Resin compositions, prepregs, resin-coated films, resin-coated metal foils, metal-clad laminates, and wiring boards

Abstract

To provide a resin composition that achieves excellent heat resistance, moldability, and storage stability. [Solution] The resin composition contains a polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond, a maleimide compound (B), a reactive compound (C) different from the polyphenylene ether compound (A), a polymerization inhibitor (D), and an inorganic filler (E). The reactive compound (C) includes at least one selected from the group consisting of groups represented by formula (1) and formula (2). JPEG2026062051000070.jpg11170JPEG2026062051000071.jpg11170In formulas (1) and (2), Ar represents an aromatic structure.The polymerization inhibitor (D) comprises a free radical compound (D1) having a molecular weight of 160 or more and 800 or less.

Description

Technical Field

[0001] The present disclosure generally relates to resin compositions, prepregs, resin-coated films, resin-coated metal foils, metal-clad laminates, and wiring boards, and more particularly to resin compositions containing polyphenylene ether compounds, prepregs containing the resin compositions, resin-coated films, resin-coated metal foils, metal-clad laminates, and wiring boards.

Background Art

[0002] Patent Document 1 discloses a thermosetting resin composition. This thermosetting resin contains a maleimide compound (A) having at least two maleimide groups in one molecule, a compound (B) having a substituent containing an ethylenic unsaturated bond at its terminal and having a polyphenylene ether skeleton, and an inorganic filler. The above compound (B) contains a compound (B1) having a structural unit derived from butadiene.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, in the thermosetting resin composition of Patent Document 1, when a large amount of inorganic filler is contained to improve heat resistance, there are problems such as deterioration of the film-forming property of the resin composition, the moldability such as the filling property during the production of the wiring board, and the storage stability.

[0005] An object of the present disclosure is to provide a resin composition, a prepreg, a resin-coated film, a resin-coated metal foil, a metal-clad laminate, and a wiring board that achieve excellent heat resistance, moldability, and storage stability.

Means for Solving the Problems

[0006] A resin composition according to one aspect of the present disclosure contains a polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond, a maleimide compound (B), a reactive compound (C) different from the polyphenylene ether compound (A), a polymerization inhibitor (D), and an inorganic filler (E). The reactive compound (C) includes at least one selected from the group consisting of chemical structures represented by formula (1) and formula (2).

[0007] [ka]

[0008] [ka]

[0009] In formulas (1) and (2), Ar represents an aromatic structure. The polymerization inhibitor (D) includes a free radical compound (D1) having a molecular weight of 160 to 800.

[0010] A prepreg according to one aspect of the present disclosure comprises the resin composition or a semi-cured product of the resin composition and a fibrous substrate.

[0011] A resin-coated film according to one aspect of the present disclosure comprises a resin layer containing the resin composition or a semi-cured product of the resin composition, and a support film.

[0012] A resin-coated metal foil according to one aspect of the present disclosure comprises a resin layer containing the resin composition or a semi-cured product of the resin composition, and a metal foil.

[0013] A metal-clad laminate according to one aspect of the present disclosure comprises an insulating layer containing a cured product of the resin composition and a metal foil.

[0014] A metal-clad laminate according to one aspect of the present disclosure comprises an insulating layer containing a cured prepreg and a metal foil.

[0015] A wiring board according to one aspect of the present disclosure comprises an insulating layer containing a cured product of the resin composition and wiring.

[0016] A wiring board according to one aspect of the present disclosure comprises an insulating layer containing a cured prepreg and wiring. [Effects of the Invention]

[0017] According to this disclosure, it is possible to provide resin compositions, prepregs, resin-coated films, resin-coated metal foils, metal-clad laminates, and wiring boards that achieve excellent heat resistance, moldability, and storage stability. [Brief explanation of the drawing]

[0018] [Figure 1] Figure 1 is a schematic cross-sectional view of a prepreg according to one embodiment of the present disclosure. [Figure 2] Figure 2 is a schematic cross-sectional view of a resin-coated film according to one embodiment of the present disclosure. [Figure 3] Figure 3 is a schematic cross-sectional view of a resin-coated metal foil according to one embodiment of the present disclosure. [Figure 4] Figure 4 is a schematic cross-sectional view of a metal-clad laminate according to one embodiment of the present disclosure. [Figure 5] Figure 5 is a schematic cross-sectional view of a wiring board according to one embodiment of the present disclosure. [Modes for carrying out the invention]

[0019] The embodiments described below are only a selection of the various embodiments of this disclosure. Furthermore, the embodiments described below can be modified in various ways depending on the design, etc., as long as the objectives of this disclosure are achieved. In addition, while the mechanisms of operation in the embodiments may be described, these descriptions of mechanisms of operation include explanations based on speculation, and this disclosure is not bound by the descriptions of mechanisms of operation.

[0020] 1. Overview The resin composition of this disclosure contains a polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond, a maleimide compound (B), a reactive compound (C) different from the polyphenylene ether compound (A), a polymerization inhibitor (D), and an inorganic filler (E). The reactive compound (C) includes at least one selected from the group consisting of chemical structures represented by formula (1) and formula (2).

[0021] [ka]

[0022] [ka]

[0023] In formulas (1) and (2), Ar represents an aromatic structure. The polymerization inhibitor (D) includes a free radical compound (D1) having a molecular weight of 160 to 800.

[0024] The resin composition in this disclosure, having the above-described structure, can achieve excellent heat resistance, moldability, and storage stability. Specifically, it contains a polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond, a maleimide compound (B), a reactive compound (C) different from the polyphenylene ether compound (A), and an inorganic filler (E), and the reactive compound (C) contains at least one selected from the group consisting of chemical structures represented by formulas (1) and (2), thus achieving good heat resistance. Furthermore, the resin composition contains a polymerization inhibitor (D), and the polymerization inhibitor (D) contains a free radical compound (D1) with a molecular weight of 160 to 800, so the reaction of the polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond, the maleimide compound (B), and the reactive compound (C) different from the polyphenylene ether compound (A) can be homogenized, thus achieving good moldability and storage stability.

[0025] The prepreg of this disclosure comprises the above-mentioned resin composition or a semi-cured product thereof. That is, since the prepreg is manufactured from the resin composition, a prepreg can be obtained that achieves excellent heat resistance, moldability, and storage stability.

[0026] The resin-coated film and resin-coated metal foil of this disclosure comprises a resin layer containing the above-mentioned resin composition or a semi-cured product thereof. That is, since the resin layer of the prepreg, resin-coated film, and resin-coated metal foil is manufactured from the resin composition, it is possible to obtain resin-coated film and resin-coated metal foil that achieve excellent heat resistance, moldability, and storage stability.

[0027] The metal-clad laminates and wiring boards of this disclosure include an insulating layer containing the above-mentioned resin composition or a cured prepreg. That is, since the insulating layer of the metal-clad laminates and wiring boards is manufactured from the resin composition, metal-clad laminates and wiring boards with excellent heat resistance can be obtained.

[0028] In this disclosure, "polyfunctional" means having two or more functional groups in one molecule. For example, each of the polyfunctional maleimide compound, polyfunctional reactive compound, and polyfunctional benzoxazine compound has two or more maleimide groups, at least one chemical structure represented by formula (1) and formula (2), and benzoxazine rings in one molecule.

[0029] 2.Details (1) Resin composition The resin composition according to this embodiment will be described.

[0030] (1.1) Components <Polyphenylene ether compounds> As described above, the resin composition contains a polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond. Polyphenylene ether compound (A) is a component that can reduce dielectric properties such as the dielectric loss tangent of the cured resin composition and improve heat resistance.

[0031] A carbon-carbon unsaturated double bond is a reactive unsaturated bond. Through radical polymerization, the carbon-carbon unsaturated double bond exhibits crosslinking reactions between polyphenylene ethers (A), as well as with maleimide compounds (B) and reactive compounds (C). In this disclosure, the carbon-carbon unsaturated double bond does not include aromatic structures. Examples of carbon-carbon unsaturated double bonds include methacryloyl groups, acryloyl groups, crotonoyl groups, and alkenyl groups.

[0032] The polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond preferably has at least one group selected from the group consisting of formulas (6) and (7) at its molecular terminus. That is, the polyphenylene ether compound having a carbon-carbon unsaturated bond is preferably terminally modified by at least one group selected from the group consisting of formulas (6) and (7).

[0033] [ka]

[0034] In formula (6), a represents an integer between 0 and 10. Z represents an arylene group. R1 to R3 are independent of each other; that is, R1 to R3 may be the same group or different groups. R1 to R3 represent hydrogen atoms or alkyl groups. In formula (6), if a is 0, it indicates that Z is directly bonded to the end of the polyphenylene ether compound (A). Specific examples of arylene groups include, for example, phenylene groups or naphthylene groups. This arylene group may also include derivatives in which the hydrogen atom bonded to the aromatic ring is substituted with a functional group such as an alkenyl group, alkynyl group, formyl group, alkylcarbonyl group, alkenylcarbonyl group, or alkynylcarbonyl group. The alkyl group is not particularly limited, but for example, preferably has 1 to 18 carbon atoms, and more preferably has 1 to 10 carbon atoms. Specific examples of alkyl groups include, for example, methyl, ethyl, propyl, hexyl, or decyl groups.

[0035] [ka]

[0036] In formula (7), R4 represents a hydrogen atom or an alkyl group. The alkyl group is not particularly limited, but preferably has 1 to 18 carbon atoms, and more preferably has 1 to 10 carbon atoms. Specifically, examples include a methyl group, ethyl group, propyl group, hexyl group, or decyl group. In addition, examples of the group represented by formula (7) include a methacryloyl group or an acryloyl group.

[0037] Furthermore, more specific examples of the group represented by formula (6) include, for example, the vinylbenzyl group (hereinafter also called the ethenylbenzyl group) or vinylphenyl group represented by formula (15). Also, more specific examples of the vinylbenzyl group include, for example, the o-vinylbenzyl group, m-vinylbenzyl group, or p-vinylbenzyl group.

[0038] [ka]

[0039] The polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond preferably has a polyphenylene ether chain in its molecule and a repeating unit represented by formula (16) in its molecule.

[0040] [ka]

[0041] In formula (16), b represents an integer between 1 and 50. Also, R5 to R8 are independent of each other. That is, R5 to R8 may be the same group or different groups. Furthermore, R5 to R8 represent 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. R5 to R8 are preferably a hydrogen atom and an alkyl group.

[0042] In R5 to R8, the functional groups listed are specifically as follows:

[0043] The alkyl group is not particularly limited, but preferably has 1 to 18 carbon atoms, and more preferably has 1 to 10 carbon atoms. Specific examples of alkyl groups include, for example, a methyl group, an ethyl group, a propyl group, a hexyl group, or a decyl group.

[0044] The alkenyl group is not particularly limited, but preferably has 2 to 18 carbon atoms, and more preferably 2 to 10 carbon atoms. Specific examples of alkenyl groups include vinyl groups, allyl groups (2-propenyl groups), and 3-butenyl groups.

[0045] The alkynyl group is not particularly limited, but preferably has 2 to 18 carbon atoms, and more preferably 2 to 10 carbon atoms. Specific examples of alkynyl groups include, for example, an ethynyl group or a propargyl group (propa-2-in-1-yl group).

[0046] The alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group, but preferably has 2 to 18 carbon atoms, and more preferably has 2 to 10 carbon atoms. Specific examples of alkylcarbonyl groups include, for example, acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, hexanoyl group, octanoyl group, or cyclohexylcarbonyl group.

[0047] The alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group, but preferably has 3 to 18 carbon atoms, and more preferably has 3 to 10 carbon atoms. Specific examples of alkenylcarbonyl groups include, for example, acryloyl, methacryloyl, or crotonoyl groups.

[0048] The alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group, but preferably has 3 to 18 carbon atoms, and more preferably 3 to 10 carbon atoms. Specific examples of alkynylcarbonyl groups include, for example, the propioloyl group.

[0049] The weight-average molecular weight (Mw) of the polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond is preferably 500 to 5000. In this case, the heat resistance of the cured resin composition can be improved. It is presumed that the reason why the heat resistance of the cured resin composition can be improved when the weight-average molecular weight of the polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond is within the above range is as follows. For example, in the case of a normal polyphenylene ether compound that is not terminally modified by a group having a carbon-carbon unsaturated double bond, if its weight-average molecular weight is in the range of 500 to 5000, it is a relatively low molecular weight, and therefore the heat resistance of the cured resin composition containing the polyphenylene ether compound tends to decrease. In contrast, the polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond has a carbon-carbon unsaturated double bond at its molecular end, so the heat resistance of the cured resin composition is easily improved. This weight-average molecular weight is more preferably 800 or more, and even more preferably 1000 or more. Furthermore, the weight-average molecular weight is more preferably 4500 or less, and even more preferably 4000 or less. The weight-average molecular weight can be measured by any general molecular weight measurement method, specifically, by measuring it using gel permeation chromatography (GPC) and converting it to polystyrene equivalent.

[0050] Furthermore, if the polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond has a repeating unit represented by formula (16) in its molecule, it is preferable that b is a value such that the weight-average molecular weight of the polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond is in the range of 500 to 5000. Specifically, it is preferable that b is between 1 and 50.

[0051] The average number of carbon-carbon unsaturated double bond groups (terminal functional groups) per molecule of the polyphenylene ether compound (A) having carbon-carbon unsaturated double bonds is preferably 1 to 5. When this number of terminal functional groups is 1 or more, the heat resistance of the cured resin composition can be further improved. When this number of terminal functional groups is 5 or less, the reactivity of the resin composition can be adjusted, thereby improving the fluidity of the resin composition during molding and improving the storage stability of the resin composition. This number of terminal functional groups is more preferably 1.5 or more. Furthermore, this number of terminal functional groups is more preferably 3 or less.

[0052] The number of terminal functional groups in a polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond is a numerical value representing the average number of terminal functional groups per molecule of the polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond present in one mole of the compound. This number of terminal functional groups can be measured, for example, by measuring the number of hydroxyl groups remaining in the polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond and calculating the decrease from the number of hydroxyl groups of the polyphenylene ether compound before terminal modification. This decrease from the number of hydroxyl groups of the polyphenylene ether compound before terminal modification is the number of terminal functional groups. The number of hydroxyl groups remaining in the polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond can be determined by adding a quaternary ammonium salt such as tetraethylammonium hydroxide, which associates with hydroxyl groups, to a solution of the polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond and measuring the UV absorbance of the mixed solution.

[0053] The polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond preferably contains at least one of the compounds represented by formulas (17) and (18).

[0054] [ka]

[0055]

Chem.

[0056] In formulas (17) and (18), R9 to R

[0058] as well as R 17 ~R 24 are each independent. That is, R9 to R 16 as well as R 17 ~R 24 may each be the same group or different groups. They represent 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. X1 and X2 each independently represent a group having a carbon-carbon unsaturated double bond. Each of A and B represents a repeating unit represented by formula (19) or formula (20). Further, in formula (18), Y represents a linear, branched or cyclic hydrocarbon group having 20 or fewer carbon atoms.

[0057]

Chem.

[0058]

Chem.

[0059] In formulas (19) and (20), each of c and d represents an integer of 0 or more and 20 or less. In formulas (19) and (20), R 25 ~R 28 as well as R 29 ~R 32 are each independent. That is, R 25 ~R 28 as well as R 29 ~R 32 may each be the same group or different groups. Further, R 25 ~R 28 as well as R 29 ~R 32R 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. 25 ~R 28 R 29 ~R 32 R is preferably a hydrogen atom and an alkyl group. 25 ~R 32 These may be the same as R5 to R8 in equation (16).

[0060] Furthermore, for c and d in formulas (19) and (20), the sum of c and d is preferably an integer between 1 and 30. More preferably, c is an integer between 0 and 20, d is an integer between 0 and 20, and the sum of c and d is an integer between 1 and 30.

[0061] In formula (18), Y is a linear, branched, or cyclic hydrocarbon group having 20 or fewer carbon atoms. Examples of Y include the group represented by formula (21).

[0062] [ka]

[0063] In formula (21), R 33 and R 34 Each of these independently represents either a hydrogen atom or an alkyl group. Examples of alkyl groups include the methyl group. Furthermore, specific examples of groups represented by formula (21) include the methylene group, methylmethylene group, or dimethylmethylene group. 33 and R 34 The group is preferably a methyl group, and the group represented by formula (21) is preferably a dimethylmethylene group.

[0064] Furthermore, in formulas (17) and (18), X1 and X2 are independent of each other. X1 and X2 are, for example, groups having a carbon-carbon unsaturated double bond. Each of X1 and X2 is, for example, a group represented by formula (6) or formula (7). In the polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond represented by formulas (17) and (18), X1 and X2 may be the same group or different groups.

[0065] A more specific example of the polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond represented by formula (17) is, for example, the polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond represented by formula (22).

[0066] [ka]

[0067] More specific examples of polyphenylene ether compounds (A) having a carbon-carbon unsaturated double bond represented by formula (18) include, for example, polyphenylene ether compounds (A) having a carbon-carbon unsaturated double bond represented by formula (23) or formula (24).

[0068] [ka]

[0069] [ka]

[0070] In equations (22) to (24), c and d are the same as c and d in equations (19) and (20). Also, in equations (22) and (23), R1 to R3, a and Z are the same as R1 to R3, a and Z in equation (6). Also, in equations (23) and (24), Y is the same as Y in equation (18). Also, in equation (24), R4 is the same as R4 in equation (7).

[0071] A method for synthesizing polyphenylene ether compounds (A) having carbon-carbon unsaturated double bonds will be described. Specifically, this method involves reacting a starting polyphenylene ether compound with a compound to which a group having a carbon-carbon unsaturated double bond and a halogen atom are bonded.

[0072] The polyphenylene ether compound used as a raw material is not particularly limited, as long as it can synthesize a polyphenylene ether compound (A) having a predetermined carbon-carbon unsaturated double bond. Specifically, examples include polyphenylene ethers composed of 2,6-dimethylphenol and at least one of a difunctional phenol and a trifunctional phenol, and polyphenylene ether compounds such as poly(2,6-dimethyl-1,4-phenylene oxide). A difunctional phenol is a phenol compound having two phenolic hydroxyl groups in one molecule, such as tetramethylbisphenol A. A trifunctional phenol is a phenol compound having three phenolic hydroxyl groups in one molecule.

[0073] The method for synthesizing the polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond is the method described above. Specifically, the polyphenylene ether compound described above and a compound to which a group having a carbon-carbon unsaturated double bond and a halogen atom are bonded are dissolved in a solvent and stirred. As a result, the polyphenylene ether compound and the compound to which the group having a carbon-carbon unsaturated double bond and a halogen atom are bonded react to obtain the polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond.

[0074] It is preferable that the reaction between a polyphenylene ether compound and a compound having a carbon-carbon unsaturated double bond and a halogen atom be carried out in the presence of an alkali metal hydroxide. This is thought to allow the reaction to proceed favorably. This is because the alkali metal hydroxide is thought to function as a dehalogenating agent. In other words, the alkali metal hydroxide removes hydrogen halides from the phenolic hydroxyl group of the polyphenylene ether compound and the compound having a carbon-carbon unsaturated double bond and a halogen atom, and it is thought that the group having a carbon-carbon unsaturated double bond replaces the hydrogen atom of the phenolic hydroxyl group of the polyphenylene ether compound by bonding to the oxygen atom of the phenol group.

[0075] Alkali metal hydroxides are not particularly limited as long as they act as dehalogenating agents, but examples include sodium hydroxide. Furthermore, alkali metal hydroxides are usually used in aqueous solution form, specifically as an aqueous solution of sodium hydroxide.

[0076] The reaction conditions, such as reaction time and reaction temperature, vary depending on the compound, including the group having a carbon-carbon unsaturated double bond and the halogen atom, and are not particularly limited as long as the above-mentioned reaction proceeds favorably. Specifically, the reaction temperature is preferably 20°C to 100°C, and more preferably 30°C to 100°C. The reaction time is preferably 0.5 hours to 20 hours, and more preferably 0.5 hours to 10 hours.

[0077] The solvent used in the reaction between a polyphenylene ether compound and a compound to which a group having a carbon-carbon unsaturated double bond and a halogen atom are bonded is not particularly limited, as long as it can dissolve the polyphenylene ether compound and the compound to which the group having a carbon-carbon unsaturated double bond and a halogen atom are bonded, and does not inhibit the reaction between the polyphenylene ether compound and the compound to which the group having a carbon-carbon unsaturated double bond and a halogen atom are bonded. Specifically, examples include toluene.

[0078] The reaction between a polyphenylene ether compound and a compound having a carbon-carbon unsaturated double bond and a halogen atom is preferably carried out in the presence of not only an alkali metal hydroxide but also a phase-transfer catalyst. In other words, the above reaction is preferably carried out in the presence of an alkali metal hydroxide and a phase-transfer catalyst. This is thought to allow the above reaction to proceed more favorably. This is thought to be because the phase-transfer catalyst has the function of incorporating alkali metal hydroxides, is soluble in both the polar solvent phase such as water and the non-polar solvent phase such as an organic solvent, and can move between these phases. Specifically, when an aqueous sodium hydroxide solution is used as the alkali metal hydroxide and an organic solvent such as toluene, which is immiscible with water, is used as the solvent, even if the aqueous sodium hydroxide solution is added dropwise to the solvent being used in the reaction, the solvent and the aqueous sodium hydroxide solution will separate, and it is thought that the sodium hydroxide will not easily migrate into the solvent. In that case, it is thought that the aqueous sodium hydroxide solution added as the alkali metal hydroxide will not contribute much 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 the aqueous sodium hydroxide solution is thought to contribute more readily to promoting the reaction. For this reason, the above reaction is thought to proceed more favorably when 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.

[0079] The content of polyphenylene ether compound (A) is preferably 10% by mass or more, and more preferably 20% by mass or more, relative to the total amount of polyphenylene ether compound (A), maleimide compound (B), and reactive compound (C). In this case, the dielectric loss tangent of the cured resin composition can be reduced. Alternatively, the content of polyphenylene ether compound (A) is preferably 50% by mass or less, and more preferably 40% by mass or less, relative to the total amount of polyphenylene ether compound (A), maleimide compound (B), and reactive compound (C). In this case, a decrease in the heat resistance of the resin composition can be suppressed.

[0080] <Maleimide compounds> As described above, the resin composition contains maleimide compound (B). Maleimide compound (B) is a component that can improve the heat resistance and desmear resistance of the cured resin composition, as well as reduce dielectric properties such as dielectric loss tangent.

[0081] Maleimide compound (B) may contain only one compound or two or more compounds. Examples of maleimide compound (B) include monofunctional maleimide compounds having one maleimide group in one molecule or polyfunctional maleimide compounds having two or more maleimide groups in one molecule.

[0082] Examples of monofunctional maleimide compounds having one maleimide group in one molecule include chlorophenyl maleimides such as o-chlorophenylmaleimide, methylphenyl maleimides such as o-methylphenylmaleimide, hydroxyphenyl maleimides such as p-hydroxyphenylmaleimide, carboxyphenyl maleimides such as p-carboxyphenylmaleimide, N-dodecylmaleimide, or phenylmethanemaleimide.

[0083] Examples of polyfunctional maleimide compounds having two or more maleimide groups in one molecule include 4,4'-diphenylmethanebismaleimide, bisphenol A bis(4-maleimidephenyl ether), 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyletherbismaleimide, 4,4'-diphenylsulfonebismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, or polyphenylmethanemaleimide.

[0084] The maleimide compound (B) preferably has a phenylmaleimide group. The number of phenylmaleimide groups in one molecule of the maleimide compound (B) is not particularly limited, but is preferably two or more.

[0085] The maleimide compound (B) more preferably includes a maleimide compound (B1) selected from the group consisting of compounds represented by formulas (34) and (35).

[0086] [ka]

[0087] In equation (34), g represents an integer between 1 and 5, inclusive. 45 ~R 48 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group. The alkyl group having 1 to 5 carbon atoms may be linear or branched, and examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, pentyl group, or neopentyl group.

[0088] Also, R in equation (34) 45 and R 46It is bonded to the benzene ring of the phenylmaleimide group that is not included in the repeating unit. On the other hand, R 47 and R 48 It is bonded to the benzene ring of the phenylmaleimide group contained in the repeating unit. Furthermore, R 47 and R 48 Each repeating unit is independent, and R in each repeating unit 47 and R 48 Each of these may be the same or different.

[0089] [ka]

[0090] In equation (35), h represents an integer greater than or equal to 1.

[0091] The weight-average molecular weight of maleimide compound (B) is preferably 150 or more, more preferably 300 or more, and even more preferably 400 or more. In this case, the heat resistance of the cured resin composition may be improved. Alternatively, the weight-average molecular weight of maleimide compound (B) is preferably 2500 or less, more preferably 2000 or less, and even more preferably 1500 or less. In this case, the moldability may be improved. The weight-average molecular weight can be measured by any general molecular weight measurement method, specifically, by measuring using gel permeation chromatography (GPC) and converting it to polystyrene equivalent.

[0092] Maleimide compound (B) can be a commercially available product. Examples of such commercially available products include MIR-5000-60T and MIR-3000-70MT manufactured by Nippon Kayaku Co., Ltd.; BMI-5100 manufactured by Yamato Kasei Co., Ltd.; and BMI-80 manufactured by K.I. Kasei Co., Ltd.

[0093] The content of maleimide compound (B) is preferably 30% by mass or more, and more preferably 40% by mass or more, relative to the total amount of polyphenylene ether compound (A), maleimide compound (B), and reactive compound (C). In this case, heat resistance and processability can be improved. Alternatively, the content of maleimide compound (B) is preferably 60% by mass or less, and more preferably 55% by mass or less, relative to the total amount of polyphenylene ether compound (A), maleimide compound (B), and reactive compound (C). In this case, deterioration of the dielectric loss tangent can be suppressed.

[0094] <Reactive Compounds> As described above, the resin composition contains a reactive compound (C) different from the polyphenylene ether compound (A). The reactive compound (C) is a component that can improve the heat resistance of the cured product of the resin composition.

[0095] The reactive compound (C) has at least one selected from the group consisting of chemical structures represented by formula (1) and formula (2).

[0096] [ka]

[0097] [ka]

[0098] In formulas (1) and (2), Ar represents an aromatic structure. Since the reactive compound (C) has at least one selected from the group consisting of the chemical structures represented by formulas (1) and (2), the heat resistance of the cured resin composition is improved.

[0099] The chemical structures represented by formulas (1) and (2) have reactive groups. Specifically, the chemical structures represented by formulas (1) and (2) are aromatic structures having an allyl group or a 1-propenyl group. That is, the chemical structures represented by formulas (1) and (2) have a carbon-carbon unsaturated double bond as a reactive group. Therefore, reactive compound (C) has a carbon-carbon unsaturated double bond as a reactive group. Consequently, the chemical structures represented by formulas (1) and (2) exhibit crosslinking reactions with other reactive compounds (C), as well as with polyphenylene ether compound (A) and maleimide compound (B) through radical polymerization.

[0100] The reactive compound (C) is different from the polyphenylene ether compound (A). That is, the reactive compound (C) does not have repeating units represented by formulas (16), (19), and (20), for example, in its molecule. On the other hand, the carbon-carbon unsaturated double bond in the reactive compound (C) may be the same as or different from the carbon-carbon unsaturated double bond in the polyphenylene ether (A).

[0101] When the resin composition contains no reactive compound (C), the cured product of the resin composition is more likely to have improved heat resistance and adhesion than when it contains the reactive compound (C). The reason is speculated as follows. When a resin composition containing a polyphenylene ether compound (A) and a maleimide compound (B) and not containing the reactive compound (C) is cured, the polyphenylene ether compound (A) and the maleimide compound (B) are difficult to mix and react with each other, so a complex of the polyphenylene ether compound (A) and the maleimide compound (B) is likely to be difficult to form. On the other hand, when a resin composition containing a polyphenylene ether compound (A) and a maleimide compound (B) and containing the reactive compound (C) is cured, the reactive compound (C) can promote the formation of a complex of the polyphenylene ether compound (A) and the maleimide compound (B), so a complex of the polyphenylene ether compound (A) and the maleimide compound (B) can be easily formed. Thereby, it is speculated that the heat resistance and adhesion of the cured product of the resin composition can be improved. The ease of formation of the complex of the polyphenylene ether compound (A) and the maleimide compound (B) can be confirmed by measuring the loss tangent (tanδ) of the cured product of the resin composition using a dynamic viscoelasticity measuring device (DMA). Specifically, when curing, in the case of a resin composition in which a complex of the polyphenylene ether compound (A) and the maleimide compound (B) is difficult to form, in the graph of the loss tangent obtained by measuring the dynamic viscoelasticity of the cured product, the maximum peak is broad in a broad shape or a large number of peaks are confirmed. On the other hand, in the case of the resin composition of the present disclosure in which a complex of the polyphenylene ether compound (A) and the maleimide compound (B) is likely to be formed when cured, in the graph of the loss tangent obtained by measuring the dynamic viscoelasticity of the cured product, the maximum peak is confirmed as a sharp single peak.

[0102] Further, the reactive compound (C) preferably contains a polyfunctional reactive compound (C1) having two or more chemical structures represented by the formula (3) in one molecule. When the reactive compound (C) contains a polyfunctional reactive compound, in addition to improving the heat resistance of the cured product of the resin composition, the adhesion can be improved and the coefficient of thermal expansion can be reduced.

[0103] [ka]

[0104] R in equation (3) 35 and R 36 They are all independent of each other. 35 R represents an allyl group or a 1-propenyl group. 36 R represents a hydrogen atom, a methyl group, a methoxy group, a hydroxyl group, an aldehyde group, an allyl ether group, a 1-propenyl ether group, or a phenyl group. In other words, the chemical structure represented by formula (3) is such that in the chemical structure represented by formula (1) or (2), Ar is a benzene ring, R is... 35 is an allyl group or a 1-propenyl group, R 36 This is a hydrogen atom. That is, the polyfunctional reactive compound (C1) may have other substituents in addition to the allyl group or 1-propenyl group in one molecule. With respect to the aromatic structure in formula (3), R may be used as long as it does not impair the effects of this disclosure. 35 and R 36 In addition, other substituents, such as organic groups, may be bonded to the carbon atoms of the aromatic ring. Furthermore, each of the chemical structures represented by formula (3) in the polyfunctional reactive compound (C1) may be identical or different.

[0105] For a polyfunctional reactive compound (C1), the chemical structures represented by formula (3) are bonded to each other, for example, via a linking group. In this disclosure, a linking group means a divalent organic group in a polyfunctional reactive compound (C1) that links one of the carbon atoms of the aromatic structure in one of the chemical structures represented by formula (3) to one of the carbon atoms of the aromatic structure in the other chemical structure represented by formula (3). That is, if a polyfunctional reactive compound (C1) has a linking group in one molecule, the linking group is bonded to one of the carbon atoms of the aromatic structure in the chemical structure represented by formula (3). In this disclosure, polyfunctional reactive compound (C1) also includes cases where the two chemical structures represented by formula (3) are directly bonded to one of the carbon atoms of the aromatic structure in one of the chemical structures represented by formula (3) without the use of a linking group.

[0106] A polyfunctional reactive compound (C1) may have, for example, only one linking group in a single molecule, or it may have two or more. Furthermore, if a polyfunctional reactive compound (C1) has two or more linking groups, each of these linking groups is independent. That is, each of the linking groups of a polyfunctional reactive compound (C1) may have the same structure or different structures.

[0107] Specific examples of the linking group structure of the polyfunctional reactive compound (C1) include the chemical structures represented by formulas (25) to (30).

[0108] [ka]

[0109] [ka]

[0110] [ka]

[0111] [ka]

[0112] [ka]

[0113] In formula (29), R 37 and R 38 Each of these independently represents a hydrogen atom, a methyl group, an ethyl group, a phenyl group, or a trifluoromethyl group.

[0114] [ka]

[0115] In equation (30), e represents an integer between 0 and 35, inclusive. 39 and R 41 Each of these independently represents a substituent containing a carbonate ester. Furthermore, R 40 R represents a cyclic aliphatic hydrocarbon group. In formula (30), R 39 and R 41 Specifically, an example of this is the chemical structure represented by formula (31).

[0116] [ka]

[0117] Also, in equation (30), R 40 The cyclic aliphatic hydrocarbon group may be a monocyclic aliphatic hydrocarbon group or a polycyclic aliphatic hydrocarbon group. The cyclic aliphatic hydrocarbon group is not particularly limited, but preferably has 6 to 20 carbon atoms. It is preferable that the cyclic aliphatic hydrocarbon group does not have an unsaturated bond. More specifically, the cyclic aliphatic hydrocarbon group may have a chemical structure represented by formula (32), for example.

[0118] [ka]

[0119] Here, in equation (30), if e is an integer greater than or equal to 2, then the R included in the repeating unit in equation (30) 39 and R 40 Each of these may be the same or different, independently of the repeating unit.

[0120] With respect to the benzene ring structure or cyclic aliphatic hydrocarbon group in formulas (25) to (28) and formulas (29) to (32), substituents such as alkyl groups and halogen atoms may be bonded to the carbon atoms of the benzene ring structure or cyclic aliphatic hydrocarbon group, as long as the effects of the present disclosure are not impaired.

[0121] The polyfunctional reactive compound (C1) more preferably further comprises a polyfunctional reactive compound (C2) which is at least one selected from the group consisting of compounds represented by formulas (4) and (5). In this case, the heat resistance and adhesion of the cured product of the resin composition can be further improved, and the coefficient of thermal expansion can be further reduced.

[0122] [ka]

[0123] In equation (4), f represents an integer between 1 and 4, inclusive. 42 R represents an allyl group or a 1-propenyl group. 43 This represents a hydrogen atom. Also, the R included in the repeating unit 42 Each repeating unit is independent, and R in each repeating unit 42 They may be the same or they may be different.

[0124] In equation (4), R 42 and R 43 Each of these is R in equation (3). 35 and R 36It is the same as in equation (4), and the linking group in equation (29) is R 37 and R 38 These are groups (methylene groups) where each atom is a hydrogen atom.

[0125] [ka]

[0126] In formula (5), R 44 Each of these independently represents either an allyl group or a 1-propenyl group. Also, in formula (5), R 44 R in equation (3) is 35 And the hydroxyl group is R in formula (3). 36 Furthermore, the linking group in equation (5) is R in equation (29). 37 and R 38 These are methyl groups (dimethylmethylene groups).

[0127] The content of reactive compound (C) is preferably 10% by mass or more, and more preferably 15% by mass or more, relative to the total amount of polyphenylene ether compound (A), maleimide compound (B), and reactive compound (C). In this case, the heat resistance of the cured resin composition may be improved. Alternatively, the content of reactive compound (C) is preferably 30% by mass or less, and more preferably 25% by mass or less, relative to the total amount of polyphenylene ether compound (A), maleimide compound (B), and reactive compound (C). In this case, the decrease in the heat resistance of the cured resin composition may be suppressed.

[0128] <Polymerization inhibitor> As described above, the resin composition contains polymerization inhibitor (D). Polymerization inhibitor (D) is a component that can improve the storage stability and moldability of the resin composition, as well as the interlayer peel strength of its cured product.

[0129] The polymerization inhibitor (D) of this disclosure is a compound used to control radical polymerization reactions. Polyphenylene ether compound (A) has high radical polymerization reactivity and readily polymerizes with other polyphenylene ether compounds (A), so the radical polymerization reaction between polyphenylene ether compound (A) and maleimide compound (B) and reactive compound (C) does not proceed uniformly. Therefore, by adding polymerization inhibitor (D), the polymerization reaction between polyphenylene ether compounds (A) is suppressed, and it is presumed that the radical polymerization reaction between polyphenylene ether compound (A) and maleimide compound (B) and reactive compound (C) proceeds uniformly. In this way, the high radical polymerization reactivity of polyphenylene ether compound (A) can be reduced, which improves the resin flowability of the resin composition, and as a result, improves moldability. Furthermore, since the radical polymerization reaction between polyphenylene ether compound (A) and maleimide compound (B) and reactive compound (C) proceeds uniformly, the crosslinking density of the cured resin composition improves, which can improve heat resistance.

[0130] The polymerization inhibitor (D) includes a free radical compound (D1) having a molecular weight of 160 to 800. In particular, if the molecular weight is less than 160, the polymerization inhibitor (D) may volatilize, and the radical polymerization reaction may not be controllable. The free radical compound (D1) has at least one free radical in its molecule. More specifically, it is preferable that the free radical compound (D1) has at least one selected from the group consisting of structures represented by formulas (8), (9), (10), and (11).

[0131] [ka]

[0132] [ka]

[0133] [ka]

[0134] [ka]

[0135] Furthermore, it is more preferable that the free radical compound (D1) further comprises at least one selected from the group consisting of structures represented by formulas (12), (13), and (14).

[0136] [ka]

[0137] In formula (12), X A This group exhibits an ether bond with an amino group, cyano group, hydroxyl group, isothiocyanate group, carboxyl group, oxo group, amide group, acyloxy group, or organic group. Examples of amide groups include acetamide. Examples of acyloxy groups include benzoyloxy, formyloxy, and acetyloxy groups. Examples of organic groups include alkyl groups, specifically methyl groups.

[0138] [ka]

[0139] In formula (13), X B This group exhibits an ether bond with a cyano group, isothiocyanate group, carboxyl group, amide group, acyloxy group, or organic group. Examples of amide groups include acetamide. Examples of acyloxy groups include benzoyloxy, formyloxy, and acetyloxy groups. Examples of organic groups include alkyl groups, specifically methyl groups.

[0140] [ka]

[0141] In formula (14), X C The symbol represents an alkylene group, an aromatic structure, a carbonyl group, an amide group, or an oxygen atom. Examples of alkylene groups include methylene group, dimethylmethylene group, ethylene group, propylene group, n-butylene group, sec-butylene group, tert-butylene group, n-pentylene group, n-hexylene group, n-heptylene group, and n-octylene group. Examples of aromatic structures include phenylene group, naphthalene group, and biphenyl structure.

[0142] Polymerization inhibitor (D) may contain only one compound or may contain two or more compounds.

[0143] The content of polymerization inhibitor (D) is preferably 0.1 parts by mass or more, and more preferably 0.3 parts by mass or more, based on 100 parts by mass of the total of the polyphenylene ether compound (A), maleimide compound (B), and reactive compound (C). In this case, the storage stability and moldability of the resin composition, as well as the interlayer peel strength of its cured product, can be improved. Alternatively, the content of polymerization inhibitor (D) is preferably 1.0 part by mass or less, and more preferably 0.7 parts by mass or less, based on 100 parts by mass of the total of the polyphenylene ether compound (A), maleimide compound (B), and reactive compound (C). In this case, deterioration of the dielectric loss tangent and heat resistance of the cured product of the resin composition can be suppressed.

[0144] <Inorganic filler> As described above, the resin composition contains inorganic filler (E). Inorganic filler (E) is a component that can reduce the dielectric loss tangent and linear expansion coefficient of the cured resin composition and improve its heat resistance.

[0145] The inorganic filler (E) is not particularly limited, but examples include silica such as synthetic silica, fused silica, or crystalline silica, talc, boehmite, magnesium hydroxide, aluminum hydroxide, magnesium hydroxide, aluminum silicate, magnesium silicate, clay, and mica. The inorganic filler (E) contained in the resin composition may be one type or two or more types.

[0146] The inorganic filler (E) is preferably surface-treated with a silane coupling agent. The silane coupling agent is not particularly limited, but examples include silane coupling agents having hydrophobic groups and silane coupling agents having hydrophilic groups. Examples of silane coupling agents having hydrophobic groups include silane coupling agents having vinyl groups such as vinyltriethoxysilane and vinyltrimethoxysilane; silane coupling agents having methacryloyl groups such as methacryloxypropylmethyldimethoxysilane and methacryloxypropyltriethoxysilane; and silane coupling agents having styryl groups such as p-styryltrimethoxysilane and p-styryltriethoxysilane. Examples of silane coupling agents having hydrophilic groups include silane coupling agents having a phenylamino group or a benzylamino group, such as N-phenyl-3-aminopropyltrimethoxysilane and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropylethyldiethoxysilane, N-2-(aminoethyl Examples include silane coupling agents having alkylamino groups such as N-2-(aminoethyl)-3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, and 3-aminopropyltriethoxysilane; silane coupling agents having epoxy groups such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and glycidoxypropyltriethoxysilane; and silane coupling agents having isocyanate groups such as isocyanatepropyltriethoxysilane. It is more preferable that the inorganic filler (E) is surface-treated with a silane coupling agent having vinyl groups or a silane coupling agent having phenylamino groups. When surface-treated with a silane coupling agent having vinyl groups, the adhesion between the inorganic filler (E) and the hydrophobic resin may be improved. When surface-treated with a silane coupling agent having phenylamino groups, the adhesion between the inorganic filler (E) and the hydrophilic resin may be improved.The silane coupling agent used may be a single type or a combination of two or more types.

[0147] The inorganic filler (E) content is preferably 100 parts by mass or more, more preferably 120 parts by mass or more, based on 100 parts by mass of the total of the polyphenylene ether compound (A), maleimide compound (B), and reactive compound (C). In this case, the dielectric loss tangent and linear expansion coefficient of the cured resin composition may be reduced, and the heat resistance may be improved. Alternatively, the inorganic filler (E) content is preferably 300 parts by mass or less, more preferably 180 parts by mass or less, based on 100 parts by mass of the total of the polyphenylene ether compound (A), maleimide compound (B), and reactive compound (C). In this case, deterioration of the moldability and heat resistance of the resin composition can be suppressed.

[0148] <Elastomer> The resin composition may further contain elastomer (F). Elastomer (F) is a component that can improve the tensile elongation of the cured resin composition and suppress cracking. This is because elastomer (F) has sufficient dispersibility in the resin composition and can impart flexibility to the cured product.

[0149] The elastomer (F) is not particularly limited as long as it is a viscoelastic polymer compound, and for example, thermosetting resins, thermoplastic resins, etc., can be used. Examples of elastomers (F) include styrene-butadiene resin, butadiene resin, isoprene resin, silicone resin, acrylic resin, methacrylic resin, styrene resin, etc. The elastomer (F) may contain only one type, or it may contain two or more types.

[0150] The composition of the elastomer (F) can be determined by its tensile elongation and the desired properties of the resin composition. For example, to improve dielectric properties, an elastomer having nonpolar groups should be selected.

[0151] Furthermore, the elastomer (F) preferably includes a core-shell rubber (F1). The core-shell rubber (F1) has a core and a shell covering the core. Both the core and the shell contain at least one of a thermosetting resin and a thermoplastic resin. Examples of the core include styrene-butadiene resin, butadiene resin, isoprene resin, acrylic resin, silicone resin, etc. Examples of the shell include acrylic resin, methacrylic resin, styrene resin, etc.

[0152] The core shell rubber (F1) can be a commercially available product. Examples of such commercially available products include the Metabren Type S series, Type W series, Type C series, and Type E series from Mitsubishi Chemical Corporation; the Kaneace MX series from Kaneka Corporation; the PARALOID series such as PARALOID-TMS-2670 from Dow Inc.; the Stafiloid series from Aica Kogyo Co., Ltd.; and the GENIOPERL series such as GENIOPERL P52 from WACKER Chemie AG.

[0153] Furthermore, while the average particle size of the core-shell rubber is not particularly limited, it is, for example, 0.001 μm or more and 1 μm or less. Preferably, this average particle size is 0.5 μm or less.

[0154] The elastomer (F) content is preferably 1 part by mass or more, and more preferably 3 parts by mass or more, per 100 parts by mass of the total of the polyphenylene ether compound (A), maleimide compound (B), and reactive compound (C). In this case, the tensile elongation of the cured resin composition may be improved. Alternatively, the elastomer (F) content is preferably 30 parts by mass or less, and more preferably 15 parts by mass or less, per 100 parts by mass of the total of the polyphenylene ether compound (A), maleimide compound (B), and reactive compound (C). In this case, deterioration of moldability can be suppressed.

[0155] <Other hardening agents> The resin composition may further contain, in addition to the polyphenylene ether compound (A), maleimide compound (B), and reactive compound (C), other thermosetting compounds (hereinafter also referred to as "other curing agents") that are different from these, as long as they do not impair the effects of the present disclosure. The other curing agents are different from the polyphenylene ether compound (A), maleimide compound (B), and reactive compound (C). That is, the other curing agents do not have at least the repeating structure represented by formula (16), the maleimide group, or the chemical structures represented by formulas (1) and (2). The other curing agents are not particularly limited, but examples include benzoxazine compounds, epoxy compounds, unsaturated imide compounds, cyanate compounds, isocyanate compounds, oxetane compounds, amino compounds, unsaturated polyester compounds, silicone compounds, triazine compounds, melamine compounds, etc. Among these, it is preferable that the resin composition contains a benzoxazine compound. In this case, the peel strength may be further improved.

[0156] Benzooxazine compounds have one or more benzooxazine rings in one molecule. Preferably, there are two or more benzooxazine rings in one molecule. In other words, it is preferable that the benzooxazine compound contains a polyfunctional benzooxazine compound. The polyfunctional benzooxazine compound can form a three-dimensional crosslinked structure by reacting with a polyphenylene ether compound (A), a maleimide compound (B), and a reactive compound (C). Therefore, the heat resistance of the cured resin composition can be improved. From the viewpoint of resistance to cracking of the cured product, it is preferable that there are four or fewer benzooxazine rings. Furthermore, benzooxazine compounds do not have allyl groups in the aromatic structure within the molecule, but have allyl groups in parts other than the aromatic structure within the molecule. That is, benzooxazine compounds do not have the chemical structures represented by formulas (1) and (2), and are therefore not included in the reactive compound (C).

[0157] The benzoxazine compound preferably contains a benzoxazine compound represented by formula (33).

[0158] [ka]

[0159] In formula (33), R 49 Examples include single bonds, methylene groups, oxygen atoms, carbonyl groups, dimethylmethylene groups, -C(CF3)2, phenylene groups, naphthylene groups, dicyclopentadiene groups, etc. Among these, R 49 A dicyclopentadiene group is preferred.

[0160] Furthermore, the benzoxazine compound is not limited to the benzoxazine compound represented by formula (33), but may also include Pd-type benzoxazine compounds, Fa-type benzoxazine compounds, ALP-d-type benzoxazine compounds, etc. The benzoxazine compound may contain only one compound, or it may contain two or more compounds.

[0161] The weight-average molecular weight of the benzoxazine compound is preferably between 200 and 5000. A weight-average molecular weight of 200 or higher can increase the glass transition temperature of the cured product. A weight-average molecular weight of 5000 or lower can improve circuit packing. The weight-average molecular weight can be measured using any general molecular weight measurement method; specifically, it can be measured using gel permeation chromatography (GPC) and converted to a polystyrene equivalent.

[0162] Commercially available benzoxazine compounds can be used. Examples of such commercially available products include ALP-d type benzoxazine, Pd type benzoxazine, and Fa type benzoxazine manufactured by Shikoku Chemicals, Inc.; 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.

[0163] <Additives> The resin composition may, if necessary, contain additives in addition to the components described above, as long as they do not impair the effects of this embodiment. The components of the additives and their content are not particularly limited.

[0164] The additives are not particularly limited, but examples include flame retardants, colorants, coupling agents, heat stabilizers, antioxidants, polymerization initiators, defoamers, antistatic agents, dyes, pigments, lubricants, and the like.

[0165] (1.2) Physical properties The properties of the resin composition, its semi-cured product, and its cured product will be described. Each evaluation method will be explained in the respective examples.

[0166] <Resin flowability> Resin flowability is a physical property related to moldability. Resin compositions and their semi-cured products have good resin flowability. If resin flowability is too low, the spaces between the wires in a wiring board will not be sufficiently filled, and gaps, voids, etc., will occur in the insulating layer of the wiring board. In other words, good resin flowability results in good circuit filling.

[0167] The resin flowability of the resin composition and its semi-cured product is preferably 5% to 50%. When it is 5% or more, the insulating layer of the wiring board can be sufficiently filled between the wires. When it is 50% or less, variations in the thickness of the insulating layer of the wiring board can be reduced.

[0168] <Bステージライフ> B-stage life is a physical property related to storage stability. Semi-cured resin compositions have a good B-stage life. B-stage life can be evaluated by the rate of change in resin flowability due to deterioration over time. If the B-stage life is insufficient, the resin flowability decreases due to deterioration over time, and moldability deteriorates. In other words, if the B-stage life is good, moldability remains good even after deterioration over time.

[0169] The B-stage life (rate of change in resin flowability) is preferably 50% or less.

[0170] <Circuit filling properties> Circuit filling ability is a physical property related to moldability. Resin compositions and their semi-cured products have good circuit filling ability. If circuit filling ability is insufficient, voids and the like will occur in the insulating layer inside the circuit when the product is cured after molding.

[0171] <Resin separability> Resin separation properties are physical properties related to moldability. Resin compositions and their semi-cured products have good resin separation properties. Resin separation properties refer to the dispersibility of inorganic fillers (E) in the cured product when the filled resin composition or its semi-cured product is cured. That is, when resin separation properties are good, the inorganic fillers (E) in the cured product of the resin composition are uniformly dispersed. On the other hand, if resin separation properties are insufficient, the inorganic fillers (E) in the cured product of the resin composition are not uniformly dispersed, and the inorganic fillers (E) separate from resin components such as polyphenylene ether compounds (A), maleimide compounds (B), and reactive compounds (C), and the desired physical properties of the cured product do not appear.

[0172] <Heat resistance> The cured product of the resin composition has good heat resistance. Specifically, the cured product of the resin composition has good reflow resistance. Reflow resistance refers to the property that mechanical damage does not occur even when reflow soldering is performed using a reflow oven. The upper limit of the temperature inside the reflow oven is not particularly limited, but for example, it is 260°C or less. If the reflow resistance is not good, delamination, cracks, etc. will occur between cured products and between cured products and metals when reflow soldering is performed using a reflow oven. If this mechanical damage occurs in products equipped with wiring, it can lead to the breakage of the wiring, etc. Since the cured product of the resin composition of this disclosure has good reflow resistance, metal-clad laminates and wiring boards containing it have excellent reliability.

[0173] <Interlayer Peel Strength> The cured resin composition exhibits good interlayer peel strength. Specifically, it has good peel strength between adhered cured resin compositions. That is, the adhesion between cured resin compositions is good and they are resistant to delamination, resulting in metal-clad laminates and wiring boards manufactured from the resin composition having excellent reliability.

[0174] The metal peel strength of the cured resin composition is preferably 0.5 kN / m or more.

[0175] <Tensile stretch> The cured product of the resin composition has good tensile elongation. If the tensile elongation is insufficient, the cured product of the resin composition will have poor flexibility, leading to mechanical damage such as cracking.

[0176] The tensile elongation of the cured resin composition is preferably 2.5% or more. In this case, the cured resin composition has appropriate flexibility, which can suppress the occurrence of cracks and other damage.

[0177] (1.3) Preparation method Methods for preparing the resin composition include, but are not limited to, a method of mixing a polyphenylene ether compound (A), a maleimide compound (B), a reactive compound (C), a polymerization inhibitor (D), and an inorganic filler (E) in predetermined amounts. Furthermore, an elastomer (F) and additives may be added and mixed as needed.

[0178] Furthermore, the resin composition may contain an organic solvent. That is, it is preferable that the resin composition be used as a varnish-state resin composition containing an organic solvent. A varnish-state resin composition is one in which an organic solvent is further added to the components contained in the above-mentioned resin composition.

[0179] The above-mentioned varnished resin composition is prepared as follows. First, components of the resin composition that can be dissolved in an organic solvent are added to the organic solvent, stirred, and mixed to prepare a mixture. Alternatively, this mixture may be prepared by stirring and mixing while heating. Next, components that cannot be dissolved in the organic solvent are added to the above mixture, and the mixture is dispersed using a ball mill, bead mill, planetary mixer, etc., until the desired dispersion state is reached, thereby preparing a varnished resin composition. The organic solvent used here is not particularly limited, but it is preferable that it can dissolve, for example, polyphenylene ether compounds (A), maleimide compounds (B), reactive compounds (C), polymerization inhibitors (D), etc., and does not inhibit the curing reaction of the resin composition. Specifically, examples of organic solvents include toluene and methyl ethyl ketone (MEK).

[0180] (2) Examples of applications of resin compositions Examples of applications of the resin composition will be explained with reference to Figures 1 to 5.

[0181] By using a resin composition, a prepreg 1, a resin-coated film 2, a resin-coated metal foil 3, a metal-clad laminate 4, and a wiring board 5 can be obtained.

[0182] More specifically, the prepreg 1 includes at least one of the resin composition and a semi-cured product of the resin composition. The resin layer 21 of the resin-coated film 2 includes at least one of the resin composition and a semi-cured product of the resin composition. The resin layer 31 of the resin-coated metal foil 3 includes at least one of the resin composition and a semi-cured product of the resin composition. The insulating layer 41 of the metal-clad laminate 4 includes a cured product of the resin composition. The insulating layer 51 of the wiring board 5 includes a cured product of the resin composition.

[0183] In this embodiment, the resin composition is in an initial stage, being uncured, soluble in certain liquids, and fusible. That is, the resin composition is in Stage A.

[0184] Furthermore, in this embodiment, a semi-cured product is a resin composition that has been partially cured to the extent that it can be further cured. For example, when the resin composition according to this embodiment is heated, the viscosity gradually decreases at the beginning of heating, but gradually increases as the curing of the resin composition begins. Thus, a semi-cured product is a resin composition that has been partially cured, and is what is known as a B-stage resin composition.

[0185] (2.1) Prepreg Figure 1 is a schematic cross-sectional view showing an example of prepreg 1 according to this embodiment.

[0186] The prepreg 1 comprises at least one of a resin composition and a semi-cured product of the resin composition. The prepreg 1 may also comprise a resin layer 11, as shown in Figure 1. That is, the resin layer 11 comprises at least one of a resin composition and a semi-cured product of the resin composition. The resin layer 11 further comprises a fibrous substrate 12. In other words, the prepreg 1 may comprise a resin layer 11 formed by impregnating a fibrous substrate 12 with at least one of a resin composition and a semi-cured product of the resin composition.

[0187] Furthermore, the prepreg 1 obtained using the resin composition may include a semi-cured product of the resin composition, as described above, or it may include an uncured resin composition, i.e., an uncured product of the resin composition.

[0188] As described above, the prepreg 1 may include a resin layer 11 formed by impregnating a fibrous substrate 12 with at least one of a resin composition and a semi-cured product of the resin composition. When impregnating the fibrous substrate 12 with at least one of the resin composition and the semi-cured product of the resin composition, it is preferable to use a varnish manufactured from the resin composition. Also, as shown in Figure 1, the prepreg 1 has one fibrous substrate 12, but it may have two or more fibrous substrates 12.

[0189] The fibrous base material 12 is a reinforcing material and is not particularly limited, but examples include glass cloth, aramid cloth, polyester cloth, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper, linter paper, etc. By using glass cloth, a laminate with excellent mechanical strength can be obtained. It is particularly preferable that the glass cloth is flattened. Specifically as a flattening process, a method of continuously pressing the glass cloth with a press roll at an appropriate pressure to flatten the yarn can be used. The thickness of the fibrous base material 12 used is not particularly limited, but for example, it is 10 μm or more and 300 μm or less. The glass cloth contains glass fibers, but may also contain reinforcing fibers other than glass fibers. The glass cloth may be surface-treated with a coupling agent or the like before impregnation with the varnish-state resin composition. Surface treatment of the glass cloth can improve the adhesion between the glass cloth and the resin composition. The coupling agent used for surface treatment is not particularly limited, but examples include those that can be used with the inorganic filler (E) mentioned above.

[0190] Furthermore, in order to obtain the resin layer 11, the fibrous substrate 12 is impregnated with varnish by either immersing it in varnish or applying varnish to the fibrous substrate 12, and this impregnation can be repeated multiple times as needed. In addition, by repeatedly impregnating with multiple varnishes having different compositions and concentrations, it is possible to ultimately obtain a resin layer 11 containing a resin composition or a semi-cured resin composition with the desired composition and impregnation amount.

[0191] Furthermore, regarding the method for producing the prepreg 1, for example, the organic solvent may be reduced or removed from the resin layer 11 by heating the resin layer 11, which is produced by impregnating a fibrous substrate 12 with a varnish containing a resin composition and an organic solvent. When reducing or removing the organic solvent from the resin layer 11 by heating the resin layer 11, for example, the temperature is 80°C or higher and 180°C or lower, and the time is 1 minute or higher and 10 minutes or lower.

[0192] The method for producing the prepreg 1 comprising at least one of the resin composition and the semi-cured product of the resin composition according to this embodiment, and a fibrous base material 12, is not limited to the method described above. In other words, the prepreg 1 produced using the resin composition according to this embodiment can be produced by any appropriate method.

[0193] Since the prepreg 1 according to this embodiment is manufactured using the resin composition according to this embodiment, it can achieve excellent heat resistance, moldability, and storage stability.

[0194] (2.2) Resin-coated film Figure 2 is a schematic cross-sectional view showing an example of a resin-coated film 2 according to this embodiment.

[0195] The resin-coated film 2 comprises a resin layer 21 containing at least one of a resin composition and a semi-cured product of the resin composition, and a support film 22. That is, the resin-coated film 2 comprises a resin layer 21 containing at least one of a resin composition and a semi-cured product of the resin composition, and a support film 22 overlapping the resin layer 21. The resin-coated film 2 may also have other layers between the resin layer 21 and the support film 22.

[0196] Furthermore, as described above, the resin layer 21 may contain a semi-cured product of the resin composition, or it may contain an uncured product of the resin composition that has not yet hardened. In other words, the resin-coated film 2 may be a resin-coated film 2 comprising a resin layer 21 containing a semi-cured product of the resin composition and a support film 22, or it may be a resin-coated film 2 comprising a resin layer 21 containing an uncured product of the resin composition before hardening and a support film 22.

[0197] The resin layer 21 may or may not contain a fibrous substrate (not shown). Furthermore, if the resin layer 21 contains a fibrous substrate, the same type of fibrous substrate as the fibrous substrate 12 of the prepreg 1 can be used. In other words, the resin layer 21 may be manufactured from the prepreg 1.

[0198] The support film 22 supports the resin layer 21. Thus, by the support film 22 supporting the resin layer 21, the resin layer 21 can be made easier to handle. The support film 22 is not particularly limited, but for example, it is an electrically insulating film. Examples of the support film 22 include a polyethylene terephthalate (PET) film, a polyimide film, a polyester film, a polyparabanic acid film, a polyether ether ketone film, a polyphenylene sulfide film, a polyamide film, a polycarbonate film, a polyarylate film, and the like.

[0199] A release agent layer (not shown) may be provided on the surface of the support film 22 that supports the resin layer 21. By this release agent layer, the support film 22 can be peeled from the resin layer 21 as necessary. Preferably, after the resin layer 21 is cured to form an insulating layer, the support film 22 is peeled from this insulating layer.

[0200] In FIG. 2, one surface of the resin layer 21 is covered with the support film 22, but the other surface of the resin layer 21 may be covered with a cover film (not shown). By covering both surfaces of the resin layer 21, the resin layer 21 can be made even easier to handle, and the adhesion of foreign matter to the resin layer 21 can be suppressed.

[0201] The cover film is not particularly limited, but for example, it is an electrically insulating film. Examples of the cover film include a polyethylene terephthalate (PET) film, a polyolefin film, a polyester film, a polymethylpentene film, and the like. Also, a release agent layer may be further provided between the resin layer 21 and the cover film. By the release agent layer, the cover film can be peeled from the resin layer 21 as necessary.

[0202] Note that the support film 22 and the cover film may be subjected to surface treatments such as matte treatment, corona treatment, release treatment, or roughening treatment as necessary.

[0203] The resin layer 21 is manufactured by applying the resin composition to the support film 22. The method of applying the resin composition is not particularly limited, but for example, a bar coater, die coater, doctor blade, baker applicator, etc., can be used. When applying the resin layer 21 to the support film 22, it is preferable to use the resin composition in a varnish state. As described above, by heating the varnish applied on the support film 22, 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 to 180°C for a time of 1 minute to 10 minutes. That is, the conditions for reducing or removing the organic solvent from the resin layer 21 by heating the resin layer 21 may be the same as the conditions for reducing or removing the organic solvent from the resin layer 11 by heating the resin layer 11 when manufacturing the prepreg 1. In this way, a resin layer 21 containing at least one of the resin composition and a semi-cured product of the resin composition is formed on the support film 22, thereby manufacturing the resin-coated film 2.

[0204] The method for producing the resin-coated film 2, which comprises a resin layer 21 containing the resin composition or a semi-cured product of the resin composition according to this embodiment, and a support film 22 supporting the resin layer 21, is not limited to the method described above. In other words, the resin-coated film 2 produced using the resin composition according to this embodiment can be produced by any appropriate method.

[0205] Since the resin-coated film 2 according to this embodiment is manufactured using the resin composition according to this embodiment, it can achieve excellent heat resistance, moldability, and storage stability.

[0206] (2.3) Metal foil with resin coating Figure 3 is a schematic cross-sectional view showing an example of a resin-coated metal foil 3 according to this embodiment.

[0207] The resin-coated metal foil 3 comprises a resin layer 31 containing at least one of a resin composition and a semi-cured product of the resin composition, and a metal foil 32. The resin-coated metal foil 3 may also have other layers between the resin layer 31 and the metal foil 32.

[0208] As described above, the resin layer 31 may contain a semi-cured resin composition or an uncured resin composition. That is, the resin-coated metal foil 3 may be a resin-coated metal foil 3 comprising a resin layer 31 containing a semi-cured resin composition and a metal foil 32, or it may be a resin-coated metal foil 3 comprising a resin layer 31 containing an uncured resin composition before curing and a metal foil 32.

[0209] The resin layer 31 may or may not contain a fibrous substrate (not shown). Furthermore, if the resin layer 31 contains a fibrous substrate, the same type of fibrous substrate as the fibrous substrate 12 of the prepreg 1 can be used. In other words, the resin layer 31 can be manufactured from the prepreg 1.

[0210] The metal foil 32 is not particularly limited, but examples include copper foil and aluminum foil. The metal foil 32 can be used as wiring 52 of the wiring board 5 after unnecessary portions are removed by etching using a subtractive method or the like.

[0211] Furthermore, the resin-coated metal foil 3 may be equipped with a cover film (not shown) or the like, if necessary. The same cover film used for the resin-coated film 2 described above can be used.

[0212] The resin layer 31 is manufactured by applying a resin composition to the metal foil 32. The method of applying the resin composition is not particularly limited, but examples include using a bar coater, die coater, doctor blade, baker applicator, etc. When applying the resin composition to the metal foil 32, it is preferable to use a resin composition in a varnish state.

[0213] As described above, by heating the varnish applied to the metal foil 32, 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 to 180°C for a time of 1 minute to 10 minutes. In other words, the conditions for reducing or removing the organic solvent from the resin layer 31 by heating the resin layer 31 may be the same as the conditions for reducing or removing the organic solvent from the resin layer 11 by heating the resin layer 11 when preparing the prepreg 1.

[0214] The method for producing the resin-coated metal foil 3, which comprises a resin layer 31 containing the resin composition or a semi-cured product of the resin composition according to this embodiment, and a metal foil 32 adhered to the resin layer 31, is not limited to the method described above. In other words, the resin-coated metal foil 3 produced using the resin composition according to this embodiment can be produced by any appropriate method.

[0215] Since the resin-coated metal foil 3 according to this embodiment is manufactured using the resin composition according to this embodiment, it can achieve excellent heat resistance, moldability, and storage stability.

[0216] (2.4) Metal-clad laminate Figure 4 is a schematic cross-sectional view showing an example of a metal-clad laminate 4 according to this embodiment. The metal-clad laminate 4 comprises an insulating layer 41 containing a cured product of the resin composition according to this embodiment, and a metal foil 42 overlapping the insulating layer 41.

[0217] One method for manufacturing the metal-clad laminate 4 is to layer a resin composition or a semi-cured resin composition with a metal foil 42, heat and pressurize it to cure the resin composition and form an insulating layer 41, thereby manufacturing the metal-clad laminate 4. More specifically, a metal foil 42 such as copper foil is layered on one or both sides of a resin composition or a semi-cured resin composition, the resin composition or semi-cured resin composition and the metal foil 42 are heated and pressurized to cure the resin composition and form an insulating layer 41, and the insulating layer 41 containing the cured resin composition and the metal foil 42 are laminated and integrated to manufacture a metal-clad laminate 4 in which the metal foil 42 is in close contact with one or both sides of the insulating layer 41 containing the cured resin composition.

[0218] Furthermore, the insulating layer 41 may be manufactured using the prepreg 1 described above. More specifically, the prepreg 1 and metal foil 42 can be heated and pressurized to cure the prepreg 1 and form the insulating layer 41. By laminating and integrating the insulating layer 41 containing the cured prepreg 1 and the metal foil 42, a metal-clad laminate 4 can be manufactured in which the metal foil 42 is in close contact with one or both sides of the insulating layer 41 containing the cured prepreg 1. When the metal-clad laminate 4 is manufactured using the prepreg 1, the insulating layer 41 contains a fibrous base material (not shown). There may be only one fibrous base material, or there may be two or more.

[0219] Furthermore, the insulating layer 41 may be manufactured using the resin-coated film 2 and resin-coated metal foil 3 described above. More specifically, the resin layer 21 of the resin-coated film 2 or the resin layer 31 of the resin-coated metal foil 3 and the metal foil 42 are heated and pressurized to cure the resin layer 21 of the resin-coated film 2 or the resin layer 31 of the resin-coated metal foil 3 to form the insulating layer 41. By laminating and integrating the insulating layer 41, which includes the cured resin layer 21 of the resin-coated film 2 or the cured resin layer 31 of the resin-coated metal foil 3, with the metal foil 42, a metal-clad laminate 4 can be manufactured in which the metal foil 42 is adhered to one or both sides of the insulating layer 41, which includes the cured resin layer 21 of the resin-coated film 2 or the cured resin layer 31 of the resin-coated metal foil 3. In this case, when manufactured using the resin-coated metal foil 3, the metal foil 32 of the resin-coated metal foil 3 becomes the metal foil 42 in the metal-clad laminate 4.

[0220] In manufacturing the metal-clad laminate 4, the thickness of the metal foil 42 can be appropriately set according to the desired purpose. Further, the heat and pressure conditions in manufacturing the metal-clad laminate 4 can be appropriately set according to the thickness of the metal-clad laminate 4 to be manufactured, the type, components, etc. of the resin composition forming the insulating layer 41. Furthermore, when using an ultra-thin metal foil as the metal foil 42, a carrier-attached metal foil provided with a release layer and a carrier may be used to improve handling properties.

[0221] Note that the method for manufacturing the metal-clad laminate 4 including the insulating layer 41 containing the cured product of the resin composition or prepreg 1 according to this embodiment and the metal foil 42 adhered to the insulating layer 41 is not limited to the above method. That is, the metal-clad laminate 4 manufactured using the resin composition or prepreg 1 according to this embodiment can be manufactured by an appropriate method.

[0222] Since the metal-clad laminate 4 according to this embodiment is manufactured using the resin composition according to this embodiment, it can have excellent heat resistance.

[0223] (2.5) Wiring board FIG. 5 is a schematic cross-sectional view showing an example of the wiring board 5 according to this embodiment. The wiring board 5 includes an insulating layer 51 containing a cured product of a resin composition and a wiring 52 overlapping the insulating layer 51. The wiring 52 may be formed on only one side of the insulating layer 51 or on both sides.

[0224] The insulating layer 51 may contain the cured product of the above-described prepreg 1. That is, the wiring board 5 includes an insulating layer 51 manufactured using the prepreg 1 and a wiring 52 overlapping the insulating layer 51. The wiring 52 may be formed on only one side of the insulating layer 51 or on both sides. When the wiring board 5 is manufactured using the prepreg 1, it has a fibrous substrate (not shown). The fibrous substrate may have only one sheet or two or more sheets.

[0225] Furthermore, the wiring board 5 may be manufactured using the metal-clad laminate 4 described above. More specifically, the wiring 52 can be formed by etching or the like on the metal foil 42 on the surface of the metal-clad laminate 4. That is, the wiring board 5 can be formed by partially removing the metal foil 42 on the surface of the metal-clad laminate 4. In this way, a wiring board 5 can be manufactured that comprises an insulating layer 51 and wiring 52 as circuits on one or both sides of the insulating layer 51.

[0226] In addition to the methods described above, other methods for circuit formation are not limited to the above, but examples include circuit formation using the semi-additive process (SAP) and the modified semi-additive process (MSAP).

[0227] Since the wiring board 5 according to this embodiment is manufactured using the resin composition according to this embodiment, it may have excellent heat resistance.

[0228] 3. Appearance As is clear from the embodiments described above, this disclosure includes the following aspects. In the following, reference numerals are enclosed in parentheses solely to indicate their correspondence with the embodiments.

[0229] A resin composition according to a first aspect of this disclosure contains a polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond, a maleimide compound (B), a reactive compound (C) different from the polyphenylene ether compound (A), a polymerization inhibitor (D), and an inorganic filler (E). The reactive compound (C) includes at least one selected from the group consisting of chemical structures represented by formula (1) and formula (2).

[0230] [ka]

[0231] [ka]

[0232] In formulas (1) and (2), Ar represents an aromatic structure. The polymerization inhibitor (D) includes a free radical compound (D1) having a molecular weight of 160 to 800.

[0233] According to this embodiment, a resin composition that achieves excellent heat resistance, moldability, and storage stability can be obtained.

[0234] In the first embodiment, the resin composition according to the second aspect of the present disclosure comprises a polyfunctional reactive compound (C1) having two or more chemical structures represented by formula (3) in one molecule, where the reactive compound (C) is a polyfunctional reactive compound (C1).

[0235] [ka]

[0236] In formula (3), R 35 R represents an allyl group or a 1-propenyl group. 36 This represents a hydrogen atom, a methyl group, a methoxy group, a hydroxyl group, an aldehyde group, an allyl ether group, a 1-propenyl ether group, or a phenyl group.

[0237] In a third aspect of the present disclosure, the resin composition further comprises, in a second aspect, a polyfunctional reactive compound (C2) in which the reactive compound (C) is at least one selected from the group consisting of compounds represented by formulas (4) and (5).

[0238] [ka]

[0239] In formula (4), R 42 R represents an allyl group or a 1-propenyl group. 43 represents a hydrogen atom. f represents an integer between 1 and 4 (inclusive).

[0240] [ka]

[0241] In formula (5), R 44 Each of these independently represents either an allyl group or a 1-propenyl group.

[0242] In the fourth aspect of the present disclosure, the resin composition, in any one of the first to third aspects, comprises a polyphenylene ether compound (A) having at least one selected from the group consisting of groups represented by formula (6) and formula (7).

[0243] [ka]

[0244] In formula (6), a represents an integer between 0 and 10, Z represents an arylene group, and R1 to R3 each independently represent a hydrogen atom or an alkyl group.

[0245] [ka]

[0246] In formula (7), R4 represents a hydrogen atom or an alkyl group.

[0247] A resin composition according to a fifth aspect of the present disclosure, in any one aspect of the first to fourth aspects, comprises at least one free radical compound (D1) selected from the group consisting of structures represented by formulas (8), (9), (10), and (11).

[0248] [ka]

[0249] [ka]

[0250] [ka]

[0251] [ka]

[0252] A resin composition according to a sixth aspect of the present disclosure further comprises, in a fifth aspect, at least one free radical compound (D1) selected from the group consisting of structures represented by formulas (12), (13), and (14).

[0253] [ka]

[0254] In formula (12), X A This indicates an ether bond with an amino group, cyano group, hydroxyl group, isothiocyanate group, carboxyl group, oxo group, amide group, acyloxy group, or organic group.

[0255] [ka]

[0256] In formula (13), X B This indicates an ether bond with a cyano group, isothiocyanate group, carboxyl group, amide group, acyloxy group, or organic group.

[0257] [ka]

[0258] In formula (14), X C This represents an alkylene group, an aromatic structure, a carbonyl group, an amide group, or an oxygen atom.

[0259] The resin composition according to the seventh aspect of this disclosure further contains an elastomer (F) in any one of the first to sixth aspects. The elastomer (F) is present in an amount of 1 to 30 parts by mass per 100 parts by mass of the total of the polyphenylene ether compound (A), the maleimide compound (B), and the reactive compound (C).

[0260] The resin composition according to the eighth aspect of this disclosure, in any one of the first to seventh aspects, comprises an elastomer (F) containing a core-shell rubber (F1).

[0261] In the resin composition according to the ninth aspect of this disclosure, in any one of the first to eighth aspects, the content of the polymerization inhibitor (D) is 0.1 parts by mass or more and 1.0 part by mass or less, based on 100 parts by mass of the polyphenylene ether compound (A), maleimide compound (B), and reactive compound (C).

[0262] In the resin composition according to the tenth aspect of the present disclosure, in any one aspect of the first to ninth aspects, the content of the inorganic filler (E) is 100 parts by mass or more and 300 parts by mass or less, based on 100 parts by mass of the total of the polyphenylene ether compound (A), maleimide compound (B), and reactive compound (C).

[0263] A prepreg (1) according to the eleventh aspect of the present disclosure comprises a resin composition or a semi-cured product of a resin composition according to any one of the first to tenth aspects, and a fibrous substrate (12).

[0264] A resin-coated film (2) according to the twelfth aspect of the present disclosure comprises a resin layer (21) containing a resin composition or a semi-cured product of a resin composition according to any one of the first to tenth aspects, and a support film (22).

[0265] A resin-coated metal foil (3) according to the thirteenth aspect of this disclosure comprises a resin layer (31) containing a resin composition or a semi-cured product of a resin composition according to any one of the first to tenth aspects, and a metal foil (32).

[0266] A metal-clad laminate (4) according to a fourteenth aspect of the present disclosure comprises an insulating layer (41) containing a cured resin composition according to any one of the first to tenth aspects, and a metal foil (42).

[0267] A metal-clad laminate (4) according to a 15th aspect of the present disclosure comprises an insulating layer (41) containing a cured product of the prepreg (1) according to the 11th aspect, and a metal foil (42).

[0268] A wiring board (5) according to the sixteenth aspect of the present disclosure comprises an insulating layer (51) containing a cured product of a resin composition according to any one of the first to tenth aspects, and wiring (52).

[0269] A wiring board (5) according to the 17th aspect of this disclosure comprises an insulating layer (51) containing a cured prepreg (1) according to the 11th aspect, and wiring (52). [Examples]

[0270] The present disclosure will be described in detail below with reference to examples. However, the present disclosure is not limited to the following examples.

[0271] (1) Preparation of resin composition The components shown in Table 1 were used as raw materials for the resin compositions. Polyphenylene ether compound (A), maleimide compound (B), reactive compound (C), polymerization inhibitor (D), inorganic filler (E), elastomer (F), etc., were blended in the amounts shown in Table 1. The mixture was diluted with a solvent (methyl ethyl ketone), and then stirred and mixed to homogenize it, thereby preparing the varnish-state resin compositions of the examples and comparative examples, each with a solid content concentration of 60% by mass. Details of each component used are as follows.

[0272] <Polyphenylene ether compound (A)> -Polyphenylene ether compound #1: Manufactured by Mitsubishi Gas Chemical Company, Inc., catalog number "OPE-2St-2200", a polyphenylene ether compound having a carbon-carbon unsaturated group in which the terminal hydroxyl groups of a polyphenylene ether compound are terminally modified with vinyl benzyl groups (represented by formula (22), in which R1 to R3 are hydrogen atoms, Z is a phenylene group, and a is 1), weight-average molecular weight 2200.

[0273] <Maleimide compound (B)> - Maleimide compound #1: Manufactured by Nippon Kayaku Co., Ltd., catalog number "MIR-5000-60T", polyphenylmethanemaleimide represented by formula (35).

[0274] <Reactive compound (C)> -Reactive compound #1: Manufactured by Gun-ei Chemical Industry Co., Ltd., product number "LVA01", allylphenol resin -Reactive compound #2: Manufactured by Yokkaichi Synthetic Co., Ltd., catalog number "DABPA", compound name "2,2'-diallylbisphenol A", represented by formula (5), R 44 A reactive compound in which the group is an allyl group.

[0275] <Polymerization inhibitor (D)> - Polymerization inhibitor #1: Manufactured by ADEKA Corporation, product number "ADEKA Stab LA-7RD", compound name "4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical", represented by formula (12), where X A A compound in which the group is a hydroxyl group, molecular weight 172 - Polymerization inhibitor #2: Manufactured by Tokyo Chemical Industry Co., Ltd., product number "H0878", compound name "4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxylbenzoate free radical", represented by formula (12), where X A A compound in which the group is a benzoyloxy group, with a molecular weight of 276. -Polymerization inhibitor #3: Manufactured by Tokyo Chemical Industry Co., Ltd., product number "B5642", compound name "bis(2,2,6,6-tetramethyl-4-piperidyl-1-oxyl) sebacate", represented by formula (14), where X CA compound in which the group is an octylene group, molecular weight 510 - Polymerization inhibitor #4: Manufactured by Tokyo Chemical Industry Co., Ltd., product number "G0020", compound name "Galvinoxyl free radical", a compound having the structure of formula (11), molecular weight 421 - Polymerization inhibitor #5: Manufactured by Tokyo Chemical Industry Co., Ltd., product number "C1406", compound name "3-Carboxy-2,2,5,5-tetramethylpyrrolidine-1-oxyl free radical", represented by formula (13), X in formula (13) B is a compound in which the group is a carboxy group, molecular weight 186.

[0276] <Inorganic filler (E)> - Inorganic filler #1: Manufactured by Admatechs Co., Ltd., product number "SC2500-SXJ", silica, a product treated with a phenylaminosilane coupling agent.

[0277] <Elastomer (F)> - Elastomer #1: Manufactured by Kaneka Corporation, product number "MX-910", core-shell rubber.

[0278] <Other curing agents> - Benzoxazine compound: Manufactured by Kolon Industries, Inc., product number "KZH-5031", represented by formula (33), R in formula (33) 49 is a polyfunctional benzoxazine compound in which the group is dicyclopentadiene - Phenol compound: Manufactured by Gun Ei Chemical Industry Co., Ltd., product number "ELP83H", long-chain alkylphenol resin.

[0279] <Additives> - Polymerization initiator: Manufactured by NOF Corporation, product number "Perbutyl P", compound name "1,3-Bis(tert-butylperoxyisopropyl)benzene".

[0280] (2) Preparation of evaluation substrate <Preparation of metal foil with resin> As the metal foil, a thin copper foil with a carrier copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd., product number "MT18FL", thickness of the thin copper foil: 3 μm, thickness of the carrier copper foil: 18 μm) was prepared. The resin compositions of the examples and comparative examples in varnish state, prepared above, were applied to the surface of the thin copper foil of this thin copper foil with a carrier copper foil. The resin composition applied to the thin copper foil with a carrier copper foil was heated and dried at 130°C for 3 minutes until it became a semi-cured product. This removed the solvent from the resin composition, and a resin-coated metal foil was obtained comprising a resin layer containing the semi-cured resin composition and a metal foil containing the thin copper foil with a carrier copper foil overlapping one side of the resin layer. The content of the resin composition in this resin-coated metal foil was 25% by mass, with the total mass of the resin-coated metal foil being 100% by mass.

[0281] <Fabrication of evaluation board> First, two resin-coated metal foils obtained as described above were prepared, and these were arranged so that the resin-coated sides of the metal foils were in contact with each other. This laminate of resin-coated metal foil copper foil and carrier copper foil thin copper foil was subjected to vacuum conditions at a temperature of 220°C and a pressure of 30 kg / cm². 2 The substrate was heated and pressurized for 120 minutes under these conditions. Subsequently, by peeling off each of the carrier copper foils of the thin copper foils with carrier copper foils placed on both outer sides, an evaluation substrate with a thickness of 80 μm was obtained, comprising an insulating layer including a resin layer of resin-coated metal foil and metal layers including thin copper foils on both sides of this insulating layer.

[0282] (3) Evaluation <Resin flowability> The prepared resin-coated metal foil was cut to 100±1mm × 100±1mm. Two of these cut resin-coated metal foils were prepared, and the laminate, with the resin-coated sides of these two pieces in close contact, was weighed using an electronic balance. The weight of the laminate, rounded to one decimal place, was defined as A(g). In addition, two thin copper foils (MT18FL) with carrier copper foil, which were used as metal foil, were cut to 100±1mm × 100±1mm. The carrier copper foil was peeled off the cut metal foils, and then the metal foils from which the carrier copper foil had been peeled off were weighed. The weight of the metal foils, rounded to one decimal place, was defined as B(g). The above laminates were sandwiched between release films, then between iron plates, and then pressed using an automatic temperature-controlled press (flow tester) at a temperature of 170±2℃ and a pressure of 20±0.3kg / cm². 2 The material was hot-pressed for 5 minutes under the specified conditions. Next, a disc with a diameter of 81.1 ± 0.05 mm was punched out from the center of the laminate, and this disc was weighed using an electronic balance. The value of this weighing result, rounded to one decimal place, was defined as C (g). Then, the resin flowability was calculated using the following formula, and the integer value obtained by rounding the calculated value to the first decimal place was defined as the evaluation value.

[0283] Resin flow (%) = (A - 2C) / (AB) × 100.

[0284] <Bステージライフ> The laminate [weight C (g)] used in the resin flow evaluation described above was subjected to degradation treatment by being left in a constant temperature and humidity chamber set to 23°C and 50% RH for 90 days. After the time had elapsed, the degraded laminate was recovered, and a disc with a diameter of 81.1 ± 0.05 (mm) was punched out from the center of the laminate. This disc was weighed using an electronic balance. The value of this weighing result, rounded to one decimal place, was defined as D (g). The integer value obtained by rounding the value calculated using the following formula to the first decimal place was defined as the rate of change. The weighing value of the metal foil was the value [B (g)] used in the resin flow evaluation described above.

[0285] Resin flow after time changes (%) = (C - 2D) / (CB) × 100.

[0286] Furthermore, the rate of change due to the change in resin flow over time was calculated using the following formula. The resin flow used was the one calculated based on the resin flow properties described above.

[0287] Rate of change (%) = {(Resin flow) - (Resin flow after change over time)} / (Resin flow) × 100 The rate of change was classified according to the following evaluation criteria, and Stage B life was evaluated.

[0288] A: 5% or more and 50% or less B: Less than 5% or more than 50%.

[0289] <Circuit filling properties> A printed circuit board was obtained by etching a grid-like pattern of conductive wiring onto the metal foil on both sides of the evaluation substrate, with residual copper percentages of 20%, 50%, and 80%, respectively. On each of the conductive wirings on both sides of this printed circuit board, a resin-coated metal foil was laminated so that the resin layer side was in close contact. Then, the temperature was set to 220°C and 30 kgf / cm². 2 A laminate was obtained by heating and pressurizing under pressure for 120 minutes. The carrier copper foil of the obtained laminate was peeled off, and the thin copper foil on the outermost surface of the laminate was further removed by etching. This laminate was cut in the thickness direction between the circuits of the conductive wiring, and the presence or absence of voids in the cut surface was observed visually. The observation results were classified according to the evaluation criteria below, and the circuit filling ability was evaluated.

[0290] A: The resin composition derived from the resin layer of the resin-coated metal foil is sufficiently embedded between the circuits of the conductor wiring, and no voids are observed in any of the patterns. B: Insufficient penetration of the resin composition derived from the resin layer of the resin-coated metal foil into the circuits of the conductive wiring resulted in voids being observed in some patterns. C: The resin composition derived from the resin layer of the resin-coated metal foil did not penetrate sufficiently between the circuits of the conductor wiring, and voids were observed in all patterns.

[0291] <Resin separability> Using the cut laminates from the circuit filling performance evaluation described above, the separation of the resin component and inorganic filler at the cut surface was visually observed. The observation results were classified according to the following evaluation criteria, and the resin separation properties were evaluated.

[0292] A: In cured resin compositions derived from the resin layer of resin-coated metal foil filled between the circuits of conductive wiring, separation of the resin component and the inorganic filler was not observed in any of the patterns. B: In cured resin compositions derived from the resin layer of resin-coated metal foil filled between conductive wiring circuits, separation of the resin component and inorganic filler was observed in some patterns. C: In cured resin compositions derived from the resin layer of resin-coated metal foil filled between conductive wiring circuits, separation of the resin component and inorganic filler was confirmed in all patterns.

[0293] <Heat resistant (reflow resistant)> The evaluation substrate was placed in a constant temperature and humidity chamber set to 60°C and 60%RH for 48 hours to absorb moisture. Next, the moisture-treated evaluation substrate was heated in a reflow oven set to a maximum temperature of 260°C. After heating, it was cooled to room temperature. Then, the evaluation substrate was cut through the resin composition filling area, and the cut surface was observed. The observation results were classified according to the following evaluation criteria to assess reflow resistance.

[0294] A: There is no change in appearance, and the interface between the resin compositions in the filling area or between the resin composition and the copper foil has not peeled off. B: Delamination is occurring at the interface between the resin compositions in the filled area or between the resin composition and the copper foil.

[0295] <Interlayer Peel Strength> The evaluation substrate was cut to obtain test specimens measuring 100 mm x 10 mm. For these specimens, in accordance with JIS C6481 (1996), the insulating layer, which is a cured resin-coated metal foil, was peeled off together with the copper foil using a tensile testing machine at a speed of 50 mm / min, and the peel strength was measured. The measurement results were classified according to the following evaluation criteria, and the peel strength was evaluated.

[0296] A: 0.8kN / m or more B: Less than 0.8 kN / m.

[0297] <Tensile stretch> The evaluation substrate was cut to obtain a test specimen measuring 76.2 mm × 12.7 mm. The tensile elongation of this specimen was measured using a universal testing machine (Shimadzu Corporation, Autograph "ACS-X") 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. The measurement results were classified according to the following evaluation criteria, and the tensile elongation was evaluated.

[0298] A: 5% or more B: Over 2% and less than 5% C: 2% or less.

[0299] [Table 1] [Explanation of Symbols]

[0300] 1 Prepreg 11 Resin layer 12. Fibrous base material 2. Resin-coated film 21 Resin layer 22 Support film 3. Metal foil coated with resin 31 Resin layer 32 Metal foil 4 Metal-clad laminate 41 Insulating layer 42 Metal foil 5 Wiring board 51 Insulating layer 52 Wiring

Claims

1. It contains a polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond, a maleimide compound (B), a reactive compound (C) different from the polyphenylene ether compound (A), a polymerization inhibitor (D), and an inorganic filler (E). The reactive compound (C) comprises at least one selected from the group consisting of chemical structures represented by formula (1) and formula (2), 【Chemistry 1】 【Chemistry 2】 In formulas (1) and (2), Ar represents an aromatic structure. The polymerization inhibitor (D) comprises a free radical compound (D1) having a molecular weight of 160 or more and 800 or less. Resin composition.

2. The reactive compound (C) comprises a polyfunctional reactive compound (C1) having two or more chemical structures represented by formula (3) in one molecule. 【Transformation 3】 In formula (3), R ３５ R represents an allyl group or a 1-propenyl group. ３６ This represents a hydrogen atom, a methyl group, a methoxy group, a hydroxyl group, an aldehyde group, an allyl ether group, a 1-propenyl ether group, or a phenyl group. The resin composition according to claim 1.

3. The reactive compound (C) further comprises a polyfunctional reactive compound (C2) which is at least one selected from the group consisting of compounds represented by formula (4) and formula (5). 【Chemistry 4】 In formula (4), R ４２ R represents an allyl group or a 1-propenyl group. ４３ represents a hydrogen atom, and f represents an integer between 1 and 4. 【Transformation 5】 In formula (5), R ４４ This represents an allyl group or a 1-propenyl group. The resin composition according to claim 2.

4. The polyphenylene ether compound (A) has at least one selected from the group consisting of groups represented by formula (6) and formula (7), 【Transformation 6】 In formula (6), a represents an integer between 0 and 10, Z represents an arylene group, and R １ ~R ３ Each of these independently represents a hydrogen atom or an alkyl group. 【Transformation 7】 In formula (7), R ４ This represents a hydrogen atom or an alkyl group. The resin composition according to claim 1.

5. The free radical compound (D1) has at least one selected from the group consisting of structures represented by formulas (8), (9), (10), and (11). The resin composition according to claim 1. 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】

6. The free radical compound (D1) further comprises at least one selected from the group consisting of structures represented by formulas (12), (13), and (14), 【Chemistry 12】 In formula (12), X Ａ represents an amino group, a cyano group, a hydroxy group, an isothiocyanate group, a carboxy group, an oxo group, an amide group, an acyloxy group or an ether bond with an organic group, 【Chemistry 13】 In formula (13), X Ｂ This exhibits an ether bond with a cyano group, isothiocyanate group, carboxyl group, amide group, acyloxy group, or organic group. 【Chemistry 14】 In formula (14), X Ｃ This represents an alkylene group, an aromatic structure, a carbonyl group, an amide group, or an oxygen atom. The resin composition according to claim 5.

7. It further contains elastomer (F), The elastomer (F) is in an amount of 1 to 30 parts by mass relative to 100 parts by mass of the total of the polyphenylene ether compound (A), the maleimide compound (B), and the reactive compound (C). The resin composition according to claim 1.

8. The elastomer (F) includes core shell rubber (F1), The resin composition according to claim 7.

9. The content of the polymerization inhibitor (D) is 0.1 parts by mass or more and 1.0 part by mass or less, based on 100 parts by mass of the polyphenylene ether compound (A), the maleimide compound (B), and the reactive compound (C). The resin composition according to claim 1.

10. The amount of the inorganic filler (E) is 100 parts by mass or more and 300 parts by mass or less, relative to 100 parts by mass of the total of the polyphenylene ether compound (A), the maleimide compound (B), and the reactive compound (C). The resin composition according to claim 1.

11. A resin composition according to any one of claims 1 to 10 or a semi-cured product of the resin composition, and a fibrous substrate, Prepreg.

12. A resin layer comprising a resin composition according to any one of claims 1 to 10 or a semi-cured product of the resin composition, and a support film, Resin-coated film.

13. A resin layer comprising a resin composition according to any one of claims 1 to 10 or a semi-cured product of the resin composition, and a metal foil, Metal foil coated with resin.

14. The insulating layer comprises a cured resin composition according to any one of claims 1 to 10, and a metal foil. Metal-clad laminate.

15. The insulating layer comprises a cured prepreg according to claim 11 and a metal foil, Metal-clad laminate.

16. The device comprises an insulating layer containing a cured resin composition according to any one of claims 1 to 10, and wiring. wiring board.

17. The system comprises an insulating layer containing a cured prepreg according to claim 11, and wiring, wiring board.

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