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

Abstract

This resin composition comprises a resin component (R), a core-shell rubber (D), and an inorganic filler (E). The resin component (R) contains a polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond, a maleimide compound (B), and a phenol compound (C) having a carbon-carbon unsaturated double bond. The core-shell rubber (D) is contained in an amount of 1-20 parts by mass with respect to the resin component (R).

Description

Resin composition, prepreg, metal-clad laminate, wiring board, resin-coated metal foil and resin-coated film

[0001] The present disclosure relates to a resin composition, a prepreg, a metal-clad laminate, a wiring board, a resin-coated metal foil, and a resin-coated film, and more particularly to a resin composition containing a thermosetting resin, and a prepreg, a metal-clad laminate, a wiring board, a resin-coated metal foil, and a resin-coated film made from the resin composition.

[0002] A printed circuit board or the like made from the polyphenylene ether resin composition described in Patent Document 1 has a low dielectric constant and a low dielectric loss, and can stably maintain the dielectric constant and dielectric loss of the substrate during long-term use.

[0003] Patent No. 6514405

[0004] An object of the present disclosure is to provide a resin composition that can favorably achieve circuit filling properties and a linear expansion coefficient of the cured product, and that can achieve high tensile strength of the cured product, as well as a prepreg, a metal-clad laminate, a wiring board, a resin-coated metal foil, and a resin-coated film made from the resin composition.

[0005] A resin composition according to one embodiment of the present disclosure contains a resin component (R), a core-shell rubber (D), and an inorganic filler (E). The resin component (R) contains a polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond, a maleimide compound (B), and a phenol compound (C) having a carbon-carbon unsaturated double bond. The core-shell rubber (D) is present in an amount of 1 part by mass or more and 20 parts by mass or less relative to the resin component (R).

[0006] A prepreg according to one aspect of the present disclosure includes a resin layer containing at least one of the resin composition and a semi-cured product of the resin composition, and the resin layer further includes a fibrous base material.

[0007] A metal-clad laminate according to one embodiment of the present disclosure includes an insulating layer containing a cured product of the resin composition, and a metal foil.

[0008] A wiring board according to one embodiment of the present disclosure includes an insulating layer containing a cured product of the resin composition, and wiring.

[0009] A resin-attached metal layer according to one aspect of the present disclosure includes a resin layer containing at least one of the resin composition and a semi-cured product of the resin composition, and a metal foil.

[0010] A resin-coated film according to one embodiment of the present disclosure includes a resin layer containing at least one of the resin composition and a semi-cured product of the resin composition, and a support film.

[0011] Fig. 1 is a schematic cross-sectional view showing an example of a prepreg according to an embodiment of the present disclosure. Fig. 2 is a schematic cross-sectional view showing an example of a metal-clad laminate according to an embodiment of the present disclosure. Fig. 3 is a schematic cross-sectional view showing an example of a wiring board according to an embodiment of the present disclosure. Fig. 4 is a schematic cross-sectional view showing an example of a resin-coated metal foil according to an embodiment of the present disclosure. Fig. 5 is a schematic cross-sectional view showing an example of a resin-coated film according to an embodiment of the present disclosure.

[0012] [Embodiments] (Summary) The embodiments will be described with reference to FIGS. 1 to 5. Note that the following embodiments are merely a portion of various embodiments of the present disclosure. Furthermore, the following embodiments can be modified in various ways depending on the design, etc., as long as the object of the present disclosure can be achieved. Furthermore, all of the drawings referred to below are schematic drawings, and the dimensional ratios of the components in the drawings do not necessarily reflect the actual dimensional ratios.

[0013] Printed circuit boards can be produced from cured products of resin compositions containing polyphenylene ether. To prevent cracking of the cured products of such resin compositions, improved tensile strength is required. One method for improving tensile strength is to incorporate a component that can impart flexibility to the cured product of the resin composition. However, there are problems with sufficiently filling the spaces between circuits with the resin composition (circuit filling ability) and maintaining the linear expansion coefficient of the cured product. Therefore, the inventors conducted extensive research and development, leading to the present disclosure.

[0014] The resin composition of the present disclosure (hereinafter also referred to as composition (M)) contains a resin component (R), a core-shell rubber (D), and an inorganic filler (E). The resin component (R) contains a polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond, a maleimide compound (B), and a phenol compound (C) having a carbon-carbon unsaturated double bond. The core-shell rubber (D) is present in an amount of 1 part by mass or more and 20 parts by mass or less relative to the resin component (R). By virtue of having the above-described configuration, composition (M) can achieve a favorable linear expansion coefficient and circuit filling ability of the cured product, and can also achieve high tensile strength of the cured product.

[0015] To explain in more detail, the resin component (R) contains a polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond, a maleimide compound (B), and a phenol compound (C) having a carbon-carbon unsaturated double bond. This allows for an improvement in the linear expansion coefficient and circuit filling ability of the cured product. In addition, the composition (M) contains a specific component, the core-shell rubber (D), in a specific range of 1 part by mass to 20 parts by mass relative to the resin component (R). This allows for an improvement in tensile strength without impairing the enhanced circuit filling ability of the composition (M) or the enhanced linear expansion coefficient of the cured product.

[0016] In the present disclosure, the term "circuit filling ability" refers to the ease with which a resin composition fills between circuits. By increasing the circuit filling ability of the composition (M), it is possible to suppress the generation of voids in the cured product disposed between circuits.

[0017] [Components] The components contained in the composition (M) will be described.

[0018] As described above, the composition (M) contains the resin component (R), the core-shell rubber (D), and the inorganic filler (E). The resin component (R) contains the polyphenylene ether compound (A), the maleimide compound (B), and the phenol compound (C).

[0019] <Polyphenylene ether compound> As described above, the resin component (R) contains the polyphenylene ether compound (A). This can reduce the dielectric constant and dielectric dissipation factor of the cured product. The polyphenylene ether compound (A) also has a carbon-carbon unsaturated double bond. This can improve the curability of the composition (M). Furthermore, the polyphenylene ether compound (A) preferably contains a modified polyphenylene ether compound (A1) (hereinafter also simply referred to as modified polyphenylene ether compound (A1)) that has been terminally modified with a substituent having a carbon-carbon unsaturated double bond. In this case, the curability of the composition (M) can be further improved.

[0020] With regard to the modified polyphenylene ether compound (A1), examples of the substituent having a carbon-carbon unsaturated double bond include a substituent represented by formula (1).

[0021]

[0022] In formula (1), p represents an integer of 0 to 10. Z represents an arylene group. １ ~R ３ are each independent. That is, R １ ~R ３ may be the same group or different groups. １ ~R ３represents a hydrogen atom or an alkyl group. In addition, when p is 0 in formula (1), this indicates that Z is directly bonded to the terminal of the polyphenylene ether. Specific examples of the arylene group include monocyclic aromatic groups such as a phenylene group and polycyclic aromatic groups such as a naphthalene ring. In addition, this arylene group may contain a derivative in which a hydrogen atom bonded to the aromatic ring is substituted with a functional group such as an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. In addition, the alkyl group is not particularly limited, but is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group.

[0023] In addition, with regard to the modified polyphenylene ether compound (A1), examples of the substituent having a carbon-carbon unsaturated double bond include a substituent represented by formula (2).

[0024]

[0025] In formula (2), R ４ represents a hydrogen atom or an alkyl group. The alkyl group is not particularly limited, but is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group. Examples of the substituent represented by formula (2) include an acrylate group and a methacrylate group.

[0026] Further, more specific examples of the group represented by formula (1) include a vinylbenzyl group (ethenylbenzyl group) or a vinylphenyl group represented by formula (3). Further, more specific examples of the vinylbenzyl group include an o-ethenylbenzyl group, an m-ethenylbenzyl group, and a p-ethenylbenzyl group.

[0027]

[0028] The modified polyphenylene ether compound (A1) terminally modified with a substituent having a carbon-carbon unsaturated double bond has a polyphenylene ether chain in the molecule, and preferably has a repeating unit represented by formula (4) in the molecule.

[0029]

[0030] In formula (4), t represents an integer of 1 or more and 50 or less. ５ ~R ８ are each independent. That is, R ５ ~R ８ may be the same group or different groups. ５ ~R ８ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group, among which a hydrogen atom and an alkyl group are preferred.

[0031] R ５ ~R ８ Specific examples of the functional groups mentioned in the above include the following:

[0032] The alkyl group is not particularly limited, but is preferably an alkyl group having from 1 to 18 carbon atoms, and more preferably an alkyl group having from 1 to 10 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group.

[0033] The alkenyl group is not particularly limited, but is preferably an alkenyl group having from 2 to 18 carbon atoms, and more preferably an alkenyl group having from 2 to 10 carbon atoms. Specific examples of the alkenyl group include a vinyl group, an allyl group, and a 3-butenyl group.

[0034] The alkynyl group is not particularly limited, but is preferably an alkynyl group having from 2 to 18 carbon atoms, and more preferably an alkynyl group having from 2 to 10 carbon atoms. Specific examples of the alkynyl group include an ethynyl group and a prop-2-yn-1-yl group (propargyl group).

[0035] The alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group, but is preferably an alkylcarbonyl group having from 2 to 18 carbon atoms, and more preferably an alkylcarbonyl group having from 2 to 10 carbon atoms. Specific examples of the alkylcarbonyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a hexanoyl group, an octanoyl group, and a cyclohexylcarbonyl group.

[0036] The alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group, but for example, an alkenylcarbonyl group having from 3 to 18 carbon atoms is preferred, and an alkenylcarbonyl group having from 3 to 10 carbon atoms is more preferred. Specific examples of the alkenylcarbonyl group include an acryloyl group, a methacryloyl group, and a crotonoyl group.

[0037] The alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group, but for example, an alkynylcarbonyl group having from 3 to 18 carbon atoms is preferred, and an alkynylcarbonyl group having from 3 to 10 carbon atoms is more preferred. Specific examples of the alkynylcarbonyl group include a propioloyl group.

[0038] The weight-average molecular weight (Mw) of the modified polyphenylene ether compound (A1) is preferably 500 or more and 5,000 or less. In this case, the heat resistance and circuit filling ability of the cured product can be improved. The reason why the heat resistance and circuit filling ability of the cured product can be improved when the weight-average molecular weight of the modified polyphenylene ether compound (A1) is within the above range is presumed to be due to the following reasons. For example, when the weight-average molecular weight of a normal polyphenylene ether that is not terminally modified is within the range of 500 or more and 5,000 or less, the molecular weight is relatively low, and therefore the heat resistance of the cured product produced from the resin composition containing the polyphenylene ether tends to be reduced. In contrast, the modified polyphenylene ether compound (A1) has an unsaturated double bond at the terminal, which makes it easy to improve the heat resistance of the cured product. Furthermore, since the weight-average molecular weight of the modified polyphenylene ether compound (A1) is within the range of 5,000 or less and is relatively low, the circuit filling ability of the cured product can also be improved. This weight-average molecular weight is more preferably 800 or more, and even more preferably 1,000 or more. The weight-average molecular weight is preferably not more than 4500, and more preferably not more than 4000. The weight-average molecular weight may be measured by a general molecular weight measurement method, and specifically, the weight-average molecular weight may be measured by gel permeation chromatography (GPC) and converted into polystyrene equivalent.

[0039] When the modified polyphenylene ether compound (A1) has a repeating unit represented by formula (4) in the molecule, t is preferably a numerical value such that the weight-average molecular weight of the polyphenylene ether compound (A) is in the range of 500 to 5000. Specifically, t is preferably 1 to 50.

[0040] The average number of substituents having a carbon-carbon unsaturated double bond (number of terminal functional groups) per molecule of the modified polyphenylene ether compound (A1) is preferably 1 or more and 5 or less. When the number of terminal functional groups is 1 or more, the heat resistance of the cured product can be further improved. When the number of terminal functional groups is 5 or less, the reactivity of the composition (M) can be adjusted, thereby increasing the fluidity of the composition (M) during molding and improving the storage stability of the composition (M). More preferably, the number of terminal functional groups is 1.5 or more. More preferably, the number of terminal functional groups is 3 or less.

[0041] The number of terminal functional groups in the modified polyphenylene ether compound (A1) is a numerical value representing the average number of substituents per molecule of all modified polyphenylene ether compounds (A1) present in 1 mole of the modified polyphenylene ether compound (A1). This number of terminal functional groups can be measured, for example, by measuring the number of hydroxyl groups remaining in the obtained modified polyphenylene ether compound (A1) and calculating the difference from the number of hydroxyl groups in the polyphenylene ether before modification. This difference from the number of hydroxyl groups in the polyphenylene ether before modification is the number of terminal functional groups. The number of hydroxyl groups remaining in the modified polyphenylene ether compound (A1) can be determined by adding a quaternary ammonium salt (tetraethylammonium hydroxide) that associates with hydroxyl groups to a solution of the modified polyphenylene ether compound (A1) and measuring the UV absorbance of the resulting mixed solution.

[0042] The intrinsic viscosity of the modified polyphenylene ether compound (A1) is preferably 0.03 dl / g or more and 0.12 dl / g or less. When this intrinsic viscosity is 0.03 dl / g or more, the dielectric constant and dielectric dissipation factor of the cured product can be reduced. Furthermore, when the intrinsic viscosity is 0.12 dl / g or less, the fluidity of the composition (M) during molding can be easily ensured. This can improve the circuit filling ability of the composition (M). This intrinsic viscosity is more preferably 0.04 dl / g or more, and even more preferably 0.06 dl / g or more. This intrinsic viscosity is more preferably 0.11 dl / g or less, and even more preferably 0.095 dl / g or less.

[0043] The intrinsic viscosity of the modified polyphenylene ether compound (A1) is the intrinsic viscosity measured in methylene chloride at 25° C., and more specifically, is the value measured, for example, using a 0.18 g / 45 ml methylene chloride solution (liquid temperature: 25° C.) with a viscometer. As the viscometer, for example, an AVS500 Visco System manufactured by Schott can be used.

[0044] The modified polyphenylene ether compound (A1) preferably contains, for example, at least one of a modified polyphenylene ether compound (A1-1) represented by formula (5) and a modified polyphenylene ether compound (A1-2) represented by formula (6).

[0045]

[0046]

[0047] In formula (5) and formula (6), R ９ ~R １６ and R １７ ~R ２４ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. １ and X ２ each independently represents a substituent having a carbon-carbon unsaturated double bond. A and B each represent a repeating unit represented by formula (7) and formula (8), respectively. In formula (6), Y represents a linear, branched, or cyclic hydrocarbon group having 20 or less carbon atoms.

[0048]

[0049]

[0050] In formula (7) and formula (8), m and n each represent 0 to 20. In formula (7) and formula (8), R ２５ ~R ２８ and R ２９ ~R ３２ are each independent. That is, R ２５ ~R ２８ and R ２９~R ３２ may be the same group or different groups. ２５ ~R ２８ and R ２９ ~R ３２ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. Among these, a hydrogen atom and an alkyl group are preferred. ２５ ~R ３２ is R in formula (4). ５ ~R ８ may be the same as

[0051] Furthermore, it is preferable that the sum of m and n in formula (7) and formula (8) is a numerical value of 1 or more and 30 or less. Therefore, it is more preferable that m is 0 or more and 20 or less, n is 0 or more and 20 or less, and the sum of m and n is 1 or more and 30 or less.

[0052] In formula (6), Y is a linear, branched, or cyclic hydrocarbon group having up to 20 carbon atoms. Examples of Y include a group represented by formula (9).

[0053]

[0054] In formula (9), R ３３ and R ３４ are each independently a hydrogen atom or an alkyl group. Examples of the alkyl group include a methyl group. Specific examples of the group represented by formula (9) include a methylene group, a methylmethylene group, and a dimethylmethylene group. Among these, a dimethylmethylene group is preferred.

[0055] In addition, in the formulas (5) and (6), X １ and X ２ are each independent. １ and X ２ is, for example, a substituent having a carbon-carbon unsaturated double bond. １ and X ２is, for example, a substituent represented by formula (1) or a substituent represented by formula (2). In the modified polyphenylene ether compound (A1-1) represented by formula (5) and the modified polyphenylene ether compound (A1-2) represented by formula (6), X １ and X ２ may be the same substituent or different substituents.

[0056] More specific examples of the modified polyphenylene ether compound (A1-1) represented by formula (5) include modified polyphenylene ether compounds (A1-11) represented by formula (10).

[0057]

[0058] More specific examples of the modified polyphenylene ether compound (A1-2) represented by formula (6) include a modified polyphenylene ether compound (A1-21) represented by formula (11) or a modified polyphenylene ether compound (A1-22) represented by formula (12).

[0059]

[0060]

[0061] In formulas (10) to (12), m and n are the same as m and n in formulas (7) and (8). １ ~R ３ , p and Z are R in formula (1). １ ~R ３ , p, and Z. In formulas (11) and (12), Y is the same as Y in formula (6). In formula (12), R ４ is R in formula (2). ４ is the same as

[0062] A method for synthesizing the modified polyphenylene ether compound (A1) will be described below. Specifically, a method of reacting a polyphenylene ether compound as a raw material with a compound in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded to the compound can be mentioned.

[0063] The polyphenylene ether compound used as a raw material is not particularly limited as long as it can synthesize the desired modified polyphenylene ether compound (A1). Specific examples include polyphenylene ether compounds such as poly(2,6-dimethyl-1,4-phenylene oxide) and polyphenylene ethers composed of 2,6-dimethylphenol and at least one of a bifunctional phenol and a trifunctional phenol. A bifunctional phenol is a phenol compound having two phenolic hydroxyl groups per molecule, such as tetramethylbisphenol A. A trifunctional phenol is a phenol compound having three phenolic hydroxyl groups per molecule.

[0064] The modified polyphenylene ether compound (A1) can be synthesized by the method described above. Specifically, the polyphenylene ether compound described above and a compound having a substituent with a carbon-carbon unsaturated double bond and a halogen atom bonded thereto are dissolved in a solvent and stirred. By doing so, the polyphenylene ether compound reacts with the compound having a substituent with a carbon-carbon unsaturated double bond and a halogen atom bonded thereto, thereby obtaining the modified polyphenylene ether compound (A1).

[0065] The reaction between a polyphenylene ether compound and a compound having a substituent having a carbon-carbon unsaturated double bond and a halogen atom bonded thereto is preferably carried out in the presence of an alkali metal hydroxide. It is believed that this allows the reaction to proceed smoothly. This is believed to be because the alkali metal hydroxide functions as a dehydrohalogenation agent, specifically, a dehydrochlorination agent. That is, it is believed that the alkali metal hydroxide eliminates hydrogen halide from the phenolic hydroxyl group of the polyphenylene ether compound and the compound having a substituent having a carbon-carbon unsaturated double bond and a halogen atom bonded thereto, and thereby the substituent having a carbon-carbon unsaturated double bond bonds to the oxygen atom of the phenolic group in place of the hydrogen atom of the phenolic hydroxyl group of the polyphenylene ether compound.

[0066] The alkali metal hydroxide is not particularly limited as long as it can act as a dehalogenating agent, and examples thereof include sodium hydroxide, etc. The alkali metal hydroxide is usually used in the form of an aqueous solution, specifically, an aqueous sodium hydroxide solution.

[0067] The reaction conditions, such as the reaction time and reaction temperature, vary depending on the substituent having a carbon-carbon unsaturated double bond and the compound to which a halogen atom is bonded, and are not particularly limited as long as the conditions are such that the reaction proceeds favorably. Specifically, the reaction temperature is preferably from room temperature (20°C) to 100°C, and more preferably from 30°C to 100°C. The reaction time is preferably from 0.5 hours to 20 hours, and more preferably from 0.5 hours to 10 hours.

[0068] The solvent used in the reaction of the polyphenylene ether compound with the compound having a substituent with a carbon-carbon unsaturated double bond and a halogen atom bonded thereto is not particularly limited, as long as it can dissolve the polyphenylene ether compound with the compound having a substituent with a carbon-carbon unsaturated double bond and a halogen atom bonded thereto and does not inhibit the reaction between the polyphenylene ether compound with the compound having a substituent with a carbon-carbon unsaturated double bond and a halogen atom bonded thereto. Specific examples include toluene.

[0069] The reaction between a polyphenylene ether compound and a compound having a substituent group having a carbon-carbon unsaturated double bond and a halogen atom bonded thereto is preferably carried out in the presence of not only an alkali metal hydroxide but also a phase transfer catalyst. That is, the reaction is preferably carried out in the presence of an alkali metal hydroxide and a phase transfer catalyst. Doing so is believed to allow the reaction to proceed more smoothly. This is believed to be due to the following: A phase transfer catalyst has the function of incorporating an alkali metal hydroxide, is soluble in both a polar solvent phase such as water and a nonpolar solvent phase such as an organic solvent, and is capable of transferring between these phases. Specifically, when an aqueous solution of sodium hydroxide is used as the alkali metal hydroxide and an organic solvent such as toluene that is incompatible with water is used as the solvent, even if the aqueous solution of sodium hydroxide is added dropwise to the solvent being used for the reaction, the solvent and the aqueous solution of sodium hydroxide separate, and it is believed that the sodium hydroxide is unlikely to migrate to the solvent. In this case, it is believed that the aqueous solution of sodium hydroxide added as the alkali metal hydroxide is unlikely to contribute to promoting the reaction. In contrast, when the reaction is carried out in the presence of an alkali metal hydroxide and a phase transfer catalyst, the alkali metal hydroxide is incorporated into the phase transfer catalyst and migrates to the solvent, and it is believed that the aqueous sodium hydroxide solution is more likely to contribute to promoting the reaction. Therefore, it is believed that the reaction proceeds more smoothly when the reaction is carried out in the presence of an alkali metal hydroxide and a phase transfer catalyst. The phase transfer catalyst is not particularly limited, but examples include quaternary ammonium salts such as tetra-n-butylammonium bromide.

[0070] <Maleimide Compound> As described above, the resin component (R) contains the maleimide compound (B), which can increase the glass transition temperature of the cured product.

[0071] The maleimide compound (B) may contain only one type of compound or may contain two or more types of compounds. Examples of the maleimide compound (B) include a monofunctional maleimide compound having one maleimide group per molecule and a polyfunctional maleimide compound having two or more maleimide groups per molecule.

[0072] Examples of monofunctional maleimide compounds having one maleimide group per molecule include chlorophenylmaleimides such as o-chlorophenylmaleimide, methylphenylmaleimides such as o-methylphenylmaleimide, hydroxyphenylmaleimides such as p-hydroxyphenylmaleimide, carboxyphenylmaleimides such as p-carboxyphenylmaleimide, N-dodecylmaleimide, and phenylmethanemaleimide.

[0073] Specific examples of polyfunctional maleimide compounds having two or more maleimide groups per molecule include 4,4'-diphenylmethane bismaleimide, bisphenol A bis(4-maleimidophenyl ether), 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, and polyphenylmethane maleimide. Among these, it is preferable that the maleimide compound (B) contains polyphenylmethane maleimide. In this case, the dielectric constant and dielectric dissipation factor of the cured product can be reduced, and the glass transition temperature of the cured product can be increased.

[0074] The polyphenylmethane maleimide preferably contains at least one of a maleimide compound (B1) represented by formula (13) (hereinafter also referred to as maleimide compound (B1)) and a maleimide compound (B2) represented by formula (14). In this case, the dielectric constant and dielectric dissipation factor of the cured product can be further reduced, and the glass transition temperature of the cured product can be further increased.

[0075]

[0076] In formula (13), s represents the number of repeating units, which is the average value of the degree of polymerization, and is from 1 to 5. In other words, the maleimide compound (B1) contains a plurality of maleimide compounds represented by formula (13), and it is sufficient that the average value of the number of repeating units in formula (13) among these plurality of maleimide compounds is from 1 to 5.

[0077] R ３５ ~R ３８ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group. Among these, a hydrogen atom is preferred. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, and a neopentyl group.

[0078] In addition, in formula (13), R ３５ ~R ３８ represents a group carried by the aromatic ring directly bonded to the maleimide ring. ３５ and R ３６ is bonded to an aromatic ring that is directly bonded to a maleimide ring that is not included in a repeating unit in formula (13). ３７ and R ３８ is bonded to any of the aromatic rings directly bonded to the maleimide ring contained in the repeating unit of formula (13).

[0079] Furthermore, R contained in the repeating unit in formula (13) ３７ and R ３８ is independent for each repeating unit. Therefore, R ３７ and R ３８ may be the same or different for each repeat unit.

[0080]

[0081] In formula (14), t represents an integer of 1 or more.

[0082] The weight-average molecular weight of the maleimide compound (B) is preferably 150 or more and 2500 or less. When this weight-average molecular weight is 150 or more, the glass transition temperature of the cured product can be increased. When this weight-average molecular weight is 2500 or less, the circuit filling ability can be improved. This weight-average molecular weight is more preferably 300 or more, and even more preferably 400 or more. This weight-average molecular weight is more preferably 2000 or less, and even more preferably 1500 or less. The weight-average molecular weight of the maleimide compound (B) may be measured by a general molecular weight measurement method, and specific examples include values ​​measured using gel permeation chromatography (GPC) and converted into polystyrene equivalents.

[0083] <Curing Agent> As described above, the resin component (R) contains a phenolic compound (C) having a carbon-carbon unsaturated double bond. In this case, the glass transition temperature of the cured product and the adhesion of the cured product to metals can be increased. The carbon-carbon unsaturated double bond is not particularly limited, but examples include a vinyl group, an acrylic group, a methacrylic group, an allyl group, and a 1-propenyl group. The allyl group is a group represented by formula (15), and the 1-propenyl group is a group represented by formula (16).

[0084]

[0085]

[0086] The phenol compound (C) preferably has at least one of an allyl group and a 1-propenyl group in one molecule. In other words, the phenol compound (C) preferably has at least one of a group represented by formula (15) and a group represented by formula (16). In this case, the glass transition temperature of the cured product and the adhesion of the cured product to metals can be further increased. The reason why the phenol compound (C) has at least one of an allyl group and a 1-propenyl group in one molecule can further increase the glass transition temperature of the cured product and the adhesion of the cured product to metals is presumed to be as follows.

[0087] When a resin composition containing a polyphenylene ether compound (A) and a maleimide compound (B) but not a phenolic compound (C1) is cured, the polyphenylene ether compound (A) and the maleimide compound (B) are difficult to mix and react with each other, and therefore a composite of the polyphenylene ether compound (A) and the maleimide compound (B) tends to be difficult to form. In contrast, when a composition (M) containing a polyphenylene ether compound (A) and a maleimide compound (B) and a phenolic compound (C) having at least one of an allyl group and a 1-propenyl group per molecule is cured, the phenolic compound (C) can promote the formation of a composite of the polyphenylene ether compound (A) and the maleimide compound (B), and therefore a composite of the polyphenylene ether compound (A) and the maleimide compound (B) can be easily formed. This is presumably capable of further increasing the glass transition temperature of the cured product and the adhesion of the cured product to metals. The ease of forming a composite between the polyphenylene ether compound (A) and the maleimide compound (B) can be confirmed by measuring the loss tangent (tan δ) of the cured product of the resin composition using a dynamic viscoelasticity analyzer (DMA). Specifically, in the case of a resin composition that is unlikely to form a composite between the polyphenylene ether compound (A) and the maleimide compound (B) when cured, a graph of the loss tangent obtained by measuring the dynamic viscoelasticity of the cured product will show a broad maximum peak or multiple peaks. In contrast, in the case of the composition (M) of the present disclosure that is likely to form a composite between the polyphenylene ether compound (A) and the maleimide compound (B) when cured, a graph of the loss tangent obtained by measuring the dynamic viscoelasticity of the cured product will show a sharp single maximum peak.

[0088] The phenol compound (C) preferably contains a phenol compound (C0) having a chemical structure represented by formula (17) (hereinafter also referred to as phenol compound (C0)). When the phenol compound (C) contains the phenol compound (C0), the glass transition temperature of the cured product and the adhesion of the cured product to metal can be further increased.

[0089]

[0090] R in formula (17) ３９ ~R ４１ are each independent. ３９ is bonded to the oxygen atom in formula (17) and represents an allyl group, a 1-propenyl group, or a hydrogen atom. ４０ is bonded to any of the carbon atoms of the aromatic ring in formula (17) and represents an allyl group, a 1-propenyl group, or a hydrogen atom. ３９ and R ４０ At least one of R represents an allyl group or a 1-propenyl group. ４１ is bonded to a carbon atom of the aromatic ring in formula (17) and represents a hydrogen atom, a methyl group, a methoxy group, a hydroxy group, an aldehyde group, or a phenyl group. In other words, the phenol compound (C1-1) may have other substituents in addition to the allyl group or the 1-propenyl group in one molecule.

[0091] Regarding the aromatic ring in formula (17), R ４０ and R ４１ In addition, other substituents such as organic groups may be attached to the carbon atoms of the aromatic ring.

[0092] Furthermore, the phenol compound (C0) preferably contains a polyfunctional phenol compound (C1) (hereinafter also referred to as phenol compound (C1)) having two or more chemical structures represented by formula (17) per molecule. In this case, the glass transition temperature of the cured product and the adhesion of the cured product to metal can be particularly increased. Note that, in the phenol compound (C1), each chemical structure represented by formula (17) is independent. In other words, in the phenol compound (C1), each chemical structure represented by formula (17) may be the same or different.

[0093] In the phenolic compound (C1), the chemical structures represented by formula (17) are bonded to each other, for example, via a linking group. In the present disclosure, the linking group refers to a divalent organic group that, in the two chemical structures represented by formula (17) in the phenolic compound (C1), connects one of the carbon atoms of the aromatic ring in one of the chemical structures represented by formula (17) to one of the carbon atoms of the aromatic ring in the other chemical structure represented by formula (17). In other words, when the phenolic compound (C1) has a linking group in one molecule, one of the carbon atoms of the aromatic ring in the chemical structure represented by formula (17) is bonded to the linking group. In addition, in the present disclosure, the phenolic compound (C1) also includes a compound in which the two chemical structures represented by formula (17) are directly bonded to one of the carbon atoms of the aromatic ring in one of the chemical structures represented by formula (17) without a linking group.

[0094] The phenol compound (C1) may have, for example, only one linking group per molecule, or may have two or more linking groups. When the phenol compound (C1) has two or more linking groups, the linking groups are independent of each other. That is, the two or more linking groups in the phenol compound (C1) may have the same structure or different structures.

[0095] Specific structures of the linking group include chemical structures represented by formulas (18) to (23).

[0096]

[0097]

[0098]

[0099]

[0100]

[0101] In formula (22), R ４２ and R ４３are each independently a hydrogen atom, a methyl group, an ethyl group, a phenyl group, or a trifluoromethyl group.

[0102]

[0103] In formula (23), u represents an integer of 0 to 35. ４４ and R ４６ are each independently a substituent containing a carbonate ester group. ４４ and R ４６ is particularly preferably a chemical structure represented by formula (24).

[0104]

[0105] In formula (23), R ４５ represents a cyclic aliphatic hydrocarbon group. The cyclic aliphatic hydrocarbon group may be a monocyclic aliphatic hydrocarbon group or a polycyclic aliphatic hydrocarbon group. The cyclic aliphatic hydrocarbon group preferably does not have an unsaturated bond. The cyclic aliphatic hydrocarbon group preferably has 6 to 20 carbon atoms. The cyclic aliphatic hydrocarbon group may have a substituent such as an allyl group, an alkyl group, or a halogen atom bonded thereto. It is particularly preferable that the cyclic aliphatic hydrocarbon group has a chemical structure represented by formula (25).

[0106]

[0107] When u in formula (23) is 2 or more, R contained in the repeating unit in formula (23) ４４ and R ４５ are independent for each repeating unit. ４４ and R ４５ may be the same or different for each repeating unit.

[0108] In formula (23), R ４７ and R ４８ are independent of each other. ４７ and R ４８ Examples of R include a hydrogen atom, an allyl group, and a 1-propenyl group. ４７ and R ４８are preferably the same group. ４７ and R ４８ is a hydrogen atom, in the phenol compound (C1), R ３９ is an allyl group or a 1-propenyl group, and R ４０ is preferably a hydrogen atom. ４７ and R ４８ When either one of R is an allyl group or a 1-propenyl group, in the phenol compound (C1), R ３９ is a hydrogen atom, and R ４０ is preferably an allyl group or a 1-propenyl group.

[0109] Regarding the phenol compound (C1), preferred combinations of the chemical structure represented by formula (17) and the linking groups represented by formulas (18) to (23) will be described.

[0110] The phenol compound (C1) particularly preferably contains a phenol compound (C11) represented by formula (26) (hereinafter also referred to as phenol compound (C11)). The phenol compound (C11) has a chemical structure represented by formula (17) and a chemical structure represented by formula (22).

[0111]

[0112] In formula (26), R ３９ ~R ４１ is R in formula (17). ３９ ~R ４１ In formula (26), R ４２ ~R ４３ is R in formula (22). ４２ ~R ４３ The phenol compound (C11) represented by formula (26) is R ３９ is a hydrogen atom, and R ４０ is an allyl group or a 1-propenyl group, and R ４１is preferably a hydrogen atom. In other words, the phenol compound (C11) having the chemical structure represented by formula (26) has a bisphenol group having two aromatic rings, and is preferably a bisphenol derivative in which both of the two aromatic rings in the bisphenol group are substituted with an allyl group or a 1-propenyl group. In this case, it is preferable that these aromatic rings in the bisphenol group have only one allyl group or one 1-propenyl group. Examples of the bisphenol group include a bisphenol A group, a bisphenol AP group, a bisphenol AF group, a bisphenol BP group, a bisphenol E group, and a bisphenol F group, with a bisphenol A group being preferred.

[0113] It is particularly preferred that the phenol compound (C1) contains a phenol compound (C12) represented by formula (27) (hereinafter also referred to as phenol compound (C12)). The phenol compound (C12) has a chemical structure represented by formula (17) and a chemical structure represented by formula (22). The phenol compound (C12) contains a phenol compound represented by formula (17) and a chemical structure represented by formula (22). ４２ is a hydrogen atom, and R ４３ The repeating unit in formula (27) contains a chemical structure represented by formula (22) in which is a hydrogen atom.

[0114]

[0115] In formula (27), x represents an integer of 2 or more and 4 or less. Preferably, x is 3. In formula (27), R ３９ ~R ４０ is R in formula (17). ３９ ~R ４０ It is the same as R ４１ is a hydrogen atom, and therefore is omitted in formula (27). When x in formula (27) is 2 or more, R ３９ and R ４０ are independent for each repeating unit. ３９ and R ４０ may be the same or different for each repeating unit.

[0116] In formula (27), R ３９ and R ４０ It is preferred that one of the groups is an allyl group or a 1-propenyl group, and the other is a hydrogen atom.

[0117] The phenol compound (C1) preferably contains a phenol compound (C13) represented by formula (28) (hereinafter also referred to as phenol compound (C13)), and also preferably contains a phenol compound (C14) represented by formula (29) (hereinafter also referred to as phenol compound (C14)). That is, the phenol compound (C1) preferably contains at least one of the phenol compound (C13) and the phenol compound (C14). Both the phenol compound (C13) and the phenol compound (C14) have a chemical structure represented by formula (17) and a chemical structure represented by formula (18).

[0118]

[0119]

[0120] In formula (28), y represents an integer of 1 or more and 3 or less. In formula (29), z represents an integer of 0 or more and 15 or less. R in formulas (28) to (29) ３９ ~R ４１ Each of these is R in formula (17) ３９ ~R ４１ In addition, when y in formula (28) and z in formula (29) are each 2 or more, R contained in the repeating units in formulas (28) to (29) are the same as each of the above. ３９ ~R ４１ are independent for each repeating unit. ３９ ~R ４１ may be the same or different for each repeating unit. ３９ and R ４０ It is preferred that one of the groups is an allyl group or a 1-propenyl group, and the other is a hydrogen atom.

[0121] Furthermore, the phenol compound (C1) preferably contains a phenol compound (C15) represented by formula (30) (hereinafter also referred to as phenol compound (C15)), and also preferably contains a phenol compound (C16) represented by formula (31) (hereinafter also referred to as phenol compound (C16)). That is, the phenol compound (C1) preferably contains at least one of the phenol compound (C15) and the phenol compound (C16). Both the phenol compound (C15) and the phenol compound (C16) have a chemical structure represented by formula (17) and a chemical structure represented by formula (18).

[0122]

[0123]

[0124] In formula (30), y represents an integer of 1 or more and 3 or less. In formula (31), z represents an integer of 0 or more and 15 or less. R in formulas (30) and (31) ３９ ~R ４１ Each of these is R in formula (17) ３９ ~R ４１ Also, R ４９ is bonded to an aromatic ring contained in the chemical structure represented by formula (17) in formulas (30) and (31), and represents a hydrogen atom or an organic group. Examples of the organic group include an alkyl group such as a methyl group, an alkoxy group such as a methoxy group, an aryl group such as a phenyl group, a hydroxy group, or an aldehyde group.

[0125] In addition, when y in formula (30) and z in formula (31) are each 2 or more, R contained in the repeating units in formulas (30) to (31) ３９ ~R ４１ and R ４９ Each of R is independent. ３９ ~R ４１ and R ４９ may be the same or different for each repeating unit.

[0126] In formulas (30) to (31), R ３９ and R ４０It is preferred that one of the groups is an allyl group or a 1-propenyl group, and the other is a hydrogen atom.

[0127] The phenol compound (C1) can be a commercially available product. Examples of such commercially available products include diallyl bisphenol A (DABPA manufactured by Daiwa Chemical Industry Co., Ltd.), biphenylene resin (SBA series manufactured by Gun-ei Chemical Industry Co., Ltd.), allyl phenol resin (APG series manufactured by Gun-ei Chemical Industry Co., Ltd.), allyl phenol resin (LVA series manufactured by Gun-ei Chemical Industry Co., Ltd.), propenylated biphenylene resin (BPN series manufactured by Gun-ei Chemical Industry Co., Ltd.), allyl ether phenol resin (FTC-AE series manufactured by Gun-ei Chemical Industry Co., Ltd.), and polyfunctional allyl phenol resin (FATC series manufactured by Gun-ei Chemical Industry Co., Ltd.).

[0128] <Other Resins> In addition to the polyphenylene ether compound (A), the maleimide compound (B), and the phenol compound (C), the resin component (R) may contain other thermosetting compounds (hereinafter also referred to as thermosetting resin component (R1)). The thermosetting resin component (R1) contains, for example, at least one selected from the group consisting of a benzoxazine compound (F), an epoxy compound, an unsaturated imide compound, a cyanate compound, an isocyanate compound, an oxetane compound, an amino compound, an unsaturated polyester compound, an allyl compound, a silicone compound, a triazine compound, and a melamine compound. Among these, it is preferable that the resin component (R) contains a benzoxazine compound (F). In this case, the adhesion of the cured product to metal can be further improved.

[0129] The benzoxazine compound (F) has one or more benzoxazine rings per molecule. The number of benzoxazine rings per molecule is preferably two or more. That is, the benzoxazine compound (F) preferably contains a polyfunctional benzoxazine compound. The polyfunctional benzoxazine compound can form a three-dimensional crosslinked structure by reaction with the polyphenylene ether compound (A), the maleimide compound (B), and the phenol compound (C). This can increase the glass transition temperature of the cured product. The number of benzoxazine rings is preferably two or more. Furthermore, from the viewpoint of crack resistance of the cured product, this number is preferably four or less. Furthermore, the benzoxazine compound (F) preferably has an allyl group in the molecule. In this case, the glass transition temperature of the cured product can be further increased.

[0130] The benzoxazine compound (F) preferably contains a benzoxazine compound represented by formula (32).

[0131]

[0132] In formula (32), R ５０ Examples include a single bond, CH ２ ,O,CO,C(CH ３ ) ２ , C(CF ３ ) ２ , phenylene group, naphthylene group, dicyclopentadiene group, etc. Among these, R ５０ is preferably a dicyclopentadiene group.

[0133] The benzoxazine compound (F) is not limited to the benzoxazine compound represented by the above formula (32), and may contain at least one selected from the group consisting of P-d type benzoxazine compounds, Fa type benzoxazine compounds, ALP-d type benzoxazine compounds, etc. The benzoxazine compound (F) may contain these compounds alone or two or more types in any ratio.

[0134] The weight-average molecular weight of the benzoxazine compound (F) is preferably 200 or more and 5000 or less. If this weight-average molecular weight is 200 or more, the glass transition temperature of the cured product can be increased. If this weight-average molecular weight is 5000 or less, the circuit filling property can be improved. The weight-average molecular weight may be measured by a general molecular weight measurement method, and specifically, a value measured using gel permeation chromatography (GPC) and converted into polystyrene may be used.

[0135] Commercially available benzoxazine compounds (F) can be used. Examples of such commercially available compounds include ALP-d benzoxazine, P-d benzoxazine, and Fa benzoxazine manufactured by Shikoku Chemical Industry Co., Ltd., KZH-5031, KZH-5032, KZH-5075, KZH-5085, and KZH-5086 manufactured by Kolon Industries, Inc., and JBZ-BA100N, JBZ-FA100N, JBZ-DP100N, JBZ-OP100N, JBZ-OP100D, and JBZ-OP100I manufactured by JFE Chemical Corporation.

[0136] <Core-shell rubber> As described above, the composition (M) contains the core-shell rubber (D). The core-shell rubber (D) imparts flexibility to the cured product and has sufficient dispersibility in the composition (M). Therefore, cracking in the cured product can be suppressed. This allows the cured product to achieve high tensile strength. Note that the core-shell rubber (D) is not included in the resin component (R).

[0137] The core-shell rubber (D) has a core and a shell that covers the core. Both the core and the shell contain a resin. The core contains, for example, at least one resin selected from the group consisting of styrene-butadiene resin, butadiene resin, isoprene resin, acrylic resin, and silicone resin. The shell contains at least one resin selected from the group consisting of acrylic resin, methacrylic resin, and styrene resin.

[0138] Commercially available core-shell rubbers (D) can be used, including, for example, the Metablen Type S series, Type W series, Type C series, and Type E series manufactured by Mitsubishi Chemical Corporation, the Kane Ace MX series manufactured by Kaneka Corporation, the PARALOID series such as PARALOID-TMS-2670 manufactured by Dow Inc., the Stafiloid series manufactured by Aica Kogyo Co., Ltd., and the GENIOPERL series such as GENIOPERL P52 manufactured by WACKER Chemie AG.

[0139] The average particle size of the core-shell rubber is not particularly limited, but is, for example, 0.001 μm or more and 1 μm or less, and preferably 0.5 μm or less.

[0140] <Inorganic Filler> As described above, the composition (M) contains an inorganic filler (E). In this case, the linear expansion coefficient of the cured product can be reduced. Examples of the inorganic filler (E) include silica fillers such as spherical silica fillers, metal oxide fillers such as alumina fillers, titanium oxide fillers, and mica fillers, metal hydroxide fillers such as aluminum hydroxide fillers and magnesium hydroxide fillers, sulfate fillers such as talc fillers, aluminum borate fillers, and barium sulfate fillers, and carbonate fillers such as calcium carbonate. Among these, the inorganic filler (E) is preferably at least one selected from the group consisting of silica fillers, mica fillers, and talc fillers, and more preferably spherical silica fillers. Note that the inorganic fillers (E) may be used alone or in combination of two or more.

[0141] For example, the inorganic filler (E) may be surface-treated with a silane coupling agent. Examples of the silane coupling agent include vinyltriethoxysilane, vinyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropylethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, glycidoxypropyltriethoxysilane, and isocyanatopropyltriethoxysilane. One type of silane coupling agent may be used alone, or two or more types may be used in combination.

[0142] <Additives> In addition to the above-described components, the composition (M) may contain other components (hereinafter also referred to as additives (G)) as needed, within the scope of not impairing the effects of the present invention. The additives (G) contained in the composition (M) may include, for example, at least one component selected from the group consisting of a coupling agent, a reaction initiator, an antifoaming agent, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a dye or pigment, a polymerization inhibitor, a wetting and dispersing agent, a lubricant, and the like.

[0143] [Contents] The contents of the components contained in the composition (M) will be described.

[0144] As described above, the content of the core-shell rubber (D) is 1 part by mass or more and 20 parts by mass or less relative to the resin component (R). When this content is 1 part by mass or more, the tensile strength of the cured product can be improved. When this content is 20 parts by mass or less, a decrease in circuit filling ability can be suppressed. This content is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. This content is preferably 15 parts by mass or less, and more preferably 10 parts by mass or less.

[0145] Furthermore, the content of the core-shell rubber (D) is preferably 1 part by mass or more and 25 parts by mass or less relative to the total of the polyphenylene ether compound (A), the maleimide compound (B), and the phenol compound (C). When this content is 1 part by mass or more, the tensile strength of the cured product can be further improved. When this content is 25 parts by mass or less, the deterioration of circuit filling ability can be further suppressed. This content is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. This content is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less.

[0146] The content of the polyphenylene ether compound (A) is preferably 10% by mass or more and 50% by mass or less relative to the resin component (R). When this content is 10% by mass or more, the dielectric constant and dielectric dissipation factor of the cured product can be further reduced. When this content is 50% by mass or less, the glass transition temperature of the cured product can be further increased. This content is more preferably 15% by mass or more, and even more preferably 20% by mass or more. This content is more preferably 45% by mass or less, and even more preferably 40% by mass or less.

[0147] Furthermore, when the polyphenylene ether compound (A) contains a modified polyphenylene ether compound (A1) terminally modified with a substituent having a carbon-carbon unsaturated double bond, the content of the modified polyphenylene ether compound (A1) is preferably 10% by mass or more based on the total polyphenylene ether compound (A). In this case, the dielectric constant and dielectric dissipation factor of the cured product can be further reduced, and the glass transition temperature of the cured product can be further increased. This content is more preferably 40% by mass or more, and even more preferably 100% by mass.

[0148] The content of the benzoxazine compound (F) is preferably 1% by mass or more and 20% by mass or less relative to the resin component (R), in which case the adhesion of the cured product to metals can be further improved.

[0149] The content of the maleimide compound (B) is preferably 20% by mass or more and 75% by mass or less relative to the resin component (R). If this content is 20% by mass or more, the glass transition temperature of the cured product can be increased. If this content is 75% by mass or less, the dielectric constant and dielectric dissipation factor of the cured product can be reduced. This content is more preferably 30% by mass or more, and even more preferably 40% by mass or more. This content is more preferably 70% by mass or less, and even more preferably 60% by mass or less.

[0150] The content of the phenol compound (C) is preferably 5% by mass or more and 40% by mass or less relative to the resin component (R). If this content is 5% by mass or more, it is possible to easily improve the adhesion of the cured product to metals. If this content is 40% by mass or less, it is possible to easily increase the glass transition temperature of the cured product. This content is more preferably 10% by mass or more, and even more preferably 15% by mass or more. This content is more preferably 30% by mass or less, and even more preferably 20% by mass or less.

[0151] The content of the inorganic filler (E) is preferably 40% by mass or more and 80% by mass or less, based on the total amount of the composition (M). When this content is 40% by mass or more, the linear expansion coefficient of the cured product can be easily reduced. When this content is 80% by mass or less, the adhesion of the cured product to metal can be easily improved. This content is more preferably 50% by mass or more, and even more preferably 60% by mass or more. This content is more preferably 75% by mass or less, and even more preferably 70% by mass or less.

[0152] [Physical Properties] The physical properties of the composition (M) and the cured product of the composition (M) will be described.

[0153] For example, the cured product has high tensile strength. Specifically, the tensile elongation of the cured product is 2.5% or more. By appropriately changing the components of the composition (M) listed above, the tensile elongation of the cured product can be increased to 3.5% or more, or even 4.5% or more.

[0154] For example, the cured product has a low coefficient of linear expansion. Specifically, the coefficient of linear expansion of the cured product is 60 ppm / °C or less. By appropriately changing the components of the composition (M) listed above, the coefficient of linear expansion of the cured product can be set to 50 ppm / °C or less, or even 40 ppm / °C or less.

[0155] For example, the cured product has high heat resistance. Specifically, the glass transition temperature of the cured product is preferably 160°C or higher, more preferably 180°C or higher, and even more preferably 200°C or higher.

[0156] For example, the cured product can have high adhesion to metals. Specifically, the peel strength of the cured product is preferably 0.5 kN / m or more, and more preferably 0.7 kN / m or more.

[0157] Furthermore, the composition (M) has good circuit filling properties, and when the composition (M) is filled into a circuit and cured, the generation of voids between the circuits can be suppressed.

[0158] [Preparation Method] The preparation method of the composition (M) will be described.

[0159] The method for preparing the composition (M) is not particularly limited, and examples thereof include a method in which the resin component (R), the core-shell rubber (D), and the inorganic filler (E) are mixed to a predetermined content. If necessary, other components may be appropriately added and mixed in addition to the resin component (R), the core-shell rubber (D), and the inorganic filler (E).

[0160] The composition (M) may also contain an organic solvent. In other words, a varnish made from the composition (M) can be used. Such a varnish can be made, for example, as follows: First, among the components contained in the composition (M), components that are soluble in the organic solvent are added to the organic solvent and dissolved while stirring to prepare a mixture. This mixture may also be made by stirring while heating. Next, components that are insoluble in the organic solvent are added to the mixture and dispersed until the desired dispersion state is achieved using a ball mill, bead mill, planetary mixer, roll mill, or the like. A varnish can be made according to this method. Furthermore, the organic solvent used here is preferably one that can dissolve, for example, the resin component (R) and does not inhibit the curing reaction of the composition (M). Specific examples of the organic solvent include toluene and methyl ethyl ketone (MEK).

[0161] [Application Examples] Application examples of the composition (M) will be described with reference to Figs.

[0162] By using the composition (M), a prepreg 1, a metal-clad laminate 11, a wiring board 21, a resin-coated metal foil 31, and a resin-coated film 41 can be obtained.

[0163] More specifically, the resin layer 2 of the prepreg 1 contains at least one of the composition (M) and a semi-cured product of the composition (M). The insulating layer 12 of the metal-clad laminate 11 contains a cured product of the composition (M). The insulating layer 22 of the wiring board 21 contains a cured product of the composition (M). The resin layer 32 of the resin-coated metal foil 31 contains at least one of the composition (M) and a semi-cured product of the composition (M). The resin layer 42 of the resin-coated film 41 contains at least one of the composition (M) and a semi-cured product of the composition (M).

[0164] In this embodiment, the semi-cured product refers to a state in which the composition (M) has been partially cured to the extent that it can be further cured. For example, when the composition (M) is heated, the viscosity gradually decreases at the beginning of heating, but as the curing of the composition (M) begins, the viscosity gradually increases. In this way, the semi-cured product refers to the composition (M) in a semi-cured state, and can also be said to be the composition (M) in a B-stage.

[0165] [Prepreg] FIG. 1 is a schematic cross-sectional view showing an example of a prepreg 1 according to an embodiment of the present disclosure.

[0166] As shown in Figure 1, the prepreg 1 includes a resin layer 2. The resin layer 2 includes at least one of the composition (M) and a semi-cured product of the composition (M). The resin layer 2 further includes a fibrous base material 3. That is, the prepreg 1 may include a resin layer 2 in which the fibrous base material 3 is impregnated with at least one of the composition (M) and a semi-cured product of the composition (M).

[0167] Furthermore, the prepreg 1 obtained using the composition (M) may contain a semi-cured product of the composition (M), as described above, or may contain an uncured composition (M), i.e., an uncured product of the composition (M).

[0168] As described above, the prepreg 1 may include a resin layer 2 obtained by impregnating a fibrous base material 3 with at least one of the composition (M) and a semi-cured product of the composition (M). When impregnating the fibrous base material 3 with at least one of the composition (M) and a semi-cured product of the composition (M), it is preferable to use a varnish made from the composition (M).

[0169] Specific examples of the fibrous substrate 3 include glass cloth, aramid cloth, polyester cloth, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper, and linter paper. The use of glass cloth can produce a laminate with excellent mechanical strength. It is particularly preferable that the glass cloth be flattened. A specific example of the flattening process is a method in which the glass cloth is continuously pressed with a press roll at an appropriate pressure to compress the yarns flat. The thickness of the fibrous substrate 3 typically used is, for example, 0.01 mm or more and 0.3 mm or less.

[0170] Furthermore, in obtaining the resin layer 2, the fibrous substrate 3 is impregnated with the varnish by immersing the fibrous substrate 3 in the varnish or by applying the varnish to the fibrous substrate 3, and the impregnation can be repeated multiple times as necessary. In this case, by repeating the impregnation using multiple varnishes with different compositions and concentrations, it is possible to obtain a resin layer 2 containing the composition (M) or a semi-cured product of the composition (M) with the desired composition and impregnation amount.

[0171] Furthermore, in the method for producing the prepreg 1, for example, the resin layer 2 may be produced by impregnating the fibrous base material 3 with a varnish containing the composition (M) and an organic solvent, and then heating the resin layer 2 to reduce or remove the organic solvent from the resin layer 2. Conditions for reducing or removing the organic solvent from the resin layer 2 by heating the resin layer 2 include, for example, a temperature of 80°C or higher and 180°C or lower, and a heating time of 1 minute or higher and 10 minutes or lower.

[0172] In this way, a prepreg 1 is obtained, which includes a resin layer 2 containing at least one of an uncured product of the composition (M) (A-stage composition (M)) and a semi-cured product of the composition (M) (B-stage composition (M)). The insulating layer 12 of the metal-clad laminate 11 or the insulating layer 22 of the wiring board 21 can be produced from the prepreg 1, which includes a resin layer 2 containing at least one of the composition (M) and a semi-cured product of the composition (M). The prepreg 1 also contains at least one of the composition (M) and a semi-cured product of the composition (M). Therefore, when the prepreg 1 is used to produce the insulating layer 22 of the wiring board 21, it exhibits good circuit filling properties.

[0173] 2 is a schematic cross-sectional view showing an example of a metal-clad laminate 11. The metal-clad laminate 11 includes an insulating layer 12 containing a cured product of the composition (M) and a metal foil 13 overlying the insulating layer 12.

[0174] As described above, the insulating layer 12 contains a cured product of the composition (M). The insulating layer 12 may be made of a cured product of the composition (M). The insulating layer 12 may also be made of a cured product of the prepreg 1. That is, the metal-clad laminate 11 includes, for example, an insulating layer 12 containing a cured product of the prepreg 1 shown in FIG. 1 and a metal foil 13 overlapping the insulating layer 12. The metal-clad laminate 11 may include another layer in addition to the insulating layer 12 and the metal foil 13.

[0175] An example of a method for producing the metal-clad laminate 11 is a method in which an insulating layer 12 is produced from a cured product of the composition (M), the insulating layer 12 is formed on a metal foil 13, and the insulating layer 12 is heated and pressurized to produce the metal-clad laminate 11. More specifically, the method for producing the metal-clad laminate 11 involves overlaying a metal foil 13 such as a copper foil on both sides or one side of the insulating layer 12 containing the cured product of the composition (M), and then heating and pressurizing the metal foil 13 and the insulating layer 12 to form an integrated laminate, thereby producing a metal-clad laminate 11 with the metal foil 13 attached to both sides or one side.

[0176] Alternatively, the insulating layer 12 may be produced using the prepreg 1. More specifically, the prepreg 1 is heated and cured to produce the insulating layer 12 containing the cured product of the prepreg 1. Subsequently, a metal foil 13 such as copper foil is placed on both sides or one side of the insulating layer 12 containing the cured product of the prepreg 1, and the metal foil 13 and the insulating layer 12 are heated and pressurized to be laminated and integrated, thereby producing a metal-clad laminate 11 in which the metal foil 13 is attached to both sides or one side of the insulating layer 12 containing the cured product of the prepreg 1.

[0177] Furthermore, the insulating layer 12 can be produced using a resin-coated metal foil 31 described below. More specifically, the insulating layer 12 of the metal-clad laminate 11 can be produced by heating and curing the resin layer 32 of the resin-coated metal foil 31. In this case, the metal foil 33 of the resin-coated metal foil 31 becomes the metal foil 13 of the metal-clad laminate 11. The insulating layer 12 can also be produced by using a resin-coated film 41 described below. More specifically, the insulating layer 12 of the metal-clad laminate 11 can be produced by heating and curing the resin layer 42 of the resin-coated film 41.

[0178] The heating and pressing conditions when producing the metal-clad laminate 11 are preferably set appropriately depending on the thickness of the metal-clad laminate 11 to be produced, the type of resin composition forming the insulating layer 12, and the like.

[0179] The heating temperature when producing the metal-clad laminate 11 is, for example, 170° C. or higher and 230° C. or lower. The pressure when producing the metal-clad laminate 11 is, for example, 1.5 MPa or higher and 5.0 MPa or lower. The heating and pressing time when producing the metal-clad laminate 11 is, for example, 60 minutes or higher and 150 minutes or lower.

[0180] When producing the metal-clad laminate 11, the thickness of the metal foil 13 can be appropriately set depending on the desired purpose. For example, a metal foil 13 having a thickness of 0.2 μm or more and 70 μm or less can be used. When the metal foil has a thickness of, for example, 10 μm or less, a carrier-attached copper foil having a release layer and a carrier may be used to improve handling. The thickness of the metal foil 13 is preferably 0.2 μm or more and 35 μm or less, and more preferably 1 μm or more and 18 μm or less. Even when the metal foil 13 is thin, when the composition (M) is used to produce the metal-clad laminate 11, the adhesion between the insulating layer 12 and the metal foil 13 in the metal-clad laminate 11 is good. Furthermore, in the metal-clad laminate 11, the peel strength between the insulating layer 12 and the metal foil 13 is preferably 0.5 kN / m or more, and more preferably 0.7 kN / m or more.

[0181] As described above, the metal-clad laminate 11 of the present disclosure includes an insulating layer 12 containing at least one of a cured product of the composition (M) and a cured product of the prepreg 1, and a metal foil 13.

[0182] 3 is a schematic cross-sectional view showing an example of a wiring board 21. The wiring board 21 includes an insulating layer 22 made of the composition (M) and wiring 23 overlapping the insulating layer 22.

[0183] As described above, insulating layer 22 includes a cured product of composition (M). Insulating layer 22 may be made of a cured product of composition (M). Insulating layer 22 may also be made of a cured product of prepreg 1. In other words, wiring board 21 includes insulating layer 22 used by curing prepreg 1 shown in FIG. 1 and wiring 23 overlapping insulating layer 22.

[0184] Furthermore, wiring board 21 may be made from metal-clad laminate 11. In this case, wiring board 21 includes insulating layer 22 made from insulating layer 12, and wiring 23 that overlaps insulating layer 22 and is formed by partially removing metal foil 13.

[0185] As described above, examples of methods for producing wiring board 21 include a method of producing wiring board 21 using metal-clad laminate 11. More specifically, wiring can be formed by etching metal foil 13 on the surface of metal-clad laminate 11. That is, wiring board 21 can be obtained by forming a circuit by partially removing metal foil 13 on the surface of metal-clad laminate 11. In addition to the above methods, circuits can also be formed by, for example, a semi-additive process (SAP) or a modified semi-additive process (MSAP).

[0186] 4 is a schematic cross-sectional view showing an example of a resin-coated metal foil 31 according to this embodiment. The resin-coated metal foil 31 includes a resin layer 32 containing at least one of the composition (M) and a semi-cured product of the composition (M), and a metal foil 33 overlying the resin layer 32. The resin-coated metal foil 31 may also include another layer between the resin layer 32 and the metal foil 33.

[0187] As described above, the resin layer 32 may contain a semi-cured product of the composition (M), or may contain an uncured product of the composition (M). That is, the resin-coated metal foil 31 may be a resin-coated metal foil 31 including a resin layer 32 including a semi-cured product of the composition (M) (B-stage composition (M)) and a metal foil 33, or a resin-coated metal foil 31 including a resin layer 32 including an uncured product of the composition (M) before curing (A-stage composition (M)) and a metal foil 33.

[0188] The resin layer 32 may or may not include a fibrous base material 3. When the resin layer 32 includes a fibrous base material 3, the fibrous base material 3 may be the same as the fibrous base material 3 of the prepreg 1. In other words, the resin layer 32 can be produced from the prepreg 1.

[0189] As the metal foil 33, the same metal foil 13 used in the metal-clad laminate 11 can be used.

[0190] The resin-coated metal foil 31 may be provided with a cover film or the like as needed. By providing a cover film, it is possible to prevent the inclusion of foreign matter, etc. The cover film is not particularly limited, but examples thereof include polyolefin film, polyester film, polymethylpentene film, and films formed by providing a release agent layer on these films. Note that the cover film may be subjected to a surface treatment such as a matte treatment, corona treatment, release treatment, or roughening treatment as needed.

[0191] The resin-coated metal foil 31 can be produced, for example, by applying a varnish made from the composition (M) onto a metal foil 33 and heating it. The varnish can be applied onto the metal foil 33 by using a bar coater.

[0192] As described above, by heating the varnish applied to the metal foil 33, the organic solvent can be volatilized from the varnish, thereby reducing or removing the organic solvent. The applied varnish can be heated, for example, at a temperature of 80°C or higher and 180°C or lower for a time period of 1 minute to 10 minutes. That is, the conditions for heating the resin layer 32 to reduce or remove the organic solvent from the resin layer 32 may be the same as the conditions for heating the resin layer 2 to reduce or remove the organic solvent from the resin layer 2 when producing the prepreg 1. By heating the varnish applied to the metal foil 33 in this manner, a resin layer 32 containing at least one of the composition (M) and a semi-cured product of the composition (M) can be formed on the metal foil 33.

[0193] [Resin-Coated Film] Fig. 5 is a schematic cross-sectional view showing an example of a resin-coated film 41 according to the present embodiment. The resin-coated film 41 comprises a resin layer 42 containing at least one of the composition (M) and a semi-cured product of the composition (M), and a support film 43. That is, the resin-coated film 41 comprises a resin layer 42 containing at least one of the composition (M) and a semi-cured product of the composition (M), and a support film 43 overlapping the resin layer 42. The resin-coated film 41 may also comprise another layer between the resin layer 42 and the support film 43.

[0194] Furthermore, as described above, the resin layer 42 may contain a semi-cured product of the composition (M), or may contain an uncured product of the composition (M). That is, the resin-coated film 41 may be a resin-coated film 41 including a resin layer 42 including a semi-cured product of the composition (M) (B-stage composition (M)) and a support film 43, or may be a resin-coated film 41 including a resin layer 42 including an uncured product of the composition (M) before curing (A-stage composition (M)) and a support film 43.

[0195] The resin layer 42 may or may not include a fibrous base material 3. When the resin layer 42 includes a fibrous base material 3, the same fibrous base material 3 as the fibrous base material 3 of the prepreg 1 can be used. In other words, the resin layer 42 may be made from the prepreg 1.

[0196] The support film 43 also includes at least one electrically insulating film selected from the group consisting of, for example, polyester film, polyethylene terephthalate (PET) film, polyimide film, polyparabanic acid film, polyether ether ketone film, polyphenylene sulfide film, polyamide film, polycarbonate film, and polyarylate film.

[0197] The resin-coated film 41 may be provided with a cover film, etc., as required. The same cover film as that used for the resin-coated metal foil 31 can be used.

[0198] The support film 43 and the cover film may be subjected to surface treatment such as matte treatment, corona treatment, release treatment, or roughening treatment, if necessary.

[0199] The resin-coated film 41 can be produced, for example, by applying varnish onto the support film 43 and heating it. The varnish can be applied to the support film 43 by using a bar coater.

[0200] As described above, by heating the varnish applied to the support film 43, the organic solvent can be volatilized from the varnish, thereby reducing or removing the organic solvent. The applied varnish is heated, for example, at a temperature of 80°C or higher and 180°C or lower for a time period of 1 minute to 10 minutes. That is, the conditions for heating the resin layer 42 to reduce or remove the organic solvent from the resin layer 42 may be the same as the conditions for heating the resin layer 2 to reduce or remove the organic solvent from the resin layer 2 when producing the prepreg 1. In this way, a resin layer 42 containing at least one of the composition (M) and a semi-cured product of the composition (M) is formed on the support film 43, thereby producing the resin-coated film 41.

[0201] [Aspects] As is clear from the above embodiment, the resin composition according to the first aspect of the present disclosure contains a resin component (R), a core-shell rubber (D), and an inorganic filler (E). The resin component (R) contains a polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond, a maleimide compound (B), and a phenol compound (C) having a carbon-carbon unsaturated double bond. The core-shell rubber (D) is present in an amount of 1 part by mass or more and 20 parts by mass or less relative to the resin component (R).

[0202] According to this embodiment, it is possible to provide a resin composition resin that can achieve favorable circuit filling properties and a favorable linear expansion coefficient of the cured product, and that can also achieve high tensile strength of the cured product.

[0203] In the resin composition according to the second aspect of the present disclosure, in the first aspect, the resin component (R) further contains a benzoxazine compound (F).

[0204] In this case, the adhesion of the cured product to the metal can be further improved.

[0205] In the resin composition according to the third aspect of the present disclosure, in the first or second aspect, the phenol compound (C1) has at least one of a group represented by formula (15) and a group represented by formula (16).

[0206]

[0207]

[0208] According to this embodiment, the heat resistance of the cured product and the adhesion of the cured product to metal can be improved.

[0209] In the resin composition according to the fourth aspect of the present disclosure, in any one of the first to third aspects, the phenol compound (C) contains a polyfunctional phenol compound (C1) having two or more chemical structures represented by formula (17) in one molecule.

[0210]

[0211] (In formula (17), R ３９ represents a hydrogen atom, a formula represented by formula (15) or a formula represented by formula (16), and R ４０ represents a hydrogen atom, a formula represented by formula (15) or a formula represented by formula (16), and R ３９ and R ４０ At least one of the formulas represents a formula represented by formula (15) or a formula represented by formula (16), and R ４１ represents a hydrogen atom, a methyl group, a methoxy group, a hydroxyl group, an aldehyde group, or a phenyl group.

[0212] According to this embodiment, the glass transition temperature of the cured product and the adhesiveness of the cured product to metal can be particularly increased.

[0213] In the resin composition according to a fifth aspect of the present disclosure, in any one of the first to fourth aspects, the polyphenylene ether compound (A) contains a modified polyphenylene ether compound (A1) terminally modified with a substituent having a carbon-carbon unsaturated bond. The modified polyphenylene ether compound (A1) has at least one of a group represented by formula (1) and a group represented by formula (2).

[0214]

[0215] (In formula (1), p represents an integer of 0 to 10, Z represents an arylene group, and R １ ~R ３ each independently represents a hydrogen atom or an alkyl group.

[0216]

[0217] (In formula (2), R ４ represents a hydrogen atom or an alkyl group.

[0218] According to this embodiment, the curability of the resin composition can be further improved.

[0219] In the resin composition according to a sixth aspect of the present disclosure, in any one of the first to fifth aspects, the core-shell rubber (D) has a core and a shell covering the core. The core contains at least one resin selected from the group consisting of a styrene-butadiene resin, a butadiene resin, an isoprene resin, an acrylic resin, and a silicone resin. The shell contains at least one resin selected from the group consisting of an acrylic resin, a methacrylic resin, and a styrene resin.

[0220] In the resin composition according to the seventh aspect of the present disclosure, in any one of the first to sixth aspects, the content of the phenol compound (C1) is 5% by mass or more and 40% by mass or less relative to the resin component (R).

[0221] According to this embodiment, the adhesiveness of the cured product to metal can be easily improved, and the heat resistance of the cured product can be easily improved.

[0222] In the resin composition according to the eighth aspect of the present disclosure, in any one of the first to seventh aspects, the content of the inorganic filler (E) is 40% by mass or more and 80% by mass or less, relative to the total amount of the resin composition.

[0223] According to this embodiment, the linear expansion coefficient of the cured product can be easily reduced, and the adhesion of the cured product to metal can be easily increased.

[0224] A prepreg according to a ninth aspect of the present disclosure includes a resin layer containing at least one of the resin composition according to any one of the first to eighth aspects and a semi-cured product of the resin composition. The resin layer further includes a fibrous base material.

[0225] A metal-clad laminate according to a tenth aspect of the present disclosure comprises an insulating layer containing a cured product of the resin composition of any one of the first to eighth aspects, and a metal foil.

[0226] A wiring board according to an eleventh aspect of the present disclosure includes an insulating layer containing a cured product of the resin composition according to any one of the first to eighth aspects, and wiring.

[0227] A resin-coated metal foil according to a twelfth aspect of the present disclosure comprises a resin layer containing at least one of the resin composition of any one of the first to eighth aspects and a semi-cured product of the resin composition, and a metal foil.

[0228] A resin-coated film according to a thirteenth aspect of the present disclosure comprises a resin layer comprising at least one of the resin composition of any one of the first to eighth aspects and a semi-cured product of the resin composition, and a support film.

[0229] The present disclosure will be specifically described below with reference to examples, but the present disclosure is not limited to the examples.

[0230] 1. Preparation of Resin Compositions The components used in preparing the resin compositions of Examples 1 to 16 and Comparative Examples 1 to 4 will be described.

[0231] [Components] (Polyphenylene ether compounds) Polyphenylene ether compound #1: a polyphenylene ether compound having a vinylbenzyl group (ethenylbenzyl group) at the end (OPE-2st 1200 manufactured by Mitsubishi Gas Chemical Company, Inc., represented by formula (10), in which Z is a phenylene group and R ２ ~R ４ is a hydrogen atom and p is 1. Polyphenylene ether compound #2: a polyphenylene ether compound having a terminal vinylbenzyl group (OPE-2St 2200 manufactured by Mitsubishi Gas Chemical Company, Inc., represented by formula (10), Z is a phenylene group, R ２ ~R ４ is a hydrogen atom and p is 1.

[0232] (Maleimide Compounds) Maleimide Compound #1: Represented by formula (13), R ３５ ~R ３８is a hydrogen atom (MIR-3000-70M, manufactured by Nippon Kayaku Co., Ltd.). Maleimide compound #2: A maleimide compound represented by formula (14) (MIR-5000-60T, manufactured by Nippon Kayaku Co., Ltd.). Maleimide compound #3: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide (BMI5100, manufactured by Daiwa Kasei Kogyo Co., Ltd., molecular weight 442).

[0233] (Phenol Compounds) Phenolic compound #1: a phenolic compound having an allyl group in the molecule (LVA01EK manufactured by Gunei Chemical Industry Co., Ltd.) Phenolic compound #2: 2,2'-diallylbisphenol A (DABPA manufactured by Daiwa Chemical Industry Co., Ltd.).

[0234] (Core-shell rubber) Core-shell rubber #1: Silicone-acrylic composite rubber (SRK200A manufactured by Mitsubishi Chemical Corporation. Core: silicone / acrylic polymer. Shell: styrene-acrylonitrile copolymer. Average particle size: 0.15 μm).

[0235] (Inorganic Filler) Inorganic Filler #1: Silica particles surface-treated with a silane coupling agent having a phenylamino group in the molecule (SC2500-SXJ, manufactured by Admatechs Co., Ltd.).

[0236] (Benzoxazine Compounds) Benzoxazine Compound #1: Represented by formula (32), R ５０ A benzoxazine compound in which the carbon atom is dicyclopentadiene (KZH-5031 manufactured by Kolon Industries, Inc.).

[0237] (Additives) Additive #1: Organic peroxide 1,3-bis(butylperoxyisopropyl)benzene (Perbutyl P, manufactured by NOF Corporation).

[0238] Additive #2: Polymerization inhibitor (Q5010 manufactured by Koei Chemical Co., Ltd.).

[0239] [Preparation Method] First, the above components except for the inorganic filler were added to methyl ethyl ketone in the proportions (parts by mass) shown in Tables 1 to 3 so that the solids concentration was 60 mass% and mixed. The mixture was stirred for 60 minutes. Thereafter, the inorganic filler was added to the resulting mixture, and the inorganic filler was dispersed using a bead mill. A varnish was obtained by this method.

[0240] 2. Evaluation of Resin Compositions In measuring the tensile strength, glass transition temperature, thermal expansion coefficient, dielectric constant / dielectric loss tangent, circuit filling property, and adhesion strength, a resin-coated metal foil prepared from the resin composition (varnish) of each Example and Comparative Example, a metal-clad laminate prepared from the resin-coated metal foil (evaluation substrate 1), and an evaluation substrate 2 prepared from evaluation substrate 1 were prepared, and the evaluations were carried out using these.

[0241] <<Method of producing resin-coated metal foil, evaluation substrate 1, and evaluation substrate 2>> First, two thin copper foils with a carrier copper foil (MT18FL manufactured by Mitsui Mining & Smelting Co., Ltd.; thin copper foil thickness: 3 μm; carrier copper foil thickness: 18 μm) were prepared. Next, the resin composition (varnish) of each example and comparative example prepared in "1. Preparation of resin composition" was applied to the thin copper foil surface of each of the thin copper foils with a carrier copper foil, and this was heated and dried at 130°C for 3 minutes until it reached a semi-cured state, thereby producing a resin-coated metal foil comprising a thin copper foil with a carrier copper foil and a resin layer containing a semi-cured product of the resin composition.

[0242] Next, two resin-coated metal foils prepared by the above method are bonded together so that the resin layers are bonded to each other, and then, under vacuum conditions at a temperature of 220°C and a pressure of 20 to 40 kg / cm ２ By heating and pressing for 120 minutes under the above conditions, a metal-clad laminate (evaluation substrate 1) was obtained, which had an insulating layer with a thickness of 80 μm and thin copper foils with carrier copper foils on both sides of the insulating layer.

[0243] The carrier copper foil of this metal-clad laminate was then peeled off, and the thin copper foil was further etched to obtain an evaluation substrate 2.

[0244] [Tensile Strength] The tensile strength of the evaluation substrate 2 was measured. The evaluation substrate 2 was processed into a test piece having a length of 76.20 mm and a width of 12.70 mm. Using an autograph "ACS-X" manufactured by Shimadzu Corporation, the measurement was performed in accordance with IPC-TM-650-2.4.18.3 under conditions of a test speed of 5.08 mm / min and a chuck distance of 25.4 mm.

[0245] [Glass transition temperature] The glass transition temperature was measured for the evaluation substrate 2. The insulating layer (cured product of the resin composition) of the evaluation substrate 2 was heated from 30°C to 350°C at a heating rate of 10°C / min using a thermomechanical analyzer "TMA7100" manufactured by Hitachi High-Tech Science Corporation, and the inflection point of the thermal expansion coefficient when heated was taken as the glass transition temperature.

[0246] [Linear expansion coefficient] The linear expansion coefficient of the evaluation substrate 2 was measured. The evaluation substrate 2 was heated from 30°C to 350°C at a heating rate of 10°C / min using a thermomechanical analyzer "TMA7100" manufactured by Hitachi High-Tech Science Corporation, and the linear expansion coefficient was measured from 40°C to 80°C. A coefficient of 40 ppm / °C or less was evaluated as "A". A coefficient of more than 40 ppm / °C and less than 60 ppm / °C was evaluated as "B". A coefficient of more than 60 ppm / °C was evaluated as "C".

[0247] [Dielectric Constant and Dielectric Loss Tangent] The dielectric constant and dielectric loss tangent of the evaluation substrate 2 were measured. The dielectric constant and dielectric loss tangent of the insulating layer (cured product of the resin composition) at 10 GHz were measured by a cavity resonator perturbation method using a network analyzer "N5230A" manufactured by Keysight Technologies, Inc.

[0248] [Circuit Filling] A printed wiring board was obtained by forming a grid-patterned conductor wiring on the copper foil (18 μm) on both sides of a copper-clad laminate (manufactured by Panasonic Industries Co., Ltd., product number "R-1566") so that the residual copper ratio was 20%, 50%, and 80%, respectively. A resin-coated metal foil was laminated on each of the conductor wiring on both sides of this printed wiring board. Then, the printed wiring board was subjected to a test at 220°C and 30 kgf / cm ２ The laminate was heated and pressed under a pressure of 100 psi for 120 minutes to obtain a laminate.

[0249] The carrier copper foil of the obtained laminate was peeled off, and the thin copper foil was further etched to visually check for the presence or absence of voids. If the resin composition derived from the resin layer sufficiently penetrated between the circuits of the conductor wiring in this laminate and no voids were observed, it was rated as "A". If the resin composition derived from the resin layer did not penetrate sufficiently between the circuits of the conductor wiring and voids were observed in some patterns, it was rated as "B". If the resin composition derived from the resin layer did not penetrate sufficiently between the circuits of the conductor wiring and voids were observed in all patterns, it was rated as "C". Note that voids can be visually confirmed.

[0250] [Adhesion Strength] First, of the two thin copper foils with carrier copper foils provided on the metal-clad laminate (evaluation substrate 1), the carrier copper foil (thickness 18 μm) of one of the thin copper foils with carrier copper foil was peeled off. Next, the thin copper foil (thickness 3 μm) that overlapped the peeled carrier copper foil was plated up using electroless or electrolytic copper plating to form a metal layer (thickness 35 μm) containing the thin copper foil. The evaluation substrate 1 with this metal layer formed was cut into a size of 10 mm wide and 100 mm long to prepare a sample for adhesion strength measurement. Next, in accordance with JIS C6481 (1996), the metal layer of the cut sample was peeled off at a rate of 50 mm / min using a tensile tester, and the peel strength (kN / m) at that time was measured.

[0251]

[0252]

[0253]

[0254] REFERENCE SIGNS LIST 1 Prepreg 2, 32, 42 Resin layer 3 Fibrous base material 11 Metal-clad laminate 12, 22 Insulating layer 13 Metal foil 21 Wiring board 23 Wiring 31 Resin-coated metal foil 41 Resin-coated film 43 Support film

Claims

1. A resin composition comprising a resin component (R), a core-shell rubber (D), and an inorganic filler (E), wherein the resin component (R) comprises a polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond, a maleimide compound (B), and a phenol compound (C) having a carbon-carbon unsaturated double bond, and the core-shell rubber (D) is present in an amount of 1 part by mass or more and 20 parts by mass or less relative to the resin component (R).

2. The resin composition according to claim 1, wherein the resin component (R) further contains a benzoxazine compound (F).

3. The phenol compound (C) has at least one of a group represented by formula (15) and a group represented by formula (16). The resin composition according to claim 1.

4. The resin composition according to claim 3, wherein the phenol compound (C1) contains a polyfunctional phenol compound (C1-2) having two or more chemical structures represented by formula (17) in one molecule. (In formula (17), R ３９ represents a hydrogen atom, a group represented by formula (15) or a group represented by formula (16), R ４０ represents a hydrogen atom, a group represented by formula (15) or a group represented by formula (16), R ３９ and R ４０ At least one of R represents a group represented by formula (15) or a group represented by formula (16), ４１ represents a hydrogen atom, a methyl group, a methoxy group, a hydroxyl group, an aldehyde group, or a phenyl group.

5. The resin composition according to claim 1, wherein the polyphenylene ether compound (A) comprises a modified polyphenylene ether compound (A1) terminally modified with a substituent having a carbon-carbon unsaturated double bond, and the modified polyphenylene ether compound (A1) has at least one of a group represented by formula (1) and a group represented by formula (2). (In formula (1), p represents an integer of 0 to 10, Z represents an arylene group, and R １ ~R ３ each independently represents a hydrogen atom or an alkyl group. (In formula (2), R ４ represents a hydrogen atom or an alkyl group.

6. The resin composition according to claim 1, wherein the core-shell rubber (D) has a core and a shell covering the core, the core contains at least one resin selected from the group consisting of styrene-butadiene resin, butadiene resin, isoprene resin, acrylic resin, and silicone resin, and the shell contains at least one resin selected from the group consisting of acrylic resin, methacrylic resin, and styrene resin.

7. The resin composition according to claim 1, wherein the content of the phenol compound (C1) is 5% by mass or more and 40% by mass or less relative to the resin component (R).

8. The resin composition according to claim 1, wherein the content of the inorganic filler (E) is 40% by mass or more and 80% by mass or less based on the total amount of the resin composition.

9. A prepreg comprising a resin layer containing at least one of the resin composition according to any one of claims 1 to 8 and a semi-cured product of said resin composition, said resin layer further containing a fibrous base material.

10. A metal-clad laminate comprising an insulating layer containing a cured product of the resin composition according to any one of claims 1 to 8 and a metal foil.

11. A wiring board comprising an insulating layer containing a cured product of the resin composition according to any one of claims 1 to 8, and wiring.

12. A resin-coated metal foil comprising a resin layer containing at least one of the resin composition according to any one of claims 1 to 8 and a semi-cured product of said resin composition, and a metal foil.

13. A resin-coated film comprising a resin layer containing at least one of the resin composition according to any one of claims 1 to 8 and a semi-cured product of said resin composition, and a support film.

Images