according to any one of the first to eighth aspects or a semi-cured product of the resin composition; and a support film.

[0156] The eleventh aspect of the present invention relates to a resin-containing metal foil, which includes: a resin layer containing the resin composition according to any one of the first to eighth aspects or a semi-cured product of the resin composition; and a metal foil.

[0157] The twelfth aspect of the present invention relates to a metal foil-clad laminate, which includes: an insulating layer containing a cured product of the resin composition according to any one of the first to eighth aspects or a cured product of the prepreg according to the ninth aspect; and a metal foil.

[0158] The thirteenth aspect of the present invention relates to a wiring board, which includes: an insulating layer containing a cured product of the resin composition according to any one of the first to eighth aspects or a cured product of the prepreg according to the ninth aspect; and wiring.

[0159] Hereinafter, the present invention will be further specifically described by way of examples. However, the scope of the present invention is not limited by these examples.

[0160] Examples

[0161] First, the components used in preparing the resin composition in this embodiment will be described.

[0162] (Hydrocarbon compound (A))

[0163] · Manufacture of hydrocarbon compound 1

[0164] First, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) used in manufacturing hydrocarbon compound 1 below are values obtained by the following analysis methods.

[0165] (Analysis method)

[0166] Using a polystyrene standard solution, it is calculated by conversion to polystyrene.

[0167] GPC: DGU-20A3R, LC-20AD, SIL-20AHT, RID-20A, SPD-20A, CTO-2, CBM-20A (all manufactured by Shimadzu Corporation)

[0168] Chromatographic column: Shodex KF-603, KF-602x2, KF-601x2

[0169] Coupled eluent: Tetrahydrofuran

[0170] Flow rate: 0.5 ml / minute

[0171] Column temperature: 40 °C

[0172] Detection: RI (Differential refractive index detector)

[0173] (Synthesis example 1)

[0174] In a flask equipped with a thermometer, a condenser, and a stirrer, 296 parts of 2-bromoethylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.), 70 parts of α,α'-dichlorop-xylene (manufactured by Tokyo Chemical Industry Co., Ltd.), and 18.4 parts of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the reaction was carried out at 130 °C for 8 hours. After cooling, it was neutralized with an aqueous sodium hydroxide solution, extracted with 1200 parts of toluene, and the organic layer was washed 5 times with 100 parts of water. By distilling off the solvent and excess 2-bromoethylbenzene under heating and reduced pressure, 160 parts of an olefin compound precursor (BEB-1) having a 2-bromoethylbenzene structure was obtained as a liquid resin (Mn: 538, Mw: 649). The Figure 6 shows the GPC chromatogram of the obtained compound. The repeating unit n calculated from the area% of the GPC chromatogram is 1.7. In addition, the Figure 7 shows the 1 1H-NMR spectrum (DMSO-d6) of the obtained compound. In1 Signals from the bromoethyl group were observed at 2.95 - 3.15 ppm and 3.60 - 3.75 ppm in the H-NMR spectrum.

[0175] (Synthesis Example 2)

[0176] Next, 22 parts of BEB-1, 50 parts of toluene, 150 parts of dimethyl sulfoxide, 15 parts of water, and 5.4 parts of sodium hydroxide obtained in the above Synthesis Example 1 were added to a flask equipped with a thermometer, a condenser, and a stirrer, and reacted at 40°C for 5 hours. After cooling, 100 parts of toluene was added, and the organic layer was washed 5 times with 100 parts of water. The solvent was removed by distillation under heating and reduced pressure, whereby 13 parts of a liquid olefin compound having a styrene structure as a functional group (Mn: 432, Mw: 575) was obtained. Figure 8 The GPC spectrum of the obtained compound is shown in Figure 9 . The repeating unit n calculated from the area% of the GPC spectrum was 1.7. Further, 1 the H-NMR spectrum (DMSO-d6) of the obtained compound is shown in 1 Signals from the vinyl group were observed at 5.10 - 5.30 ppm, 5.50 - 5.85 ppm, and 6.60 - 6.80 ppm in the H-NMR spectrum.

[0177] The liquid olefin compound was designated as hydrocarbon compound 1.

[0178] (Modified polyphenylene ether compound (B))

[0179] . Modified PPE: A modified polyphenylene ether obtained by reacting polyphenylene ether with chloromethylstyrene. Specifically, the modified polyphenylene ether was obtained by the following reaction.

[0180] First, 200 g of polyphenylene ether (SA90 manufactured by Sabic Innovative Plastics, with 2 terminal hydroxyl groups and a weight-average molecular weight Mw of 1700), 30 g of a mixture of p-chloromethylstyrene and m-chloromethylstyrene with a mass ratio of 50:50 (chloromethylstyrene: CMS manufactured by Tokyo Chemical Industry Co., Ltd.), 1.227 g of tetrabutylammonium bromide as a phase transfer catalyst, and 400 g of toluene were charged into a 1-L three-necked flask equipped with a temperature regulator, a stirring device, a cooling device, and a dropping funnel, and stirred. Then, stirring was carried out until the polyphenylene ether, chloromethylstyrene, and tetrabutylammonium bromide were dissolved in toluene. At this time, heating was gradually carried out and finally heated until the liquid temperature reached 75 °C. Then, an aqueous sodium hydroxide solution (20 g of sodium hydroxide / 20 g of water) as an alkali metal hydroxide was added dropwise to this solution over 20 minutes. Then, stirring was further carried out at 75 °C for 4 hours. Next, after neutralizing the contents of the flask with 10 mass% hydrochloric acid, a large amount of methanol was added. Thereby, a precipitate was formed in the liquid in the flask. That is, the product contained in the reaction solution in the flask was reprecipitated. Then, the precipitate was taken out by filtration, washed three times with a mixed solution of methanol and water with a mass ratio of 80:20, and dried at 80 °C under reduced pressure for 3 hours.

[0181] Using 1 H-NMR (400 MHz, CDCl 3 , TMS) analyzed the obtained solid. The NMR was measured, and as a result, a peak derived from vinylbenzyl was confirmed at 5 - 7 ppm. From this, it was confirmed that the obtained solid was polyphenylene ether with vinylbenzylation at the molecular terminal.

[0182] In addition, the number of terminal functional groups of the modified polyphenylene ether was measured as follows. First, the modified polyphenylene ether was accurately weighed. Let the weight at this time be X (mg). Then, the weighed modified polyphenylene ether was dissolved in 25 mL of dichloromethane, and 100 μL of a 10 mass% tetraethylammonium hydroxide (TEAH) ethanol solution (TEAH: ethanol (volume ratio) = 15:85) was added to this solution, and the absorbance (Abs) at 318 nm was measured using a UV spectrophotometer (UV-1600 manufactured by Shimadzu Corporation). Then, based on this measurement result, the number of terminal hydroxyl groups of the modified polyphenylene ether was calculated using the following formula.

[0183] Residual OH amount (μmol / g) = [(25 × Abs) / (ε × OPL × X)] × 10 6

[0184] Here, ε represents the extinction coefficient, which is 4700 L / mol·cm. In addition, OPL is the unit optical path length, which is 1 cm.

[0185] In addition, the remaining OH amount (number of terminal hydroxyl groups) of the calculated modified polyphenylene ether is almost zero. Therefore, it can be known that almost all of the hydroxyl groups of the polyphenylene ether before modification have been modified. From this, it can be known that the reduction amount compared to the number of terminal hydroxyl groups of the polyphenylene ether before modification is the number of terminal hydroxyl groups of the polyphenylene ether before modification. That is, it can be known that the number of terminal hydroxyl groups of the polyphenylene ether before modification is the number of terminal functional groups of the modified polyphenylene ether. That is to say, the number of terminal functional groups is 2.

[0186] In addition, the intrinsic viscosity (IV) of the modified polyphenylene ether in dichloromethane at 25 °C was measured. Specifically, the intrinsic viscosity (IV) of the modified polyphenylene ether was measured for a 0.18 g / 45 ml dichloromethane solution (liquid temperature 25 °C) of the modified polyphenylene ether using a viscometer (AVS500 Visco System manufactured by Schott). As a result, the intrinsic viscosity (IV) of the modified polyphenylene ether was 0.086 dl / g.

[0187] In addition, the molecular weight distribution of the modified polyphenylene ether was measured using GPC. Then, the weight-average molecular weight (Mw) was calculated from the obtained molecular weight distribution. As a result, Mw was 2300.

[0188] (Multifunctional vinyl aromatic polymer (C))

[0189] The multifunctional vinyl aromatic polymer was obtained based on the following method.

[0190] 3.0 moles (390.6 g) of divinylbenzene, 1.8 moles (229.4 g) of ethyl vinylbenzene, 10.2 moles (1066.3 g) of styrene, and 15.0 moles (1532.0 g) of n-propyl acetate were charged into a 5.0 L reactor, and 600 mmol of boron trifluoride diethyl ether complex was added at 70 °C, and the reaction was carried out for 4 hours. After stopping the reaction of the polymerization solution with an aqueous sodium bicarbonate solution, the oil layer was washed 3 times with pure water, and volatile matter was removed under reduced pressure at 60 °C to recover a solid (polymer). The obtained solid was weighed and was 896.7 g.

[0191] Using a JNM-LA600 type nuclear magnetic resonance spectrometer manufactured by JEOL Ltd., and through 13 C-NMR and 1 H-NMR analysis, the structure of the solid (polymer) obtained above was measured. Chloroform-d1 was used as a solvent, and the resonance line of tetramethylsilane was used as an internal standard. In addition, in addition to 13 C-NMR and 1In addition to the results of \(^1H-NMR\) measurement, based on the data on the total amount of each structural unit introduced into the copolymer obtained by GC analysis, the amount of introduction of a specific structural unit was calculated, and based on the amount of introduction of the specific structural unit introduced at the terminal and the number-average molecular weight obtained by the above-mentioned GPC measurement, the amount of side-chain vinyl units contained in the polyfunctional vinyl aromatic copolymer was calculated.

[0192] For the obtained solid, by performing the above-mentioned 13 \(^{13}C-NMR\) and 1 \(^1H-NMR\) analysis, resonance lines from each monomer unit were observed. In addition, based on the NMR measurement results and GC analysis results, it was found that the solid was the polyfunctional vinyl aromatic copolymer. And, based on the NMR measurement results and GC analysis results, the structural units of the polyfunctional vinyl aromatic copolymer were calculated as follows. The structural unit derived from divinylbenzene was 30.4 mol% (33.1 mass%), the structural unit derived from styrene was 57.4 mol% (52.7 mass%), the structural unit derived from ethylvinylbenzene was 12.2 mol% (14.2 mass%), and the structural unit having a residual vinyl group derived from divinylbenzene was 23.9 mol% (25.9 mass%).

[0193] Using GPC (HLC-8120GPC manufactured by Tosoh Corporation), and using tetrahydrofuran as a solvent, at a flow rate of 1.0 ml / minute, a column temperature of 38 °C, and using a calibration line obtained from monodisperse polystyrene, the molecular weight and molecular weight distribution of the obtained solid (polyfunctional vinyl aromatic copolymer) were measured. As a result, the number-average molecular weight \(M_n\) of the obtained solid was 2980, the weight-average molecular weight \(M_w\) was 41300, and \(M_w / M_n\) was 13.9.

[0194] (Acenaphthylene compound (D))

[0195] · Acenaphthylene (manufactured by JFE Chemical Corporation)

[0196] (Inorganic filler)

[0197] · Electrochemical fused silica low dielectric loss factor type (manufactured by Denka Company Limited, spherical silica)

[0198] <Examples 1 to 3 and Comparative Examples 1 to 3>

[0199] [Preparation method]

[0200] (Resin varnish)

[0201] First, at the ratio (parts by mass) shown in Table 1, the resin component was added to toluene so that the solid content concentration became 50 mass%, and the mixture was stirred for 60 minutes to obtain a resin varnish.

[0202] (Fabrication of evaluation substrate)

[0203] The prepreg and the evaluation substrate (metal-clad laminate) were obtained as follows.

[0204] First, the obtained varnish was impregnated into a fibrous substrate (glass cloth: #2116 type manufactured by Nitto Boseki Co., Ltd., NE glass), and then heated and dried at 120 °C for 3 minutes to fabricate a prepreg with a resin thickness of 100 μm. At this time, the content of the components constituting the resin composition in the prepreg (resin content) was adjusted to be 45% by mass through a curing reaction.

[0205] Next, the evaluation substrate (metal-clad laminate) was obtained as follows.

[0206] Two pieces of the obtained prepregs were overlapped, and copper foils ("CF-T4X-SV" manufactured by Fukuda Metal Foil & Powder Co., Ltd., copper foil thickness: 18 μm) were disposed on both sides thereof. This was used as the object to be pressed, heated to a temperature of 220 °C at a heating rate of 3 °C / minute, and hot-pressed under the conditions of 220 °C, 120 minutes, and a pressure of 3 MPa to obtain an evaluation substrate (metal-clad laminate) with a resin layer thickness of approximately 200 μm having copper foils adhered to both surface sides.

[0207] The evaluation test was conducted using the evaluation substrate (metal-clad laminate) prepared as described above by the method shown below.

[0208] <Evaluation Test 1>

[0209] (Glass transition temperature (Tg))

[0210] Using the bare board obtained by removing the copper foil from the above-mentioned evaluation substrate through etching, and using a viscoelastic spectrometer "DMS6100" manufactured by Seiko Instruments Inc., the Tg was measured. At this time, dynamic viscoelastic measurement (DMA) was performed with the frequency set to 10 Hz using a tensile module, and the temperature at which tanδ exhibited a maximum when heating from room temperature to 350 °C at a heating rate of 5 °C / minute was set as the Tg. In this test, if the Tg was 240 °C or higher, it was regarded as qualified.

[0211] (Dielectric properties: Dielectric loss factor (Df))

[0212] The bare board obtained by removing the copper foil from the evaluation substrate (metal-clad laminate) through etching was used as a test piece, and the relative permittivity and dielectric loss factor at 10 GHz were measured by the resonant cavity perturbation method. Specifically, using a network analyzer (N5230A manufactured by Keysight Technologies), the dielectric loss factor of the evaluation substrate at 10 GHz was measured. In this test, if Df is 0.0023 or less, it is regarded as qualified.

[0213] (Coefficient of Thermal Expansion (CTE))

[0214] The bare board obtained by removing the copper foil from the evaluation substrate (metal-clad laminate) through etching was used as a test piece, and the coefficient of thermal expansion in the substrate surface direction (tensile direction, Y direction) at a temperature below the glass transition temperature of the resin cured product was measured by the TMA method (Thermo-mechanical analysis). Specifically, during the measurement, using a TMA device ("TMA6000" manufactured by Seiko Instruments Nano-Technology Co., Ltd.), the measurement was carried out in the tensile mode. In order to remove the influence of the thermal strain possessed by the test piece, the temperature increase-cooling cycle was repeated 2 times, and the average coefficient of thermal expansion from 50 °C to 100 °C of the second temperature displacement graph was measured. The smaller the value, the better the result. In this test, if it is 10 ppm / °C or less, it is regarded as qualified. The unit is ppm / °C.

[0215] [Measurement Conditions]

[0216] ·First cycle: Temperature increase range 30 °C → 320 °C

[0217] Temperature increase rate: 20 °C / minute, Load: 10 g

[0218] ·Second cycle: Temperature increase range 30 °C → 320 °C

[0219] Temperature increase rate: 10 °C / minute, Load: 10 g

[0220] (Thermogravimetric Analysis (TGA))

[0221] The bare board obtained by removing the copper foil from the evaluation substrate (metal-clad laminate) through etching was used as a test piece, and thermogravimetric analysis was carried out. Specifically, using TG-DTA8122 manufactured by Rigaku Corporation (equipped with an infrared furnace IRF-12), the measurement was carried out under the measurement conditions of 90 °C / minute in an air atmosphere, and the temperature when the weight reduction reached 5% was evaluated. In this test, the case where TGA is 450 °C or higher was evaluated as qualified.

[0222] The above results are shown in Table 1.

[0223]

[0224] (Examination)

[0225] It was clear from the results shown in Table 1 that a cured product having low dielectric properties and a low coefficient of thermal expansion could be obtained by the resin composition of the present invention. In addition, it was also confirmed that the cured products of the resin compositions of the examples had a high TG and TGA.

[0226] On the other hand, in the comparative examples using a resin composition not containing the hydrocarbon compound (A) or a resin composition not containing the modified polyphenylene ether compound (B), sufficient effects were not obtained in terms of low dielectric properties, low thermal expansibility, and both of these aspects.

[0227] <Evaluation Test 2>

[0228] The copper foil was peeled from the evaluation substrates (metal foil-clad laminates) of Examples 1 to 3, and the peel strength at this time was measured in accordance with JIS C 6481. Specifically, the width of the evaluation substrate was cut to 10 mm, and the copper foil was peeled at a speed of 50 mm / min using a tensile testing machine, and the peel strength (N / mm) at this time was measured. In this test, if it was 0.4 N / mm or more, it was determined that the peel strength was excellent.

[0229] The results are shown in Table 2.

[0230] Table 2

[0231]

[0232] (Examination)

[0233] It was also found from the results of Table 2 that a cured product with higher adhesion could be obtained by containing the acenaphthylene compound (D).

[0234] This application is based on Japanese Patent Application No. 2022-180984 filed on November 11, 2022, the content of which is incorporated herein.

[0235] In order to describe the present invention, the present invention has been appropriately and sufficiently described above by way of embodiments with reference to specific examples and drawings, etc., but it should be recognized that those skilled in the art can easily make changes and / or improvements to the above embodiments. Therefore, as long as the modified embodiments or improved embodiments implemented by those skilled in the art are at a level that does not depart from the scope of protection of the claims recited in the claims, such modified embodiments or such improved embodiments can be interpreted as being included within the scope of protection of the claims.

[0236] Industrial Applicability

[0237] The present invention has wide industrial applicability in technical fields such as electronic materials, electronic devices, and optical devices.

Claims

1. A resin composition, characterized in that it contains: a hydrocarbon compound (A) represented by the following formula (1), in formula (1), X represents a hydrocarbon group having 6 or more carbon atoms and containing at least one selected from an aromatic ring group and an aliphatic ring group, and n represents an integer of 1 to 10; a polyphenylene ether compound (B) having a reactive carbon-carbon unsaturated double bond; and at least one of a polyfunctional vinyl aromatic copolymer (C) and an acenaphthylene compound (D).

2. The resin composition according to claim 1, characterized in that the hydrocarbon compound (A) contains a hydrocarbon compound (A1) represented by the following formula (2), n represents an integer of 1 to 10.

3. The resin composition according to claim 1, characterized in that relative to a total of 100 parts by mass of the hydrocarbon compound (A), the polyphenylene ether compound (B), the polyfunctional vinyl aromatic copolymer (C) and the acenaphthylene compound (D), the content of the hydrocarbon compound (A) is 5 to 50 parts by mass.

4. The resin composition according to claim 1, characterized in that relative to a total of 100 parts by mass of the hydrocarbon compound (A), the polyphenylene ether compound (B), the polyfunctional vinyl aromatic copolymer (C) and the acenaphthylene compound (D), the content of the polyphenylene ether compound (B) is 5 to 50 parts by mass.

5. The resin composition according to claim 1, characterized in that relative to a total of 100 parts by mass of the hydrocarbon compound (A), the polyphenylene ether compound (B), the polyfunctional vinyl aromatic copolymer (C) and the acenaphthylene compound (D), the content of the polyfunctional vinyl aromatic copolymer (C) is 0 to 50 parts by mass.

6. The resin composition according to claim 1, characterized in that relative to a total of 100 parts by mass of the hydrocarbon compound (A), the polyphenylene ether compound (B), the polyfunctional vinyl aromatic copolymer (C) and the acenaphthylene compound (D), the content of the acenaphthylene compound is 0 to 30 parts by mass.

7. The resin composition according to claim 1, characterized in that it contains: a phosphorus-based flame retardant.

8. The resin composition according to claim 1, characterized in that it contains: an inorganic filler.

9. A prepreg, characterized in that it includes: the resin composition according to any one of claims 1 to 8 or a semi-cured product of the resin composition; and a fibrous substrate.

10. A resin-coated film, characterized in that it includes: a resin layer containing the resin composition according to any one of claims 1 to 8 or a semi-cured product of the resin composition; and a support film.

11. A resin-coated metal foil, characterized in that it includes: a resin layer containing the resin composition according to any one of claims 1 to 8 or a semi-cured product of the resin composition; and a metal foil.

12. A metal-clad laminate, characterized in that it includes: an insulating layer containing a cured product of the resin composition according to any one of claims 1 to 8; and a metal foil.

13. A wiring board, characterized in that it includes: an insulating layer containing a cured product of the resin composition according to any one of claims 1 to 8; and wiring.

14. A metal-clad laminate, characterized in that it includes: An insulating layer comprising a cured product of the prepreg according to claim 9; and a metal foil.

15. A wiring board, characterized in that it comprises: An insulating layer comprising a cured product of the prepreg according to claim 9; and a wiring.

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