JP2021152107A - Resin composition, prepreg, film with resin, metal foil with resin, metal-clad laminate, and wiring board - Google Patents

Abstract

To provide a resin composition that is low in dielectric constant and dielectric loss tangent, the resin composition to give a cured product having high interlayer adhesion.SOLUTION: A resin composition has a modified polyphenylene ether compound terminally modified with a substituent having a carbon-carbon unsaturated double bond, and an aliphatic hydrocarbon compound represented by the formula (1). In the formula (1), RA is an alkyl group having 4 or more carbon atoms or an alkenyl group having 4 or more carbon atoms, R1-R3 independently represent a hydrogen atom or an alkyl group.SELECTED DRAWING: None

Description

The present invention relates to a resin composition, a prepreg, a film with a resin, a metal foil with a resin, a metal-clad laminate, and a wiring board.

With the increase in the amount of information processing, various electronic devices are rapidly advancing mounting technologies such as high integration of mounted semiconductor devices, high density of wiring, and multi-layering. Further, the wiring board used for various electronic devices is required to be a wiring board compatible with high frequencies, for example, a millimeter-wave radar board for in-vehicle use.

When a signal is transmitted to the wiring provided on the wiring board, transmission loss due to the conductor forming the wiring, transmission loss due to the derivative around the wiring, and the like occur. It is known that these transmission losses are particularly likely to occur when a high frequency signal is transmitted to the wiring provided on the wiring board. For this reason, the wiring board is required to reduce the loss during signal transmission in order to increase the signal transmission speed. This is especially required for wiring boards that support high frequencies. In order to satisfy this requirement, it is conceivable to use a material having a low dielectric constant and a low dielectric loss tangent as the substrate material for manufacturing the insulating layer constituting the wiring board. Examples of such a substrate material include a resin composition containing a polyphenylene ether component described in Patent Document 1.

Patent Document 1 contains a polyphenylene ether compound terminally modified by a substituent having a carbon-carbon unsaturated double bond, a crosslinked curing agent having a carbon-carbon unsaturated double bond in the molecule, and a flame retardant. A resin composition is described in which the flame retardant contains a compatible phosphorus compound that is compatible with the mixture of the modified polyphenylene ether compound and the crosslinked curing agent, and an incompatible phosphorus compound that is incompatible with the mixture. Has been done. According to Patent Document 1, it is disclosed that a resin composition having excellent heat resistance and flame retardancy of a cured product can be obtained while maintaining the excellent dielectric properties of polyphenylene ether.

JP-A-2015-86330

The wiring board is required not only to reduce the loss during signal transmission in order to further increase the signal transmission speed, but also to separate the insulating delamination when the insulating layer is composed of multiple layers, and to separate the wiring from the insulating layer. It is also required to have high interlayer adhesiveness so as not to cause such problems.

The present invention has been made in view of such circumstances, and an object of the present invention is to provide a resin composition capable of obtaining a cured product having high interlayer adhesion in a resin composition having a low dielectric constant and a low dielectric loss tangent. Another object of the present invention is to provide a prepreg, a film with a resin, a metal foil with a resin, a metal-clad laminate, and a wiring board obtained by using the resin composition.

As a result of various studies, the present inventors have found that the above object can be achieved by the following invention.

The resin composition according to one aspect of the present invention comprises a modified polyphenylene ether compound terminally modified to a substituent having a carbon-carbon unsaturated double bond, and an aliphatic hydrocarbon compound represented by the following formula (1). It is a resin composition containing.

In the formula (1), _RA represents an alkyl group having 4 or more carbon atoms or an alkenyl group having 4 or more carbon atoms, and R _{1 to} R ₃ independently represent a hydrogen atom or an alkyl group.

Further, in the resin composition, it is preferable that the aliphatic hydrocarbon compound contains a compound having 6 to 45 carbon atoms.

Further, in the resin composition, the content of the compound having 6 to 45 carbon atoms is preferably 95% by mass or more with respect to the entire aliphatic hydrocarbon compound.

Further, in the resin composition, it is preferable that the aliphatic hydrocarbon compound contains a compound in which R ₂ and R ₃ are hydrogen atoms.

Further, in the resin composition, a cross-linking type curing agent further containing a curing agent, the curing agent having two or more carbon-carbon unsaturated double bonds in the molecule, and a number average molecular weight of less than 400. , And at least one selected from the group consisting of maleimide compounds having a maleimide group in the molecule.

Further, in the resin composition, the cross-linking type curing agent has a compound having two or more allyl groups in the molecule, a compound having two or more vinylphenyl groups in the molecule, and two or more methacryloyl groups in the molecule. It is preferable to contain at least one selected from the group consisting of a compound and a compound having three or more vinyl groups in the molecule. Further, the maleimide compound is at least one selected from the group consisting of a compound having two or more maleimide groups in the molecule and a compound having one maleimide group in the molecule and having a number average molecular weight of less than 200. It is preferable to include it.

Further, in the resin composition, the content of the aliphatic hydrocarbon compound is 5 to 50 mass by mass with respect to 100 parts by mass of the total mass of the modified polyphenylene ether compound, the aliphatic hydrocarbon compound, and the curing agent. It is preferably a part.

Further, in the resin composition, the content of the curing agent is 5 to 50 parts by mass with respect to 100 parts by mass of the total mass of the modified polyphenylene ether compound, the aliphatic hydrocarbon compound, and the curing agent. Is preferable.

Further, the prepreg according to another aspect of the present invention is a prepreg comprising the resin composition or a semi-cured product of the resin composition and a fibrous base material.

The resin-attached film according to another aspect of the present invention is a resin-attached film including a resin layer containing the resin composition or a semi-cured product of the resin composition, and a support film.

Further, the metal leaf with resin according to another aspect of the present invention is a metal leaf with resin including the resin composition or a resin layer containing a semi-cured product of the resin composition, and the metal foil.

The metal-clad laminate according to another aspect of the present invention is a metal-clad laminate comprising an insulating layer containing a cured product of the resin composition or a cured product of the prepreg, and a metal foil.

Further, the wiring board according to another aspect of the present invention is a wiring board including an insulating layer containing a cured product of the resin composition or a cured product of the prepreg, and wiring.

According to the present invention, it is possible to provide a resin composition capable of obtaining a cured product having high interlayer adhesion in a resin composition having a low dielectric constant and a low dielectric loss tangent. Further, according to the present invention, there are provided a prepreg, a film with a resin, a metal foil with a resin, a metal-clad laminate, and a wiring board obtained by using the resin composition.

FIG. 1 is a schematic cross-sectional view showing an example of a prepreg according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view showing an example of a metal-clad laminate according to an embodiment of the present invention. FIG. 3 is a schematic cross-sectional view showing an example of a wiring board according to an embodiment of the present invention. FIG. 4 is a schematic cross-sectional view showing an example of a metal leaf with a resin according to an embodiment of the present invention. FIG. 5 is a schematic cross-sectional view showing an example of a resin-coated film according to an embodiment of the present invention.

Hereinafter, embodiments according to the present invention will be described, but the present invention is not limited thereto.

[Resin composition]
The resin composition according to the present embodiment contains a modified polyphenylene ether compound terminally modified to a substituent having a carbon-carbon unsaturated double bond, and an aliphatic hydrocarbon compound represented by the following formula (1). It is a resin composition to be used.

In the formula (1), _RA represents an alkyl group having 4 or more carbon atoms or an alkenyl group having 4 or more carbon atoms, and R _{1 to} R ₃ independently represent a hydrogen atom or an alkyl group.

First, it is considered that the resin composition can be obtained by cross-linking the modified polyphenylene ether compound together with the aliphatic hydrocarbon compound to obtain a cured product maintaining the excellent low dielectric properties of the polyphenylene ether.

It is considered that when the aliphatic hydrocarbon compound is contained in the resin composition, the adhesiveness of the resin composition can be suitably enhanced. From this, it is considered that when the aliphatic hydrocarbon compound is contained in the resin composition, the interlayer adhesiveness of the cured product can be suitably enhanced. Further, by using the resin composition, a metal-clad laminate having excellent interlayer adhesiveness can be obtained. Specifically, it is possible to sufficiently suppress the peeling of the metal leaf from the insulating layer containing the cured product of the resin composition, and it is possible to sufficiently suppress the insulating delamination when the insulating layer is composed of multiple layers. can. Further, by manufacturing a wiring board using the resin composition, a wiring board having excellent interlayer adhesiveness capable of sufficiently suppressing peeling of wiring and delamination of insulation can be obtained. Further, in the wiring board, even if the surface roughness of the wiring is reduced in order to reduce the transmission loss caused by the conductor forming the wiring, the wiring board obtained by using the resin composition can be used. Wiring peeling can be sufficiently suppressed. Further, in order to obtain the wiring plate as described above, even if the surface roughness of the metal foil is reduced in the metal-clad laminate, the metal-clad laminate obtained by using the resin composition can be used. The peeling of the metal foil can be sufficiently suppressed.

From the above, the resin composition is a resin composition from which a cured product having high interlayer adhesiveness can be obtained in a resin composition having a low dielectric constant and a low dielectric loss tangent.

(Modified polyphenylene ether compound)
The modified polyphenylene ether compound used in the present embodiment is not particularly limited as long as it is a modified polyphenylene ether compound terminally modified by a substituent having a carbon-carbon unsaturated double bond.

The substituent having a carbon-carbon unsaturated double bond is not particularly limited. Examples of the substituent include a substituent represented by the following formula (2), a substituent represented by the following formula (3), and the like.

In equation (2), p represents an integer from 0 to 10. Further, Z represents an arylene group. Further, R _{4 to} R ₆ are independent of each other. That is, R _{4 to} R ₆ may be the same group or different groups, respectively. Further, R _{4 to} R ₆ represent a hydrogen atom or an alkyl group.

In the formula (2), when p is 0, it indicates that Z is directly bonded to the terminal of the polyphenylene ether.

This arylene group is not particularly limited. Examples of the arylene group include a monocyclic aromatic group such as a phenylene group and a polycyclic aromatic group in which the aromatic is not a monocyclic but a polycyclic aromatic such as a naphthalene ring. The arylene group also includes a derivative in which the hydrogen atom bonded to the aromatic ring is replaced with a functional group such as an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. .. The alkyl group is not particularly limited, and for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group and the like.

In formula (3), R ₇ represents a hydrogen atom or an alkyl group. The alkyl group is not particularly limited, and for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group and the like.

Preferred specific examples of the substituent represented by the formula (2) include, for example, a substituent containing a vinylbenzyl group and the like. Examples of the substituent containing a vinylbenzyl group include a substituent represented by the following formula (4). Examples of the substituent represented by the formula (3) include an acrylate group and a methacrylate group.

More specifically, the substituent includes a vinylbenzyl group (ethenylbenzyl group) such as a p-ethenylbenzyl group and an m-ethenylbenzyl group, a vinylphenyl group, an acrylate group, a methacrylate group and the like. Be done.

The modified polyphenylene ether compound has a polyphenylene ether chain in the molecule, and for example, it is preferable that the modified polyphenylene ether compound has a repeating unit represented by the following formula (5) in the molecule.

In formula (5), t represents 1 to 50. Further, R _{8 to} R ₁₁ are independent of each other. That is, R _{8 to} R ₁₁ may be the same group or different groups, respectively. Further, R _{8 to} R ₁₁ 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. Of these, a hydrogen atom and an alkyl group are preferable.

Specific examples of the functional groups listed in R _{8 to} R _{11 include the following.}

The alkyl group is not particularly limited, but for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group and the like.

The alkenyl group is not particularly limited, but for example, an alkenyl group having 2 to 18 carbon atoms is preferable, and an alkenyl group having 2 to 10 carbon atoms is more preferable. Specific examples thereof include a vinyl group, an allyl group, a 3-butenyl group and the like.

The alkynyl group is not particularly limited, but for example, an alkynyl group having 2 to 18 carbon atoms is preferable, and an alkynyl group having 2 to 10 carbon atoms is more preferable. Specific examples thereof include an ethynyl group and a propa-2-in-1-yl group (propargyl group).

The alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group, but for example, an alkylcarbonyl group having 2 to 18 carbon atoms is preferable, and an alkylcarbonyl group having 2 to 10 carbon atoms is more preferable. Specific examples thereof include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a hexanoyl group, an octanoyl group, a cyclohexylcarbonyl group and the like.

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

The alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group, but for example, an alkynylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkynylcarbonyl group having 3 to 10 carbon atoms is more preferable. Specifically, for example, a propioloyl group and the like can be mentioned.

The weight average molecular weight (Mw) of the modified polyphenylene ether compound used in the present embodiment is not particularly limited. Specifically, it is preferably 500 to 5000, more preferably 800 to 4000, and even more preferably 1000 to 3000. Here, the weight average molecular weight may be any one measured by a general molecular weight measuring method, and specific examples thereof include values measured by gel permeation chromatography (GPC). Further, when the modified polyphenylene ether compound has a repeating unit represented by the above formula (5) in the molecule, t is such that the weight average molecular weight of the modified polyphenylene ether compound is within such a range. It is preferably a numerical value. Specifically, t is preferably 1 to 50.

When the weight average molecular weight of the modified polyphenylene ether compound is within such a range, the modified polyphenylene ether has excellent low dielectric properties, and not only the heat resistance of the cured product is excellent, but also the moldability is excellent. Become. This is considered to be due to the following. When the weight average molecular weight of ordinary polyphenylene ether is within such a range, the heat resistance of the cured product tends to decrease because the molecular weight is relatively low. In this respect, since the modified polyphenylene ether compound according to the present embodiment has an unsaturated double bond or more at the terminal, it is considered that a cured product having sufficiently high heat resistance can be obtained. Further, when the weight average molecular weight of the modified polyphenylene ether compound is within such a range, the modified polyphenylene ether compound has a relatively low molecular weight, and thus it is considered that the moldability is also excellent. Therefore, it is considered that such a modified polyphenylene ether compound is not only excellent in heat resistance of the cured product but also excellent in moldability.

In the modified polyphenylene ether compound used in the present embodiment, the average number of substituents (number of terminal functional groups) at the molecular ends per molecule of the modified polyphenylene ether compound is not particularly limited. Specifically, the number is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.5 to 3. If the number of terminal functional groups is too small, it tends to be difficult to obtain sufficient heat resistance of the cured product. Further, if the number of terminal functional groups is too large, the reactivity becomes too high, and there is a possibility that problems such as a decrease in the storage stability of the resin composition and a decrease in the fluidity of the resin composition may occur. .. That is, when such a modified polyphenylene ether is used, molding defects such as voids generated during multi-layer molding occur due to insufficient fluidity, etc., and it is difficult to obtain a highly reliable printed wiring board. There was a risk of problems.

The number of terminal functional groups of the modified polyphenylene ether compound includes a numerical value representing the average value of the substituents per molecule of all the modified polyphenylene ether compounds present in 1 mol of the modified polyphenylene ether compound. The number of terminal functional groups can be measured, for example, by measuring the number of hydroxyl groups remaining in the obtained modified polyphenylene ether compound and calculating the amount of decrease from the number of hydroxyl groups of the polyphenylene ether before modification. The decrease from the number of hydroxyl groups of the polyphenylene ether before this modification is the number of terminal functional groups. Then, the method for measuring the number of hydroxyl groups remaining in the modified polyphenylene ether compound is to add a quaternary ammonium salt (tetraethylammonium hydroxide) associated with the hydroxyl group to the solution of the modified polyphenylene ether compound and measure the UV absorbance of the mixed solution. By doing so, it can be obtained.

The intrinsic viscosity of the modified polyphenylene ether compound used in this embodiment is not particularly limited. Specifically, it may be 0.03 to 0.12 dl / g, preferably 0.04 to 0.11 dl / g, and more preferably 0.06 to 0.095 dl / g. .. If this intrinsic viscosity is too low, the molecular weight tends to be low, and it tends to be difficult to obtain low dielectric constants such as low dielectric constant and low dielectric loss tangent. On the other hand, if the intrinsic viscosity is too high, the viscosity is high, sufficient fluidity cannot be obtained, and the moldability of the cured product tends to decrease. Therefore, if the intrinsic viscosity of the modified polyphenylene ether compound is within the above range, excellent heat resistance and moldability of the cured product can be realized.

The intrinsic viscosity here is the intrinsic viscosity measured in methylene chloride at 25 ° C., more specifically, for example, a 0.18 g / 45 ml methylene chloride solution (liquid temperature 25 ° C.) is used in a viscometer. It is a value measured in. Examples of this viscometer include AVS500 Visco System manufactured by Schott.

Examples of the modified polyphenylene ether compound include a modified polyphenylene ether compound represented by the following formula (6), a modified polyphenylene ether compound represented by the following formula (7), and the like. Further, as the modified polyphenylene ether compound, these modified polyphenylene ether compounds may be used alone, or these two types of modified polyphenylene ether compounds may be used in combination.

In formulas (6) and (7), R _{12 to} R _{19 and} R _{20 to} R ₂₇ are independently hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups, formyl groups, alkylcarbonyl groups, and alkenylcarbonyls. Indicates a group or an alkynylcarbonyl group. X ₁ and X ₂ each independently represent a substituent having a carbon-carbon unsaturated double bond. A and B represent repeating units represented by the following formulas (8) and (9), respectively. Further, in the formula (7), Y represents a linear, branched, or cyclic hydrocarbon having 20 or less carbon atoms.

In formulas (8) and (9), m and n represent 0 to 20, respectively. R _{28 to} R _{31 and} R _{32 to} R ₃₅ independently 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.

The modified polyphenylene ether compound represented by the formula (6) and the modified polyphenylene ether compound represented by the formula (7) are not particularly limited as long as they satisfy the above constitution. Specifically, in the above formula (6) and the above formula (7), R _{12 to} R _{19 and} R _{20 to} R ₂₇ are independent of each other as described above. That is, R _{12 to} R _{19 and} R _{20 to} R ₂₇ may be the same group or different groups, respectively. Further, R _{12 to} R _{19 and} R _{20 to} R ₂₇ 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. Of these, a hydrogen atom and an alkyl group are preferable.

In formulas (8) and (9), m and n preferably represent 0 to 20, respectively, as described above. Further, it is preferable that m and n represent numerical values in which the total value of m and n is 1 to 30. Therefore, it is more preferable that m indicates 0 to 20, n indicates 0 to 20, and the total of m and n indicates 1 to 30. Further, R _{28 to} R _{31 and} R _{32 to} R ₃₅ are independent of each other. That is, R _{28 to} R _{31 and} R _{32 to} R ₃₅ may be the same group or different groups, respectively. Further, R _{28 to} R _{31 and} R _{32 to} R ₃₅ 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. Of these, a hydrogen atom and an alkyl group are preferable.

R _{12 to} R ₃₅ are the same as _{R 8 to} R ₁₁ in the above formula (5).

In the formula (7), Y is a linear, branched, or cyclic hydrocarbon having 20 or less carbon atoms, as described above. Examples of Y include groups represented by the following formula (10).

In the above formula (10), R ₃₆ and R ₃₇ each independently represent a hydrogen atom or an alkyl group. Examples of the alkyl group include a methyl group and the like. Examples of the group represented by the formula (10) include a methylene group, a methylmethylene group, a dimethylmethylene group and the like, and among these, a dimethylmethylene group is preferable.

In the formula (6) and the formula (7), X ₁ and X ₂ are substituents each independently having a carbon-carbon unsaturated double bond. The substituents X ₁ and X ₂ are not particularly limited as long as they are substituents having a carbon-carbon unsaturated double bond. Examples of the substituents X ₁ and X ₂ include substituents represented by the above formula (2). In the modified polyphenylene ether compound represented by the formula (6) and the modified polyphenylene ether compound represented by the formula (7), X ₁ and X ₂ may be the same substituent or are different. It may be a substituent.

More specific examples of the modified polyphenylene ether compound represented by the formula (6) include, for example, the modified polyphenylene ether compound represented by the following formula (11).

More specific examples of the modified polyphenylene ether compound represented by the formula (7) include, for example, a modified polyphenylene ether compound represented by the following formula (12) and a modified polyphenylene ether represented by the following formula (13). Examples include compounds.

In the above formulas (11) to (13), m and n are the same as m and n in the above formula (8) and the above formula (9). Further, the formula (11) and the formula _(12), R 4 to R ₆ and p are the same as _R 4 to R ₆ and p in the formula (2). Further, in the above formula (12) and the above formula (13), Y is the same as Y in the above formula (7). Further, in the above formula (13), R ₇ is the same as _{R 7} in the above formula (3).

In the modified polyphenylene ether compound used in the present embodiment, the average number of the substituents (number of terminal functional groups) at the molecular terminal per molecule of the modified polyphenylene ether compound includes the above range, and examples thereof include. In the case of the modified polyphenylene ether compounds represented by the above formulas (11) to (13), specifically, the number is preferably 1 to 2, and more preferably 1.5 to 2.

The method for synthesizing the modified polyphenylene ether compound used in the present embodiment is not particularly limited as long as the modified polyphenylene ether compound terminally modified by a substituent having a carbon-carbon unsaturated double bond can be synthesized. Specific examples thereof include a method of reacting a polyphenylene ether with a compound in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded.

Examples of the compound in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded include a compound in which a substituent represented by the above formulas (2) to (4) and a halogen atom are bonded. And so on. Specific examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom, and among these, a chlorine atom is preferable. More specific examples of the compound in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded include p-chloromethylstyrene and m-chloromethylstyrene.

The raw material polyphenylene ether is not particularly limited as long as it can finally synthesize a predetermined modified polyphenylene ether compound. Specifically, a polyphenylene ether composed of 2,6-dimethylphenol and at least one of bifunctional phenol and trifunctional phenol, polyphenylene ether such as poly (2,6-dimethyl-1,4-phenylene oxide), etc. Examples thereof include those having a main component. The bifunctional phenol is a phenol compound having two phenolic hydroxyl groups in the molecule, and examples thereof include tetramethylbisphenol A and the like. The trifunctional phenol is a phenol compound having three phenolic hydroxyl groups in the molecule.

Examples of the method for synthesizing the modified polyphenylene ether compound include the methods described above. Specifically, the above-mentioned polyphenylene ether and a compound in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded are dissolved in a solvent and stirred. By doing so, the polyphenylene ether reacts with the compound in which the substituent having a carbon-carbon unsaturated double bond and the halogen atom are bonded, and the modified polyphenylene ether compound used in the present embodiment is obtained.

The reaction is preferably carried out in the presence of an alkali metal hydroxide. By doing so, it is believed that this reaction proceeds favorably. It is considered that this is because the alkali metal hydroxide functions as a dehydrohalogenating agent, specifically, a dehydrochloric acid agent. That is, the alkali metal hydroxide desorbs hydrogen halide from the phenol group of the polyphenylene ether and the compound in which the substituent having a carbon-carbon unsaturated double bond and the halogen atom are bonded to do so. Therefore, it is considered that a substituent having a carbon-carbon unsaturated double bond is bonded to the oxygen atom of the phenol group instead of the hydrogen atom of the phenol group of the polyphenylene ether.

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

Reaction conditions such as reaction time and reaction temperature differ depending on the compound or the like in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded, and the above reaction may proceed favorably. For example, there is no particular limitation. Specifically, the reaction temperature is preferably room temperature to 100 ° C, more preferably 30 to 100 ° C. The reaction time is preferably 0.5 to 20 hours, more preferably 0.5 to 10 hours.

The solvent used in the reaction can dissolve a polyphenylene ether and a compound in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded, and the polyphenylene ether and the carbon-carbon unsaturated double bond can be dissolved. It is not particularly limited as long as it does not inhibit the reaction between the substituent having a bond and the compound to which the halogen atom is bonded. Specific examples thereof include toluene and the like.

The above reaction is preferably carried out in the presence of not only the alkali metal hydroxide but also the phase transfer catalyst. That is, the above reaction is preferably carried out in the presence of an alkali metal hydroxide and a phase transfer catalyst. By doing so, it is considered that the above reaction proceeds more preferably. This is considered to be due to the following. The phase transfer catalyst has a function of taking in alkali metal hydroxide and is soluble in both a polar solvent phase such as water and a non-polar solvent phase such as an organic solvent, and is soluble between these phases. It is considered that it is a catalyst capable of moving. Specifically, when an aqueous sodium hydroxide solution is used as the alkali metal hydroxide and an organic solvent such as toluene, which is incompatible with water, is used as the solvent, the aqueous sodium hydroxide solution is subjected to the reaction. It is considered that the solvent and the aqueous sodium hydroxide solution are separated even when the solution is added dropwise to the solvent, and the sodium hydroxide is unlikely to be transferred to the solvent. In that case, it is considered that the sodium hydroxide aqueous solution added as the alkali metal hydroxide is less likely to contribute to the reaction promotion. On the other hand, when the reaction is carried out in the presence of the alkali metal hydroxide and the phase transfer catalyst, the alkali metal hydroxide is transferred to the solvent in a state of being incorporated into the phase transfer catalyst, and the sodium hydroxide aqueous solution reacts. It is thought that it will be easier to contribute to promotion. Therefore, it is considered that the above reaction proceeds more preferably when the reaction is carried out in the presence of an alkali metal hydroxide and a phase transfer catalyst.

The phase transfer catalyst is not particularly limited, and examples thereof include quaternary ammonium salts such as tetra-n-butylammonium bromide.

The resin composition used in the present embodiment preferably contains the modified polyphenylene ether compound obtained as described above as the modified polyphenylene ether compound.

(Aliphatic hydrocarbon compound)
The aliphatic hydrocarbon compound is not particularly limited as long as it is an aliphatic hydrocarbon compound represented by the formula (1). In the formula (1), _RA represents an alkyl group having 4 or more carbon atoms or an alkenyl group having 4 or more carbon atoms. R _{1 to} R ₃ each independently represent a hydrogen atom or an alkyl group. That is, R _{1 to} R ₃ may be the same group or different groups.

_{The alkyl group having 4 or more carbon atoms in RA} may be linear or branched as long as it is an alkyl group having 4 or more carbon atoms. The upper limit of the carbon number of the alkyl group having 4 or more carbon atoms in the _{RA is not particularly limited, but is preferably 40 or less.} The number of carbon atoms of the alkyl group having 4 or more carbon atoms in the _{R A} is preferably 4-40, more preferably 6-35. If the number of carbon atoms is too small or too large, the compatibility of the aliphatic hydrocarbon compound with the modified polyphenylene ether compound becomes low, and a suitable resin composition cannot be obtained or a resin composition can be obtained. Even if it is used, the adhesiveness tends not to be sufficiently increased. _{Examples of the alkyl group having 4 or more carbon atoms in RA} include a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group and a tetradecyl group. , Pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadesyl group, icosyl group, eikosyl group, henicosyl group, heneicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group. Group, Triacontyl group, Hentriacontyl group, Dotriacontyl group, Tritoriacontyl group, Tetratoriacontyl group, Pentatriacontyl group, Hexatriacontyl group, Heptatriacontyl group, Octatriacontyl group, Nonatriacon Examples thereof include a tyl group and a tetracontyl group.

_{The alkenyl group having 4 or more carbon atoms in RA} may be linear or branched as long as it is an alkenyl group having 4 or more carbon atoms. The upper limit of the carbon number of the alkenyl group having 4 or more carbon atoms in the _{RA is not particularly limited, but is preferably 40 or less.} The number of carbon atoms of the alkenyl group having 4 or more carbon atoms in the _{R A} is preferably 4-40, more preferably 6-35. If the number of carbon atoms is too small or too large, the compatibility of the aliphatic hydrocarbon compound with the modified polyphenylene ether compound becomes low, and a suitable resin composition cannot be obtained or a resin composition can be obtained. Even if it is used, the adhesiveness tends not to be sufficiently increased. _{Examples of the alkenyl group having 4 or more carbon atoms in RA} include a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, and a tetradecenyl group. , Pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadesenyl group, icosenyl group, eicosenyl group, henicosenyl group, heneicosenyl group, docosenyl group, tricosenyl group, tetracosenyl group, pentacosenyl group, hexacosenyl group, heptacosenyl group Group, Triacontenyl group, Hentriacontenyl group, Dotoriacontenyl group, Tritoriacontenyl group, Tetratoriacontenyl group, Pentatoriacontenyl group, Hexatriacontenyl group, Heptatriacontenyl group, Octatoria Examples thereof include a contenyl group, a nonatolian contenyl group, and a tetracontenyl group.

Wherein _{R A} is, among the above, preferably an alkenyl group having 6 to 35 carbon atoms.

As described above, R _{1 to} R ₃ are independently hydrogen atoms or alkyl groups. Among this, R ₂ and R _3, i.e., of the carbon atoms constituting the double bond in the formula (1), R ₂ and R ₃ is a group bonded to a carbon which is not bonded to the R _A is a hydrogen atom Is preferable. If R ₂ and R ₃ are an aliphatic hydrocarbon compound having a hydrogen atom, the effect of containing the aliphatic hydrocarbon compound, that is, the adhesiveness of the resin composition is enhanced, and the cured product of the resin composition is enhanced. The effect of enhancing the interlayer adhesiveness can be more preferably achieved.

The alkyl group in R ₁ is not particularly limited and may be linear or branched. The _{number of carbon atoms of the alkyl group in R 1} is preferably 40 or less, more preferably 4 to 40, and even more preferably 6 to 35. If the number of carbon atoms is too small or too large, the compatibility of the aliphatic hydrocarbon compound with the modified polyphenylene ether compound becomes low, and a suitable resin composition cannot be obtained or a resin composition can be obtained. Even if it is used, the adhesiveness tends not to be sufficiently increased. Examples of the alkyl group in R ₁ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group and a tridecyl group. Group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadesyl group, icosyl group, eicosyl group, henicosyl group, heneikosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, Octacosyl group, nonacosyl group, triacity group, gentriacontyl group, dotriacontyl group, tritoriacontyl group, tetratriacontyl group, pentatriacontyl group, hexatriacontyl group, heptatoriacontyl group, octatriacontyl group Examples include a group and a nonatriacontyl group.

The alkyl group in R ₂ and R ₃ is not particularly limited and may be linear or branched. Further, as described above, R ₂ and R ₃ are preferably hydrogen atoms, _{and even when R 2} and R ₃ are alkyl groups, it is preferable that the alkyl groups have a small number of carbon atoms, and the R the number of carbon atoms of the alkyl group in ₂ and R ₃ is preferably 6 or less. If the number of carbon atoms is too large, the reactivity of the double bond (double bond in the formula (1)) of the aliphatic hydrocarbon compound is lowered, and the aliphatic hydrocarbon compound and the modified polyphenylene ether compound are reduced. The reactivity with and tends to decrease. Examples of the alkyl group in R ₂ and R ₃ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like.

The aliphatic hydrocarbon compound is a compound having 6 to 45 carbon atoms, that is, an aliphatic hydrocarbon compound represented by the formula (1) and having a total carbon number of 6 to 45. It is preferable to include it. The aliphatic hydrocarbon compound preferably has 6 to 45 carbon atoms, and more preferably 10 to 40 carbon atoms. If the number of carbon atoms is too small or too large, the compatibility with the modified polyphenylene ether compound becomes low, and even if a suitable resin composition cannot be obtained or a resin composition is obtained, sufficient adhesiveness is obtained. It tends not to be enhanced. Therefore, if the compound has 6 to 45 carbon atoms, the effect of containing the aliphatic hydrocarbon compound, that is, the adhesiveness of the resin composition is enhanced, and the interlayer adhesiveness of the cured product of the resin composition is improved. The effect of enhancing can be suitably achieved.

The content of the compound having 6 to 45 carbon atoms is preferably 95% by mass or more, and may be 100% by mass, based on the total amount of the aliphatic hydrocarbon compound. That is, the aliphatic hydrocarbon compound may consist only of the compound having 6 to 45 carbon atoms. Further, even when an aliphatic hydrocarbon compound other than the compound having 6 to 45 carbon atoms (the compound having 5 or less carbon atoms and the compound having 46 or more carbon atoms) is contained, the content of the compound is contained. However, it is preferably less than 5% by mass based on the total amount of the aliphatic hydrocarbon compound. If the content of the compound having 6 to 45 carbon atoms is too small, the effect of increasing the adhesiveness of the resin composition and enhancing the interlayer adhesiveness of the cured product of the resin composition tends to be insufficiently exhibited.

Examples of the aliphatic hydrocarbon compound include 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-icosene, 1-dodecene and 1-tetracocene. , 1,13-Tetradecane, and compounds represented by the following formula (14). The aliphatic hydrocarbon compound is not limited to these exemplified compounds, and may be any aliphatic hydrocarbon compound represented by the above formula (1), and these compounds may be used alone or two kinds. The above may be used in combination.

(Hardener)
The resin composition preferably contains a curing agent. The curing agent is not particularly limited as long as it is a compound that contributes to curing of the resin composition containing the modified polyphenylene ether compound and the aliphatic hydrocarbon compound. The curing agent is preferably a crosslinked curing agent that cures the resin composition by forming crosslinks in the resin composition containing the modified polyphenylene ether compound and the aliphatic hydrocarbon compound. ..

Examples of the curing agent include a crosslinked curing agent having two or more carbon-carbon unsaturated double bonds in the molecule, an alkenyl isocyanurate compound, a styrene, a styrene derivative, and at least one allyl group in the molecule. Examples thereof include an allyl compound, a maleimide compound having at least one maleimide group in the molecule, and an acenaphthylene compound having an acenaphtylene structure in the molecule.

Examples of the compound having two or more carbon-carbon unsaturated double bonds in the molecule include a polyfunctional allyl compound having two or more allyl groups in the molecule and a polyfunctional methacrylate compound having two or more methacryloyl groups in the molecule. , Polyfunctional acrylate compounds having two or more acryloyl groups in the molecule, polyfunctional vinyl compounds having two or more vinyl groups in the molecule, polyfunctional vinylphenyl compounds having two or more vinyl phenyl groups in the molecule, etc. Can be mentioned.

Examples of the polyfunctional vinyl compound include divinylbenzene and polybutadiene.

The alkenyl isocyanurate compound may be any compound having an isocyanurate structure and an alkenyl group in the molecule, and examples thereof include trialkenyl isocyanurate compounds such as triallyl isocyanurate (TAIC).

Examples of the polyfunctional methacrylate compound include tricyclodecanedimethanol dimethacrylate and the like.

Examples of the styrene derivative include bromostyrene and dibromostyrene.

Examples of the maleimide compound include a compound having two or more maleimide groups in the molecule, a compound having one maleimide group in the molecule, and a modified maleimide compound. Among these, a compound having two maleimide groups in the molecule is preferably used. Examples of the modified maleimide compound include a modified maleimide compound in which a part of the molecule is amine-modified, a modified maleimide compound in which a part of the molecule is silicone-modified, and a part of the molecule in which the molecule is amine-modified and silicone-modified. Examples thereof include modified maleimide compounds.

Among the above, the curing agent includes the alkenyl isocyanurate compound, the polyfunctional allyl compound, the polyfunctional acrylate compound, the polyfunctional methacrylate compound, the polyfunctional vinyl compound, and the maleimide compound as the resin composition. It is preferable in that the heat resistance of the cured product can be further enhanced, and a crosslinked curing agent having two or more carbon-carbon unsaturated double bonds and having a number average molecular weight of less than 400, and the maleimide compound are more preferable. .. It is considered that this is because the cross-linking of the resin composition is more preferably formed by the curing reaction by using these curing agents. As the crosslinked curing agent having a number average molecular weight of less than 400, the polyfunctional allyl compound, the polyfunctional vinylphenyl compound, the polyfunctional methacrylate compound, and a compound having three or more vinyl groups in the molecule are preferably used. Be done.

As the curing agent, the exemplified curing agent may be used alone, or two or more kinds may be used in combination. Further, the curing agent includes not only the curing agent exemplified above, such as a compound having two or more unsaturated double bonds in the molecule, but also a compound having one unsaturated double bond in the molecule. It may be used together. Examples of the compound having one unsaturated double bond in the molecule include a monovinyl compound having one vinyl group in the molecule.

(Content)
The content of the modified polyphenylene ether compound is the total mass of the modified polyphenylene ether compound, the aliphatic hydrocarbon compound, and the curing agent (if the curing agent is not contained, the modified polyphenylene ether compound and the aliphatic). The total mass of the hydrocarbon compounds is preferably 50 to 97 parts by mass, and more preferably 60 to 95 parts by mass with respect to 100 parts by mass. If the content of the modified polyphenylene ether compound is too small, the low dielectric loss tangent tends not to be sufficiently exhibited. Further, if the content of the modified polyphenylene ether compound is too large, the content of at least one of the aliphatic hydrocarbon compound and the curing agent tends to decrease. That is, when the content of the aliphatic hydrocarbon compound becomes too small, the effect of containing the aliphatic hydrocarbon compound, that is, the adhesiveness of the resin composition is enhanced, and the layers of the cured product of the resin composition are laminated. There is a tendency that the effect of increasing the adhesiveness cannot be sufficiently achieved. On the other hand, if the content of the curing agent is too small, the effects of containing the curing agent, such as increasing heat resistance, tend to be insufficient.

The content of the aliphatic hydrocarbon compound is preferably 3 to 50 parts by mass, more preferably 5 to 40 parts by mass, based on 100 parts by mass of the total mass. If the content of the aliphatic hydrocarbon compound is too small, the effect of containing the aliphatic hydrocarbon compound, that is, the adhesiveness of the resin composition is enhanced, and the interlayer adhesiveness of the cured product of the resin composition is enhanced. There is a tendency that the effect of If the content of the aliphatic hydrocarbon compound is too high, the content of at least one of the modified polyphenylene ether compound and the curing agent tends to be low. That is, when the content of the modified polyphenylene ether compound becomes too small, the effect of containing the modified polyphenylene ether compound cannot be sufficiently exerted, and for example, the glass transition temperature of the resin composition tends to decrease. There is. When the content of the curing agent is too small, the effect of containing the aliphatic hydrocarbon compound, that is, the adhesiveness of the resin composition is enhanced, and the interlayer adhesiveness of the cured product of the resin composition is improved. Although the effect of increasing can be sufficiently achieved, the glass transition temperature of the resin composition tends to be low.

The resin composition does not have to contain the curing agent, and when the curing agent is contained, the content of the curing agent is 3 to 50% by mass with respect to 100 parts by mass of the total mass. It is preferably parts, and more preferably 5 to 40 parts by mass. If the content of the curing agent is too small, there is a tendency that the effects of containing the curing agent, such as increasing heat resistance, cannot be sufficiently exerted. If the content of the curing agent is too high, the content of at least one of the modified polyphenylene ether compound and the aliphatic hydrocarbon compound tends to be low. That is, when the content of the modified polyphenylene ether compound becomes too small, the effect of containing the modified polyphenylene ether compound cannot be sufficiently exerted, and for example, the glass transition temperature of the resin composition tends to decrease. There is. On the other hand, if the content of the aliphatic hydrocarbon compound is too small, the effect of containing the aliphatic hydrocarbon compound tends to be insufficiently exhibited.

From the above, when the contents of the modified polyphenylene ether compound, the aliphatic hydrocarbon compound, and the curing agent are within the above ranges, the obtained resin composition has a low dielectric constant and dielectric loss tangent. Moreover, a cured product having not only high interlayer adhesiveness but also high heat resistance can be obtained.

(Other ingredients)
The resin composition contains, if necessary, the modified polyphenylene ether compound, the aliphatic hydrocarbon compound, and components (other components) other than the curing agent, as long as the effects of the present invention are not impaired. May be good. Other components contained in the resin composition include, for example, a silane coupling agent, a flame retardant, an initiator, a defoaming agent, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a dye or a pigment. , Lubricants, and additives such as inorganic fillers may be further included. In addition to the modified polyphenylene ether compound, the resin composition may contain resins such as unmodified polyphenylene ether, epoxy resin, unsaturated polyester resin, and thermosetting polyimide resin.

The resin composition may contain a silane coupling agent as described above. The silane coupling agent may be contained in the resin composition, or may be contained as a silane coupling agent which has been surface-treated in advance in the inorganic filler contained in the resin composition. Among these, the silane coupling agent is preferably contained as a silane coupling agent that has been surface-treated in the inorganic filler in advance, and is contained as a silane coupling agent that has been surface-treated in the inorganic filler in this way. Furthermore, it is more preferable that the resin composition also contains a silane coupling agent. Further, in the case of a prepreg, the prepreg may be contained as a silane coupling agent that has been surface-treated on the fibrous base material in advance.

Examples of the silane coupling agent include a silane coupling agent having at least one functional group selected from the group consisting of a vinyl group, a styryl group, a methacryloyl group, an acryloyl group, and a phenylamino group. That is, this silane coupling agent has at least one of a vinyl group, a styryl group, a methacryloyl group, an acryloyl group, and a phenylamino group as a reactive functional group, and further contains a methoxy group, an ethoxy group, and the like. Examples thereof include compounds having a hydrolyzable group.

Examples of the silane coupling agent having a vinyl group include vinyltriethoxysilane and vinyltrimethoxysilane. Examples of the silane coupling agent having a styryl group include p-styryltrimethoxysilane and p-styryltriethoxysilane. Examples of the silane coupling agent include those having a methacryloyl group, such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-methacryloxypropylmethyl. Examples thereof include diethoxysilane and 3-methacryloxypropyl ethyldiethoxysilane. Examples of the silane coupling agent having an acryloyl group include 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane. Examples of the silane coupling agent having a phenylamino group include N-phenyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltriethoxysilane.

As described above, the resin composition may contain a flame retardant. By containing a flame retardant, the flame retardancy of the cured product of the resin composition can be enhanced. The flame retardant is not particularly limited. Specifically, in the field of using halogen-based flame retardants such as brominated flame retardants, for example, ethylenedipentabromobenzene, ethylenebistetrabromoimide, decabromodiphenyloxide, and tetradecabromo having a melting point of 300 ° C. or higher are used. Diphenoxybenzene is preferred. By using a halogen-based flame retardant, it is considered that desorption of halogen at high temperature can be suppressed and deterioration of heat resistance can be suppressed. Further, in the field where halogen-free is required, a phosphoric acid ester-based flame retardant, a phosphazene-based flame retardant, a bisdiphenylphosphine oxide-based flame retardant, and a phosphinate-based flame retardant can be mentioned. Specific examples of the phosphoric acid ester-based flame retardant include condensed phosphoric acid ester of dixylenyl phosphate. Specific examples of the phosphazene-based flame retardant include phenoxyphosphazene. Specific examples of the bisdiphenylphosphine oxide-based flame retardant include xylylene bisdiphenylphosphine oxide. Specific examples of the phosphinate-based flame retardant include a phosphinic acid metal salt of a dialkylphosphinic acid aluminum salt. As the flame retardant, each of the above-exemplified flame retardants may be used alone, or two or more kinds may be used in combination.

As described above, the resin composition may contain an initiator (reaction initiator). Even if the resin composition is composed of the modified polyphenylene ether compound and the aliphatic hydrocarbon compound, the curing reaction can proceed. However, depending on the process conditions, it may be difficult to raise the temperature until curing progresses, so a reaction initiator may be added. The reaction initiator is not particularly limited as long as it can accelerate the curing reaction of the modified polyphenylene ether compound. Specifically, for example, α, α'-di (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexine, benzoyl peroxide, etc. And organic peroxides such as dicumyl peroxide, 3,3', 5,5'-tetramethyl-1,4-diphenoquinone, chloranyl, 2,4,6-tri-t-butylphenoxyl, t- Examples thereof include oxidizing agents such as butylperoxyisopropyl monocarbonate and azobisisobutyronitrile, and cationic polymerization catalysts such as Lewis acid. Examples of the Lewis acid include trifluoromethanesulfonic acid and zinc triiodide. Further, if necessary, a carboxylic acid metal salt or the like can be used in combination. By doing so, the curing reaction can be further promoted. Among these, α, α'-di (t-butylperoxy) diisopropylbenzene is preferably used. Since α, α'-di (t-butylperoxy) diisopropylbenzene has a relatively high reaction start temperature, it is possible to suppress the acceleration of the curing reaction at a time when curing is not necessary, such as during prepreg drying. , It is possible to suppress a decrease in the storage stability of the resin composition. Further, since α, α'-di (t-butylperoxy) diisopropylbenzene has low volatility, it does not volatilize during prepreg drying or storage, and has good stability. In addition, the reaction initiator may be used alone or in combination of two or more.

As described above, the resin composition may contain a filler such as an inorganic filler. Examples of the filler include those added to enhance the heat resistance and flame retardancy of the cured product of the resin composition, and the filler is not particularly limited. Further, by containing a filler, heat resistance, flame retardancy and the like can be further improved. Specific examples of the filler include silica such as spherical silica, metal oxides such as alumina and titanium oxide, and mica, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, talc, aluminum borate, and sulfuric acid. Examples include barium and calcium carbonate. Further, as the filler, silica, mica, and talc are preferable, and spherical silica is more preferable. Further, as the filler, one type may be used alone, or two or more types may be used in combination. Further, as the filler, it may be used as it is, or a filler surface-treated with the silane coupling agent may be used. When a filler is contained, the content (filler content) thereof is preferably 30 to 270% by mass, more preferably 50 to 250% by mass, based on the resin composition.

(Production method)
The method for producing the resin composition is not particularly limited as long as the resin composition can be produced. As a method for producing the resin composition, the modified polyphenylene ether compound, the aliphatic hydrocarbon compound, and if necessary, the curing agent and the other components are contained in a predetermined content. Examples thereof include a method of mixing. Specifically, in the case of obtaining a varnish-like composition containing an organic solvent, a method described later and the like can be mentioned.

Further, by using the resin composition according to the present embodiment, a prepreg, a metal-clad laminate, a wiring board, a metal foil with a resin, and a film with a resin can be obtained as follows.

[Prepreg]
As shown in FIG. 1, the prepreg 1 according to the present embodiment includes the resin composition or the semi-cured product 2 of the resin composition, and the fibrous base material 3. The prepreg 1 includes the resin composition or the semi-cured product 2 of the resin composition, and the fibrous base material 3 present in the resin composition or the semi-cured product 2 of the resin composition. Note that FIG. 1 is a schematic cross-sectional view showing an example of the prepreg 1 according to the embodiment of the present invention.

In the present embodiment, the semi-cured product is a state in which the resin composition is partially cured to the extent that it can be further cured. That is, the semi-cured product is a semi-cured (B-staged) resin composition. For example, when the resin composition is heated, the viscosity gradually decreases first, then curing starts, and then curing starts and the viscosity gradually increases. In such a case, the semi-curing state includes a state between the time when the viscosity starts to increase and the time before it is completely cured.

The prepreg obtained by using the resin composition according to the present embodiment may include a semi-cured product of the resin composition as described above, or the resin composition which has not been cured. It may be provided with itself. That is, it may be a prepreg comprising a semi-cured product of the resin composition (the resin composition of the B stage) and a fibrous base material, or the resin composition before curing (the resin composition of the A stage). It may be a prepreg including a thing) and a fibrous base material. Further, the resin composition or the semi-cured product of the resin composition may be a dried or heat-dried resin composition.

When producing a prepreg, the resin composition 2 is often prepared and used in the form of a varnish in order to impregnate the fibrous base material 3 which is a base material for forming the prepreg. That is, the resin composition 2 is usually a resin varnish prepared in the form of a varnish. Such a varnish-like resin composition (resin varnish) is prepared, for example, as follows.

First, each component that can be dissolved in an organic solvent is put into an organic solvent and dissolved. At this time, if necessary, it may be heated. Then, if necessary, a component that is insoluble in an organic solvent is added and dispersed using a ball mill, a bead mill, a planetary mixer, a roll mill, or the like until a predetermined dispersion state is obtained, thereby forming a varnish-like resin. The composition is prepared. The organic solvent used here is not particularly limited as long as it dissolves the polymer, the monofunctional maleimide compound and the like and does not inhibit the curing reaction. Specific examples thereof include toluene and methyl ethyl ketone (MEK).

The method for producing the prepreg is not particularly limited as long as the prepreg can be produced. Specifically, when producing a prepreg, the resin composition used in the present embodiment described above is often prepared in the form of a varnish as described above and used as a resin varnish.

Specific examples of the fibrous substrate include glass cloth, aramid cloth, polyester cloth, glass non-woven fabric, aramid non-woven fabric, polyester non-woven fabric, pulp paper, and linter paper. When a glass cloth is used, a laminated plate having excellent mechanical strength can be obtained, and a flattened glass cloth is particularly preferable. Specific examples of the flattening process include a method in which a glass cloth is continuously pressed with a press roll at an appropriate pressure to flatten the yarn. The thickness of the generally used fibrous base material is, for example, 0.01 mm or more and 0.3 mm or less.

The method for producing the prepreg is not particularly limited as long as the prepreg can be produced. Specifically, when producing a prepreg, the resin composition according to the present embodiment described above is often prepared in the form of a varnish as described above and used as a resin varnish.

Examples of the method for producing the prepreg 1 include a method in which the fibrous base material 3 is impregnated with the resin composition 2, for example, the resin composition 2 prepared in the form of a varnish, and then dried. The resin composition 2 is impregnated into the fibrous base material 3 by dipping, coating or the like. It is also possible to repeat impregnation a plurality of times as needed. Further, at this time, by repeating impregnation using a plurality of resin compositions having different compositions and concentrations, it is possible to finally adjust the desired composition and impregnation amount.

The fibrous base material 3 impregnated with the resin composition (resin varnish) 2 is heated under desired heating conditions, for example, 80 ° C. or higher and 180 ° C. or lower for 1 minute or more and 10 minutes or less. By heating, prepreg 1 before curing (A stage) or in a semi-cured state (B stage) is obtained. The heating can volatilize the organic solvent from the resin varnish to reduce or remove the organic solvent.

The resin composition according to the present embodiment is a resin composition from which a cured product having a low dielectric constant and dielectric loss tangent and high interlayer adhesiveness can be preferably obtained. Therefore, the prepreg including this resin composition or the semi-cured product of this resin composition is a prepreg from which a cured product having a low dielectric constant and dielectric loss tangent and high interlayer adhesiveness can be preferably obtained. The prepreg is a prepreg capable of manufacturing a wiring board having an insulating layer having a low dielectric constant and a dielectric loss tangent and a high interlayer adhesiveness. This wiring board can sufficiently suppress the peeling of the wiring and the peeling of the insulating delamination.

[Metal-clad laminate]
As shown in FIG. 2, the metal-clad laminate 11 is composed of an insulating layer 12 containing a cured product of the prepreg 1 shown in FIG. 1 and a metal foil 13 laminated together with the insulating layer 12. That is, the metal-clad laminate 11 has an insulating layer 12 containing a cured product of the resin composition, and a metal foil 13 provided on the insulating layer 12. Further, the insulating layer 12 may be made of a cured product of the resin composition or may be made of a cured product of the prepreg. Note that FIG. 2 is a schematic cross-sectional view showing an example of the metal-clad laminate 11 according to the embodiment of the present invention.

The thickness of the metal foil 13 varies depending on the performance and the like required for the finally obtained wiring board, and is not particularly limited. The thickness of the metal foil 13 can be appropriately set according to a desired purpose, and is preferably 0.2 to 70 μm, for example. Examples of the metal foil 13 include a copper foil and an aluminum foil. When the metal foil is thin, the metal foil 13 is a copper foil with a carrier provided with a release layer and a carrier for improving handleability. May be good.

The method for manufacturing the metal-clad laminate 11 is not particularly limited as long as the metal-clad laminate 11 can be manufactured. Specifically, a method of manufacturing the metal-clad laminate 11 using the prepreg 1 can be mentioned. In this method, one or a plurality of prepregs 1 are stacked, and further, a metal foil 13 such as a copper foil is laminated on both upper and lower surfaces or one side thereof, and the metal foil 13 and the prepreg 1 are heat-press molded and integrated. By doing so, a method of producing a double-sided metal leaf-covered or single-sided metal leaf-covered laminated plate 11 can be mentioned. That is, the metal-clad laminate 11 is obtained by laminating a metal foil 13 on a prepreg 1 and heat-pressing molding. Further, the heating and pressurizing conditions can be appropriately set depending on the thickness of the metal-clad laminate 11 to be manufactured, the type of the composition of the prepreg 1, and the like. For example, the temperature can be 170 to 230 ° C., the pressure can be 1 to 5 MPa, and the time can be 60 to 150 minutes. Further, the metal-clad laminate may be manufactured without using a prepreg. For example, a method of applying a varnish-like resin composition on a metal foil, forming a layer containing the resin composition on the metal foil, and then heating and pressurizing the metal foil can be mentioned.

The resin composition according to the present embodiment is a resin composition from which a cured product having a low dielectric constant and dielectric loss tangent and high interlayer adhesiveness can be preferably obtained. Therefore, the metal-clad laminate provided with the insulating layer containing the cured product of this resin composition is a metal-clad laminate having an insulating layer having a low dielectric constant and dielectric loss tangent and high interlayer adhesiveness. This metal-clad laminate can sufficiently suppress the peeling of the metal foil and the peeling of the insulating delamination. Therefore, by using this metal-clad laminate, it is possible to obtain a wiring board which has an insulating layer having a low dielectric constant and a dielectric loss tangent and can sufficiently suppress wiring peeling and insulating delamination.

[Wiring board]
As shown in FIG. 3, the wiring board 21 according to the present embodiment is laminated with the insulating layer 12 used by curing the prepreg 1 shown in FIG. 1 and the insulating layer 12, and the metal foil 13 is partially removed. It is composed of the wiring 14 formed in the above. That is, the wiring board 21 has an insulating layer 12 containing a cured product of the resin composition, and a wiring 14 provided on the insulating layer 12. Further, the insulating layer 12 may be made of a cured product of the resin composition or may be made of a cured product of the prepreg. Note that FIG. 3 is a schematic cross-sectional view showing an example of the wiring board 21 according to the embodiment of the present invention.

The method for manufacturing the wiring board 21 is not particularly limited as long as the wiring board 21 can be manufactured. Specifically, a method of manufacturing the wiring board 21 using the prepreg 1 and the like can be mentioned. As this method, for example, wiring is provided as a circuit on the surface of the insulating layer 12 by forming wiring by etching the metal foil 13 on the surface of the metal-clad laminate 11 produced as described above. Examples thereof include a method of manufacturing the wiring board 21. That is, the wiring board 21 is obtained by forming a circuit by partially removing the metal foil 13 on the surface of the metal-clad laminate 11. In addition to the above methods, examples of the circuit forming method include circuit formation by a semi-additive method (SAP: Semi Adaptive Process) and a modified semi-additive method (MSAP: Modified Semi Adaptive Process). The wiring plate 21 has an insulating layer 12 having a high glass transition temperature, a low water absorption rate, and sufficiently suppressing an increase in the dielectric constant and the dielectric loss tangent due to water absorption even after water absorption.

The resin composition according to the present embodiment is a resin composition from which a cured product having a low dielectric constant and dielectric loss tangent and high interlayer adhesiveness can be preferably obtained. Therefore, the wiring board provided with the insulating layer containing the cured product of this resin composition is a wiring board provided with an insulating layer having a low dielectric constant and dielectric loss tangent and high interlayer adhesiveness. Then, this wiring board can sufficiently suppress the peeling of the wiring and the peeling of the insulating delamination.

[Metal foil with resin]
As shown in FIG. 4, the resin-attached metal foil 31 according to the present embodiment includes a resin layer 32 containing the resin composition or a semi-cured product of the resin composition, and a metal foil 13. The resin-attached metal foil 31 has the metal foil 13 on the surface of the resin layer 32. That is, the resin-attached metal foil 31 includes the resin layer 32 and the metal foil 13 laminated together with the resin layer 32. Further, the metal leaf 31 with resin may be provided with another layer between the resin layer 32 and the metal leaf 13. Note that FIG. 4 is a schematic cross-sectional view showing an example of the resin-attached metal leaf 31 according to the present embodiment.

The resin layer 32 may include the semi-cured product of the resin composition as described above, or may contain the uncured resin composition. That is, the resin-attached metal foil 31 may include a resin layer containing a semi-cured product of the resin composition (the resin composition of the B stage) and the metal foil, or the resin before curing. It may be a metal foil with a resin including a resin layer containing the composition (the resin composition of the A stage) and the metal foil. Further, the resin layer may contain the resin composition or a semi-cured product of the resin composition, and may or may not contain a fibrous base material. Further, the resin composition or the semi-cured product of the resin composition may be a dried or heat-dried resin composition. Further, as the fibrous base material, the same one as that of the prepreg fibrous base material can be used.

As the metal foil, the metal foil used for the metal-clad laminate can be used without limitation. Examples of the metal foil include copper foil and aluminum foil.

The resin-attached metal foil 31 and the resin-attached film 41 may be provided with a cover fill or the like, if necessary. By providing the cover film, it is possible to prevent foreign matter from being mixed. The cover film is not particularly limited, and examples thereof include a polyolefin film, a polyester film, a polymethylpentene film, and a film formed by providing a release agent layer on these films.

The method for producing the resin-attached metal foil 31 is not particularly limited as long as the resin-attached metal foil 31 can be produced. Examples of the method for producing the resin-attached metal foil 31 include a method in which the varnish-like resin composition (resin varnish) is applied onto the metal foil 13 and heated. The varnish-like resin composition is applied onto the metal foil 13 by using, for example, a bar coater. The applied resin composition is heated under the conditions of, for example, 40 ° C. or higher and 180 ° C. or lower, 1 second or longer and 10 minutes or shorter. The heated resin composition is formed on the metal foil 13 as an uncured resin layer 32. The heating can volatilize the organic solvent from the resin varnish to reduce or remove the organic solvent.

The resin composition according to the present embodiment is a resin composition from which a cured product having a low dielectric constant and dielectric loss tangent and high interlayer adhesiveness can be preferably obtained. Therefore, as a metal foil with a resin provided with this resin composition or a resin layer containing a semi-cured product of this resin composition, a cured product having a low dielectric constant and dielectric loss tangent and high interlayer adhesion can be preferably obtained. It is a metal foil with resin. The resin-attached metal foil can be used when manufacturing a wiring board provided with an insulating layer having a low dielectric constant and dielectric loss tangent and high interlayer adhesiveness. For example, a multi-layered wiring board can be manufactured by laminating on the wiring board. As a wiring board obtained by using such a metal foil with a resin, a wiring board having an insulating layer having a low dielectric constant and a dielectric loss tangent and a high interlayer adhesiveness can be obtained. This wiring board can sufficiently suppress the peeling of the wiring and the peeling of the insulating delamination.

[Film with resin]
As shown in FIG. 5, the resin-attached film 41 according to the present embodiment includes a resin layer 42 containing the resin composition or a semi-cured product of the resin composition, and a support film 43. The resin-attached film 41 includes the resin layer 42 and a support film 43 laminated together with the resin layer 42. Further, the resin-attached film 41 may include another layer between the resin layer 42 and the support film 43. Note that FIG. 5 is a schematic cross-sectional view showing an example of the resin-attached film 41 according to the present embodiment.

The resin layer 42 may include the semi-cured product of the resin composition as described above, or may contain the uncured resin composition. That is, the resin-attached film 41 may include a resin layer containing a semi-cured product of the resin composition (the resin composition of the B stage) and a support film, or the resin composition before curing. It may be a film with a resin including a resin layer containing a substance (the resin composition of the A stage) and a support film. Further, the resin layer may contain the resin composition or a semi-cured product of the resin composition, and may or may not contain a fibrous base material. Further, the resin composition or the semi-cured product of the resin composition may be a dried or heat-dried resin composition. Further, as the fibrous base material, the same one as that of the prepreg fibrous base material can be used.

As the support film 43, the support film used for the resin-attached film can be used without limitation. Examples of the support film include electrically insulating properties such as polyester film, polyethylene terephthalate (PET) film, polyimide film, polyparavanic acid film, polyether ether ketone film, polyphenylene sulfide film, polyamide film, polycarbonate film, and polyarylate film. Examples include films.

The resin-attached film 41 may be provided with a cover film or the like, if necessary. By providing the cover film, it is possible to prevent foreign matter from being mixed. The cover film is not particularly limited, and examples thereof include a polyolefin film, a polyester film, and a polymethylpentene film.

The support film and cover film may be subjected to surface treatment such as matte treatment, corona treatment, mold release treatment, and roughening treatment, if necessary.

The method for producing the resin-containing film 41 is not particularly limited as long as the resin-containing film 41 can be produced. Examples of the method for producing the resin-attached film 41 include a method in which the varnish-like resin composition (resin varnish) is applied onto the support film 43 and heated. The varnish-like resin composition is applied onto the support film 43, for example, by using a bar coater. The applied resin composition is heated under the conditions of, for example, 40 ° C. or higher and 180 ° C. or lower, 1 second or longer and 10 minutes or shorter. The heated resin composition is formed on the support film 43 as an uncured resin layer 42. The heating can volatilize the organic solvent from the resin varnish to reduce or remove the organic solvent.

The resin composition according to the present embodiment is a resin composition from which a cured product having a low dielectric constant and dielectric loss tangent and high interlayer adhesiveness can be preferably obtained. Therefore, the resin-coated film provided with the resin composition or the resin layer containing the semi-cured product of the resin composition is preferably a cured product having a low dielectric constant and dielectric loss tangent and high interlayer adhesion. Attached film. The resin-coated film can be used when manufacturing a wiring board provided with an insulating layer having a low dielectric constant and dielectric loss tangent and high interlayer adhesiveness. For example, a multilayer wiring board can be manufactured by laminating on a wiring board and then peeling off the support film, or by peeling off the support film and then laminating on the wiring board. As a wiring board obtained by using such a resin-coated film, a wiring board having an insulating layer having a low dielectric constant and a dielectric loss tangent and a high interlayer adhesiveness can be obtained. This wiring board can sufficiently suppress the peeling of the wiring and the peeling of the insulating delamination.

The wiring board may be manufactured by using the prepreg, the metal foil with resin, the film with resin, and the metal-clad laminated board independently, or a combination of two or more of them. The wiring board may be manufactured by using the above.

The present specification discloses various aspects of the technology as described above, of which the main technologies are summarized below.

The resin composition according to one aspect of the present invention comprises a modified polyphenylene ether compound terminally modified to a substituent having a carbon-carbon unsaturated double bond, and an aliphatic hydrocarbon compound represented by the following formula (1). It is a resin composition containing.

In the formula (1), _RA represents an alkyl group having 4 or more carbon atoms or an alkenyl group having 4 or more carbon atoms, and R _{1 to} R ₃ independently represent a hydrogen atom or an alkyl group.

According to such a configuration, it is possible to provide a resin composition capable of obtaining a cured product having high interlayer adhesiveness in a resin composition having a low dielectric constant and a low dielectric loss tangent.

This is considered to be due to the following.

First, it is considered that the resin composition can be obtained by cross-linking the modified polyphenylene ether compound together with the aliphatic hydrocarbon compound to obtain a cured product maintaining the excellent low dielectric properties of the polyphenylene ether.

It is considered that when the aliphatic hydrocarbon compound is contained in the resin composition, the adhesiveness of the resin composition can be suitably enhanced. Therefore, it is considered that when the aliphatic hydrocarbon compound is contained in the resin composition, the interlayer adhesiveness of the cured product can be suitably enhanced. Further, by using the resin composition, a metal-clad laminate having excellent interlayer adhesiveness can be obtained. Specifically, it is possible to sufficiently suppress the peeling of the metal leaf from the insulating layer containing the cured product of the resin composition, and it is possible to sufficiently suppress the insulating delamination when the insulating layer is composed of multiple layers. can. Further, by manufacturing a wiring board using the resin composition, a wiring board having excellent interlayer adhesiveness capable of sufficiently suppressing peeling of wiring and delamination of insulation can be obtained.

Further, in the resin composition, it is preferable that the aliphatic hydrocarbon compound contains a compound having 6 to 45 carbon atoms.

According to such a configuration, the interlayer adhesiveness of the cured product of the resin composition can be further enhanced. It is considered that this is because the compound having 6 to 45 carbon atoms can further enhance the adhesiveness.

Further, in the resin composition, the content of the compound having 6 to 45 carbon atoms is preferably 95% by mass or more with respect to the entire aliphatic hydrocarbon compound.

According to such a configuration, the interlayer adhesiveness of the cured product of the resin composition can be further enhanced. It is considered that this is because the compound having 6 to 45 carbon atoms, which can further enhance the adhesiveness, is contained in a large amount.

Further, in the resin composition, it is preferable that the aliphatic hydrocarbon compound contains a compound in which R ₂ and R ₃ are hydrogen atoms.

According to such a configuration, the interlayer adhesiveness of the cured product of the resin composition can be further enhanced. It is considered that this is because the compound in which the R ₂ and the R ₃ are hydrogen atoms can further enhance the adhesiveness.

Further, in the resin composition, a cross-linking type curing agent further containing a curing agent, the curing agent having two or more carbon-carbon unsaturated double bonds in the molecule, and a number average molecular weight of less than 400. , And at least one selected from the group consisting of maleimide compounds having a maleimide group in the molecule.

According to such a configuration, the heat resistance of the cured product of the resin composition can be enhanced.

Further, in the resin composition, the cross-linking type curing agent has a compound having two or more allyl groups in the molecule, a compound having two or more vinylphenyl groups in the molecule, and two or more methacryloyl groups in the molecule. It is preferable to contain at least one selected from the group consisting of a compound and a compound having three or more vinyl groups in the molecule. Further, the maleimide compound is at least one selected from the group consisting of a compound having two or more maleimide groups in the molecule and a compound having one maleimide group in the molecule and having a number average molecular weight of less than 200. It is preferable to include it.

According to such a configuration, the heat resistance of the cured product of the resin composition can be further enhanced.

Further, in the resin composition, the content of the aliphatic hydrocarbon compound is 5 to 50 mass by mass with respect to 100 parts by mass of the total mass of the modified polyphenylene ether compound, the aliphatic hydrocarbon compound, and the curing agent. It is preferably a part.

According to such a configuration, in the cured product of the resin composition, not only the dielectric constant and the dielectric loss tangent are low and the interlayer adhesiveness is high, but also the heat resistance can be high.

Further, in the resin composition, the content of the curing agent is 5 to 50 parts by mass with respect to 100 parts by mass of the total mass of the modified polyphenylene ether compound, the aliphatic hydrocarbon compound, and the curing agent. Is preferable.

According to such a configuration, in the cured product of the resin composition, not only the dielectric constant and the dielectric loss tangent are low and the interlayer adhesiveness is high, but also the heat resistance can be high.

Further, the prepreg according to another aspect of the present invention is a prepreg comprising the resin composition or a semi-cured product of the resin composition and a fibrous base material.

According to such a configuration, it is possible to provide a prepreg in which a cured product having a low dielectric constant and a dielectric loss tangent and a high interlayer adhesiveness can be obtained.

The resin-attached film according to another aspect of the present invention is a resin-attached film including a resin layer containing the resin composition or a semi-cured product of the resin composition, and a support film.

According to such a configuration, it is possible to provide a resin-coated film having a low dielectric constant and dielectric loss tangent and a cured product having high interlayer adhesiveness.

Further, the metal leaf with resin according to another aspect of the present invention is a metal leaf with resin including the resin composition or a resin layer containing a semi-cured product of the resin composition, and the metal foil.

According to such a configuration, it is possible to provide a metal foil with a resin, which has a low dielectric constant and dielectric loss tangent and can obtain a cured product having high interlayer adhesiveness.

The metal-clad laminate according to another aspect of the present invention is a metal-clad laminate comprising an insulating layer containing a cured product of the resin composition or a cured product of the prepreg, and a metal foil.

According to such a configuration, it is possible to provide a metal-clad laminate having a low dielectric constant and a low dielectric loss tangent and having a high interlayer adhesiveness. The metal-clad laminate can sufficiently suppress the peeling of the metal foil from the insulating layer and the peeling of the insulating delamination when the insulating layer is composed of multiple layers.

Further, the wiring board according to another aspect of the present invention is a wiring board including an insulating layer containing a cured product of the resin composition or a cured product of the prepreg, and wiring.

According to such a configuration, it is possible to provide a wiring board having an insulating layer having a low dielectric constant and a low dielectric loss tangent and having a high interlayer adhesiveness. The wiring board can sufficiently suppress the peeling of the wiring from the insulating layer and the peeling of the insulating delamination when the insulating layer is composed of multiple layers.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited thereto.

[Examples 1 to 14 and Comparative Examples 1 to 4]
In this example, each component used when preparing the resin composition will be described.

(Polyphenylene ether component: PPE)
Modified PPE-1: A modified polyphenylene ether in which the terminal hydroxyl group of the polyphenylene ether is modified with a methacryloyl group (represented by the above formula (13), R ₇ in the formula (13) is a methyl group, and is in the formula (13). Modified polyphenylene ether compound in which Y is a dimethylmethylene group (a group represented by the formula (10) and R ₃₆ and R ₃₇ in the formula (10) are methyl groups), SA9000 manufactured by SABIC Innovative Plastics, weight average. Molecular weight Mw2000, number of terminal functional groups 2)
Modified PPE-2: A modified polyphenylene ether compound having a vinylbenzyl group (ethenylbenzyl group) at the terminal (OPE-2st 1200, Mw1400 manufactured by Mitsubishi Gas Chemicals Corporation, represented by the above formula (11), where Z is phenylene. A _{modified polyphenylene ether compound in which R 4 to} R ₆ are hydrogen atoms and p is 0).
Unmodified PPE: Polyphenylene ether (SA90 manufactured by SABIC Innovative Plastics, intrinsic viscosity (IV) 0.083 dl / g, number of terminal hydroxyl groups, weight average molecular weight Mw1700)
(Aromatic hydrocarbon compound)
Linearlen 6: 1-Hexene (Linearlen 6 manufactured by Idemitsu Kosan Co., Ltd.)
Linearlen 18: 1-Octadesen (Linearlen 18 manufactured by Idemitsu Kosan Co., Ltd.)
Linearene 2024: 1-octadecene: 5% by mass or less, 1-icosene: 40-60% by mass, 1-docosen: 25-50% by mass, 1-tetracocene: 18% by mass or less, components having 26 or more carbon atoms: 1 Mixture of mass% or less (Linearlen 2024 manufactured by Idemitsu Kosan Co., Ltd.)
A-20: Compound represented by the above formula (14) (A-20 manufactured by Toyokuni Oil Co., Ltd.)
1,13-Tetradecadene: 1,13-Tetradecadene (polybutadiene) manufactured by Tokyo Chemical Industry Co., Ltd.
B-1000: Polybutadiene (B-1000 manufactured by Nippon Soda Corporation)
TAIC: Triallyl Isocyanurate (TAIC manufactured by Nihon Kasei Co., Ltd.)
DVB-810: Divinylbenzene (DVB-810 manufactured by Nippon Steel & Sumitomo Metal Corporation)
BMI-5100: 3,3-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide (a bifunctional maleimide compound having two maleimide groups in the molecule, BMI-5100 manufactured by Daiwa Kasei Kogyo Co., Ltd.) )
Monofunctional maleimide compound having one maleimide group in the molecule (IMIREX C manufactured by Nippon Shokubai Co., Ltd.)
Styrene: Styrene organic peroxide manufactured by Tokyo Chemical Industry Co., Ltd .: Dicumyl peroxide (Park Mill D manufactured by NOF Corporation)
Inorganic filler: Vinylsilane-treated silica (SV-C2 manufactured by Admatex Co., Ltd., average particle size: 1.5 μm)
(Preparation method)
First, each of the above components other than the inorganic filler was added to toluene with the compositions (parts by mass) shown in Tables 1 and 2 so that the solid content concentration was 55% by mass, and mixed. The mixture was stirred for 60 minutes. Then, a filler was added to the obtained liquid, and the filler was dispersed by a bead mill. By doing so, a varnish-like resin composition (varnish) was obtained.

Next, the obtained varnish was impregnated with a fibrous base material (glass cloth: L2116, # 2116 type, L glass manufactured by Asahi Kasei Corporation), and then heated and dried at 110 ° C. for about 3 to 8 minutes to prepare a prepreg. Was produced. At that time, the content (resin content) of the components constituting the resin by the curing reaction, such as the modified polyphenylene ether compound and the curing agent, with respect to the prepreg was adjusted to be about 55% by mass.

In addition, 6 sheets of each of the obtained prepregs were superposed, and copper foils (FV-WS manufactured by Furukawa Electric Co., Ltd., thickness 18 μm) were arranged on both sides thereof. Using this as a pressure-pressed body, it was heated and pressed under the conditions of a temperature of 200 ° C. for 120 minutes and a pressure of 3 MPa to obtain an evaluation substrate (metal-clad laminate) in which copper foil was adhered to both sides.

The copper foil was removed from the metal-clad laminate by etching. By doing so, an evaluation substrate (a substrate obtained by etching a copper foil of a metal-clad laminate) was obtained.

The prepreg and the evaluation substrate (a metal-clad laminate, a substrate obtained by etching the copper foil of the metal-clad laminate) prepared as described above were evaluated by the methods shown below.

[Relative permittivity (Dk) and dielectric loss tangent (Df)]
The relative permittivity and dielectric loss tangent of the evaluation substrate (the substrate obtained by etching the copper foil of the metal-clad laminate) at 10 GHz were measured by the cavity resonator perturbation method. Specifically, a network analyzer (N5230A manufactured by Keysight Technology Co., Ltd.) was used to measure the relative permittivity and the dielectric loss tangent of the evaluation substrate at 10 GHz.

[Copper foil peel strength]
The copper foil was peeled off from the evaluation substrate (metal-clad laminate), and the peel strength at that time was measured in accordance with JIS C 6481. Specifically, the copper foil of the evaluation substrate is processed to form a pattern having a width of 10 mm and a length of 100 mm, and the patterned copper foil is peeled off at a speed of 50 mm / min by a tensile tester. The peeling strength (copper foil adhesive strength) was measured. The measurement unit is N / mm.

[Interlayer peel strength]
The insulating layer (prepreg) on the uppermost surface was peeled off from the evaluation substrate (metal-clad laminate) together with the copper foil, and the peel strength at that time was measured in accordance with JIS C 6481. Specifically, the insulating layer (prepreg) on the uppermost surface of the evaluation substrate was peeled off together with the copper foil at a speed of 50 mm / min by a tensile tester, and the peel strength (N / mm) at that time was measured.

[Glass transition temperature (Tg)]
The Tg of the prepreg was measured using a viscoelastic spectrometer "DMS100" manufactured by Seiko Instruments Inc. At this time, dynamic viscoelasticity measurement (DMA) was performed with the bending module at a frequency of 10 Hz, and the temperature at which tan δ showed the maximum when the temperature was raised from room temperature to 280 ° C. under the condition of a temperature rising rate of 5 ° C./min was defined as Tg. bottom.

[Heat-resistant]
The evaluation substrate (the substrate obtained by etching the copper foil of the metal-clad laminate) was left in a constant temperature bath at 260 ° C. or 280 ° C. for 1 hour. The presence or absence of swelling generated on the substrate after being left in this constant temperature bath for 1 hour was visually observed. If the occurrence of swelling was not confirmed (if the number of swelling occurrences was 0), it was evaluated as “◯”. If the occurrence of swelling was confirmed, it was evaluated as "x".

The results of each of the above evaluations are shown in Tables 1 and 2. When a prepreg or an evaluation substrate (a substrate obtained by etching a copper foil of a metal-clad laminate and a metal-clad laminate) cannot be suitably manufactured, the evaluation is "separation" or "not cured". show. “Separation” refers to a state in which the obtained resin composition cannot be obtained as a uniform cured product even if it is cured (the components contained in the resin composition are separated from each other). Further, "not cured" means that the resin composition was not cured even when the metal-clad laminate was manufactured as described above.

As can be seen from Tables 1 and 2, the resin compositions containing the modified polyphenylene ether compound and the aliphatic hydrocarbon compound (Examples 1 to 13) are resin compositions having a low relative permittivity and dielectric loss tangent. be. Further, when the resin compositions according to Examples 1 to 13 are used, the interlayer peel strength is higher than that of the resin compositions (Comparative Example 2 and Comparative Example 4) containing a curing agent without containing the aliphatic hydrocarbon compound. Highly cured product was obtained. Further, when the resin compositions according to Examples 1 to 13 were used, a cured product having a copper foil peel strength as high as or higher than that of Comparative Examples 2 and 4 was obtained. The resin compositions according to Comparative Examples 2 and 4 are resin compositions having a low relative permittivity and dielectric loss tangent, similar to the resin compositions according to Examples 1 to 13, but in Examples 1 to 13. The interlayer peel strength was lower than that of the resin composition. Further, in the resin composition containing polybutadiene without containing the aliphatic hydrocarbon compound (Comparative Example 1), the modified polyphenylene ether compound and polybutadiene were not compatible with each other, and each was in a separated state. Further, when an unmodified polyphenylene ether compound was used instead of the modified polyphenylene ether compound (Comparative Example 3), the obtained resin composition was not sufficiently cured.

When 1,13-tetradecadiene is used as the aliphatic hydrocarbon compound (Example 5), a cured product having a low relative permittivity and dielectric adjacency and a high interlayer peel strength can be obtained. Further, as compared with the case where the other aliphatic hydrocarbon compound is used (Examples 1 to 4 and Example 6), the glass transition temperature tends to be higher, and a cured product having high heat resistance can be obtained. rice field.

Further, even when the aliphatic hydrocarbon compound other than 1,13-tetradecadien is used as the aliphatic hydrocarbon compound, the modified polyphenylene ether compound and the fat represented by the formula (1) are used. Not only the group hydrocarbon compound but also the curing agent is further contained, and the content thereof is 5 parts by mass with respect to the total mass of 100 parts by mass of the modified polyphenylene ether compound, the aliphatic hydrocarbon compound and the curing agent. In the above cases (Examples 7 to 13), a cured product having high interlayer peel strength is obtained, and when the other aliphatic hydrocarbon compound is used (Examples 1 to 4 and Example 6). In comparison, the glass transition temperature tended to be high, and a cured product having high heat resistance was obtained.

1 Prepreg 2 Resin composition or semi-cured product of resin composition 3 Fibrous base material 11 Metal-clad laminate 12 Insulation layer 13 Metal foil 14 Wiring 21 Wiring board 31 Metal foil with resin 32, 42 Resin layer 41 Film with resin 43 Support film

Claims (13)

A modified polyphenylene ether compound terminally modified to a substituent having a carbon-carbon unsaturated double bond,
A resin composition containing an aliphatic hydrocarbon compound represented by the following formula (1).

(In the formula (1), _RA represents an alkyl group having 4 or more carbon atoms or an alkenyl group having 4 or more carbon atoms, and R _{1 to} R ₃ independently represent a hydrogen atom or an alkyl group.) The resin composition according to claim 1, wherein the aliphatic hydrocarbon compound contains a compound having 6 to 45 carbon atoms. The resin composition according to claim 2, wherein the content of the compound having 6 to 45 carbon atoms is 95% by mass or more based on the total content of the aliphatic hydrocarbon compound. The resin composition according to any one of claims 1 to 3, wherein the aliphatic hydrocarbon compound contains a compound in which R ₂ and R _{3 are hydrogen atoms.} Contains more hardener,
The curing agent consists of a group consisting of a crosslinked curing agent having two or more carbon-carbon unsaturated double bonds in the molecule and a number average molecular weight of less than 400, and a maleimide compound having a maleimide group in the molecule. The resin composition according to any one of claims 1 to 4, which comprises at least one selected. The crosslinked curing agent has a compound having two or more allyl groups in the molecule, a compound having two or more vinylphenyl groups in the molecule, a compound having two or more methacryloyl groups in the molecule, and a vinyl group in the molecule. Includes at least one selected from the group consisting of three or more compounds in
A claim comprising the maleimide compound at least selected from the group consisting of a compound having two or more maleimide groups in the molecule and a compound having one maleimide group in the molecule and having a number average molecular weight of less than 200. Item 5. The resin composition according to Item 5. The content of the aliphatic hydrocarbon compound is 5 to 50 parts by mass with respect to 100 parts by mass of the total mass of the modified polyphenylene ether compound, the aliphatic hydrocarbon compound, and the curing agent. Item 6. The resin composition according to Item 6. The content of the curing agent is 5 to 50 parts by mass with respect to 100 parts by mass of the total mass of the modified polyphenylene ether compound, the aliphatic hydrocarbon compound, and the curing agent, according to claim 5 or 6. The resin composition described. A prepreg comprising the resin composition according to any one of claims 1 to 8 or a semi-cured product of the resin composition, and a fibrous base material. A film with a resin comprising a resin layer containing the resin composition according to any one of claims 1 to 8 or a semi-cured product of the resin composition, and a support film. A metal foil with a resin comprising a resin layer containing the resin composition according to any one of claims 1 to 8 or a semi-cured product of the resin composition, and a metal foil. A metal-clad laminate comprising an insulating layer containing a cured product of the resin composition according to any one of claims 1 to 8 or a cured product of a prepreg according to claim 9, and a metal foil. A wiring board including an insulating layer containing a cured product of the resin composition according to any one of claims 1 to 8 or a cured product of a prepreg according to claim 9, and wiring.

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