WO2020059562A1

WO2020059562A1 - Resin composition, prepreg using same, film with resin, metal foil with resin, metal-clad laminated board, and wiring board

Info

Publication number: WO2020059562A1
Application number: PCT/JP2019/035392
Authority: WO
Inventors: 裕輝井ノ上; 阿部　智之; 達也有沢
Original assignee: パナソニックＩｐマネジメント株式会社
Priority date: 2018-09-19
Filing date: 2019-09-09
Publication date: 2020-03-26
Also published as: CN112469750A; JPWO2020059562A1; TW202022017A

Abstract

An aspect of the present invention relates to a resin composition characterized by including: a polyphenylene ether compound having a group represented by formula (1) at the end of the molecule; and at least one from among a crosslinking agent having a carbon-carbon unsaturated double bond in the molecule or a crosslinking agent that reacts with the polyphenylene ether compound and performs curing, wherein the amount of chloride ions in the polyphenylene ether compound is 250 ppm or less. [In formula (1), R₁ represents a hydrogen atom or an alkyl group having 1-10 carbon atoms, and R₂ represents an alkylene group having 1-10 carbon atoms.]

Description

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

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

In recent years, with the increase in the amount of information processing of various electronic devices, mounting technologies such as high integration of semiconductor devices to be mounted, high density of wiring, and multi-layering are rapidly progressing. In order to increase the signal transmission speed and reduce the loss during signal transmission, the substrate material for forming the base material of the printed wiring board used in various electronic devices must have a low dielectric constant and a low dielectric loss tangent. Can be

に対し Responding to such a demand, a resin composition containing a terminal-modified polyphenylene ether (PPE) compound has been used as a material having excellent electrical properties (for example, Patent Documents 1 and 2). It has also been reported that wiring boards made of a resin composition containing a PPE compound have excellent transmission characteristics.

On the other hand, when used as a molding material such as a substrate material, it is required that the cured product not only has excellent low dielectric properties but also has a high glass transition temperature (Tg) and has heat resistance and adhesion. Can be

However, although it is considered that the resin composition described in Patent Document 1 can obtain low dielectric properties, chloride ions used in performing terminal modification (divinylbenzylation modification) according to the study of the present inventors have been proposed. It has been found that when a printed wiring board is prepared using the resin composition, sufficient insulation reliability may not be ensured due to the influence of the residue. In particular, this effect was remarkable on a wiring board provided with a conductor circuit pattern having a small distance between conductor circuits.

On the other hand, only the modified PPE used in Patent Document 2 described above has a poor reactivity and thus has a problem that Tg is lowered. To solve this, a reaction initiator is required, but there is a drawback that the electrical properties (low dielectric properties and transmission properties) are degraded by the influence of the initiator.

The present invention has been made in view of such circumstances, and provides a resin composition having low dielectric properties (low dielectric constant and dielectric loss tangent), high Tg, and insulation reliability in a cured product of the resin composition. The purpose is to do. 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 using the resin composition.

JP 2011-68713 A JP-T-2004-511580

A resin composition according to one embodiment of the present invention includes a polyphenylene ether compound having a group represented by the following formula (1) at a molecular terminal, a crosslinking agent having a carbon-carbon unsaturated double bond in a molecule, or the polyphenylene compound. The polyphenylene ether compound contains at least one of a crosslinking agent that reacts with the ether compound and cures, and the amount of chloride ions in the polyphenylene ether compound is 250 ppm or less.

[In the formula (1), R ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ₂ represents an alkylene group having 1 to 10 carbon atoms. ]

According to the present invention, a resin composition having low dielectric properties, high Tg, and excellent insulation reliability in a cured product of the resin composition can be provided. Further, according to the present invention, a prepreg, a film with a resin, a metal foil with a resin, a metal-clad laminate, and a wiring board having excellent performance can be provided by using the resin composition.

FIG. 1 is a schematic sectional view showing the configuration of a prepreg according to one embodiment of the present invention. FIG. 2 is a schematic sectional view showing the configuration of the metal-clad laminate according to one embodiment of the present invention. FIG. 3 is a schematic sectional view showing the configuration of the wiring board according to one embodiment of the present invention. FIG. 4 is a schematic sectional view showing the configuration of the metal foil with resin according to one embodiment of the present invention. FIG. 5 is a schematic sectional view showing the configuration of the resin film according to one embodiment of the present invention. FIG. 6 is a schematic diagram showing a distance (space) S between two adjacent wirings (conductor circuits) (L) on a substrate having a conductor circuit pattern according to one embodiment of the present invention. FIG. 7 is a schematic diagram showing a comb-shaped pattern for evaluating insulation reliability in the example.

The resin composition according to the embodiment of the present invention comprises a polyphenylene ether compound having a group represented by the following formula (1) at a molecular terminal, a cross-linking agent having a carbon-carbon unsaturated double bond in the molecule, or the polyphenylene ether. The polyphenylene ether compound contains at least one of a crosslinking agent that reacts with the ether compound and cures, and the amount of chloride ions in the polyphenylene ether compound is 250 ppm or less.

[In the formula (1), R ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ₂ represents an alkylene group having 1 to 10 carbon atoms. ]
Hereinafter, each component of the resin composition according to the present embodiment will be specifically described.

(Polyphenylene ether compound)
The polyphenylene ether compound used in the present embodiment is a polyphenylene ether compound having a group represented by the above formula (1) at the molecular terminal and having a chloride (Cl ⁻ ) ion content of 250 ppm or less. There is no particular limitation. By using such a polyphenylene ether compound, occurrence of ion migration can be suppressed, and excellent insulation reliability can be obtained. Further, since the polyphenylene ether compound of the present embodiment can react with a crosslinking agent described later without using a reaction initiator, it is not affected by the reaction initiator. Therefore, it is considered that the resin composition of the present embodiment can obtain higher glass transition temperature (Tg) and adhesion while maintaining excellent insulation reliability, low dielectric constant and dielectric loss tangent.

として As a material property, in a material having a high Tg of a cured product, heat resistance (such as solder heat resistance) can be one of the factors for further improving. Further, a material having a high Tg in the cured product also has an advantage that the coefficient of thermal expansion of the material in a higher temperature range becomes a small value. In general, at a temperature exceeding the glass transition temperature, the thermal expansion sharply increases. That is, when the glass transition temperature is low, the coefficient of thermal expansion increases in a high temperature region exceeding the glass transition temperature. When the glass transition temperature is low, thermal expansion in a higher temperature region becomes large, for example, the reliability of interlayer connection (barrel crack generation of a through hole, etc.) in a wiring board is deteriorated, and the wiring board may not function as a printed board. This is because the difference in the coefficient of thermal expansion at high temperature between the material of the insulating layer made of the cured resin composition in the substrate and the material of the through hole made of metal increases, so that cracks are formed on the wall surface of the metal through hole. It is considered that connection reliability deteriorates.

The amount of Cl ^- ion (hereinafter also simply referred to as Cl ion) in the polyphenylene ether compound is not particularly limited as long as it is 250 ppm or less, but is more preferably 200 ppm or less. The smaller the amount of Cl ions, the better. However, when the molecular terminal of the polyphenylene ether compound is modified with the group represented by the formula (1), the terminal is inevitably mixed to some extent. For this reason, there is a possibility that the cost will increase. Therefore, the amount of Cl ions in the polyphenylene ether compound is preferably 5 ppm or more from the viewpoint of cost. More preferably, it is 10 ppm or more, more preferably 15 ppm or more, and still more preferably 30 ppm or more.

The amount of Cl ions in the polyphenylene ether compound can be measured by the method described in Examples below.

Furthermore, in addition to the above-mentioned Cl ion, the polyphenylene ether compound of the present embodiment includes bromide ion (Br ⁻ ), nitrate ion (NO ₃ ⁻ ), sulfate ion (SO ₄ ⁻ ), and nitrite ion (NO ₂ ^−). ), Phosphate ions (PO ₄ ³⁻ ), sodium ions (Na ⁺ ), and ammonium ions (NH ₄ ⁺ ) in some cases. These impurities are not particularly limited, but are preferably as low as possible. When these impurities are contained, bromide ion (Br ⁻ ), nitrate ion (NO ₃ ⁻ ), sulfate ion (SO ₄ ⁻ ), suboxide It is preferable that nitrate ion (NO ₂ ⁻ ), phosphate ion (PO ₄ ³⁻ ), sodium ion (Na ⁺ ), and ammonium ion (NH ₄ ⁺ ) are each 50 ppm or less.

In the formula (1), R ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms is not particularly limited as long as it is an alkyl group having 1 to 10 carbon atoms, and may be linear or branched. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, etc. Is mentioned. Among them, a hydrogen atom is preferable.

In the formula (1), R ₂ represents an alkylene group having 1 to 10 carbon atoms. The alkylene group having 1 to 10 carbon atoms is not particularly limited as long as it is an alkylene group having 1 to 10 carbon atoms, and includes a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, and an octylene group. , A nonylene group, and a decylene group. Among them, a methylene group is preferable.

The group represented by the formula (1) is not particularly limited, but is at least one ethenylbenzyl group selected from a p-ethenylbenzyl group, an m-ethenylbenzyl group, and an o-ethenylbenzyl group ( (Vinyl benzyl group). Furthermore, it is preferable to have at least two kinds selected from a p-ethenylbenzyl group, an m-ethenylbenzyl group and an o-ethenylbenzyl group.

In particular, the resin composition of the present embodiment preferably contains a polyphenylene ether compound having a structure represented by the following formula (2) as the polyphenylene ether compound from the viewpoint of more reliably obtaining the above-described effects. .

In the above formula (2), R ₃ to R ₁₀ are each independent. That is, R ₃ to R ₁₀ may be the same group or different groups. R ₃ to R ₁₀ 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. Among them, a hydrogen atom and an alkyl group are preferable.

With respect to R ₃ to R ₁₀ , specific examples of the functional groups listed above include the following.

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

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

The alkynyl group is not particularly limited, but is preferably, for example, an alkynyl group having 2 to 18 carbon atoms, more preferably an alkynyl group having 2 to 10 carbon atoms. Specific examples include an ethynyl group and a prop-2-yn-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. 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 include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a hexanoyl group, an octanoyl group, and a cyclohexylcarbonyl group.

The alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group. 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 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. 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.

In the above formula (2), A is a structure represented by the following formula (3), and B is a structure represented by the following formula (4):

において In the formulas (3) and (4), the repeating units m and n each represent an integer of 0 to 20.

R ₁₁ to R ₁₈ are each independent. That is, R ₁₁ to R ₁₈ may be the same group or different groups. In the present embodiment, R ₁₁ to R ₁₈ are a hydrogen atom or an alkyl group.

Further, in the above formula (2), Y is a linear, branched or cyclic hydrocarbon having 20 or less carbon atoms. More specifically, it is a structure represented by the following formula (5):

In the formula (5), R ₁₉ and R ₂₀ each independently represent a hydrogen atom or an alkyl group. Examples of the alkyl group include a methyl group. Examples of the group represented by the formula (5) include a methylene group, a methylmethylene group, and a dimethylmethylene group.

In the present embodiment, the weight average molecular weight (Mw) of the polyphenylene ether compound is not particularly limited, but is, for example, preferably from 1,000 to 5,000, and more preferably from 1,000 to 4,000. Here, the weight average molecular weight may be a value measured by a general molecular weight measuring method, and specifically, a value measured using gel permeation chromatography (GPC) and the like can be mentioned. When the polyphenylene ether compound has a repeating unit (m, n) in the molecule, these repeating units have such a numerical value that the weight average molecular weight of the polyphenylene ether compound falls within such a range. Is preferred.

When the weight average molecular weight of the polyphenylene ether compound is within such a range, the polyphenylene ether skeleton has excellent low-dielectric properties and has not only excellent heat resistance of the cured product but also excellent moldability. Become. This is thought to be due to the following. If the weight average molecular weight is in the above-mentioned range as compared with ordinary polyphenylene ether, the cured product has a relatively low molecular weight, and thus the cured product tends to have reduced heat resistance. In this regard, since the polyphenylene ether compound according to the present embodiment has a structure represented by the above formula (1) at the terminal, it is considered that a compound having high reactivity and sufficiently high heat resistance of a cured product can be obtained. Can be Also, when the weight average molecular weight of the polyphenylene ether compound is within such a range, it has a higher molecular weight than styrene or divinylbenzene, but has a relatively low molecular weight than general polyphenylene ether. It is thought that it is also excellent. Therefore, it is considered that by using such a polyphenylene ether compound, not only the cured product having excellent heat resistance but also excellent moldability can be obtained.

平均 In the polyphenylene ether compound used in the present embodiment, the average number (the number of terminal functional groups) of the X substituents at the molecular terminal per one molecule of the modified polyphenylene ether is not particularly limited. Specifically, the number is preferably 1 to 5, more preferably 1 to 3. If the number of the terminal functional groups is too small, the cured product tends to be insufficient in heat resistance. Further, when the number of terminal functional groups is too large, the reactivity becomes too high, and for example, problems such as a decrease in storage stability of the resin composition and a decrease in fluidity of the resin composition may occur. . That is, when such a modified polyphenylene ether is used, due to lack of fluidity or the like, for example, molding defects such as generation of voids during multilayer molding occur, and it is difficult to obtain a highly reliable printed wiring board. A problem could occur.

The number of terminal functional groups of the polyphenylene ether compound includes a numerical value indicating the average value of the substituents per molecule of all the polyphenylene ether compounds present in 1 mol of the 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 polyphenylene ether compound and calculating a 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 modification is the number of terminal functional groups. The method for measuring the number of hydroxyl groups remaining in the polyphenylene ether compound is to add a quaternary ammonium salt (tetraethylammonium hydroxide) associated with a hydroxyl group to a solution of the polyphenylene ether compound and measure the UV absorbance of the mixed solution. Can be sought.

固有 Further, the intrinsic viscosity of the polyphenylene ether compound used in the present embodiment is not particularly limited. Specifically, the concentration may be 0.03 to 0.12 dl / g, preferably 0.04 to 0.11 dl / g, and more preferably 0.06 to 0.095 dl / g. . If the intrinsic viscosity is too low, the molecular weight tends to be low, and it tends to be difficult to obtain low dielectric properties such as a low dielectric constant and a 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, when the intrinsic viscosity of the polyphenylene ether compound is within the above range, excellent heat resistance and moldability of the cured product can be realized.

Note that the intrinsic viscosity here is an 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 measured using a viscometer. And the like. As the viscometer, for example, AVS500 {Visco} System manufactured by Schott and the like can be mentioned.

Note that the resin composition of the present embodiment may include a thermosetting resin other than the polyphenylene ether compound as described above. For example, other thermosetting resins that can be used include an epoxy resin, a phenol resin, an amine resin, an unsaturated polyester resin, a thermosetting polyimide resin, and a maleimide compound. The maleimide compound may be a modified maleimide compound, and specific examples include a maleimide compound in which at least a part of the molecule is modified with a silicone compound, a maleimide compound modified with an amine compound, and the like.

The method for synthesizing a polyphenylene ether compound preferably used in the present embodiment is a method for synthesizing a modified polyphenylene ether compound in which the terminal is modified with the substituent X as described above and the chloride ion content of the obtained compound is 250 ppm or less. The method is not particularly limited as long as it can be performed. Specifically, for example, a method of reacting a compound in which a substituent X and a halogen atom are bonded to polyphenylene ether and the like can be mentioned.

において In the substituent X represented by the formula (1), the position of the group having a carbon-carbon unsaturated double bond may be any of p (para), m (meta), and o (ortho). More specifically, the compound in which the substituent X is bonded to a halogen atom used in the above synthesis method is, for example, p-chloromethylstyrene, m-chloromethylstyrene, o-chloromethylstyrene and the like. One of these compounds may be used alone, or two or three of them may be used in combination. When two or more kinds of p-chloromethylstyrene, m-chloromethylstyrene, and o-chloromethylstyrene are used in combination, the ratio of use (mass ratio) is not particularly limited. When methyl styrene and m-chloromethyl styrene are used in combination, the proportion (mass ratio, the same applies hereinafter) of p-chloromethyl styrene: m-chloromethyl styrene is preferably about 5-95: 95-5. . When p-chloromethylstyrene and o-chloromethylstyrene are used in combination, the ratio of p-chloromethylstyrene: o-chloromethylstyrene is preferably about 5 to 95:95 to 5; When -chloromethylstyrene and o-chloromethylstyrene are used, the ratio of m-chloromethylstyrene: o-chloromethylstyrene is preferably about 5-95: 95-5. Further, when three are used in combination, it is preferable that the use ratio is about p-chloromethylstyrene: m-chloromethylstyrene: o-chloromethylstyrene = 20 to 90:40 to 5:40 to 5.

(4) When two or more of p-chloromethylstyrene, m-chloromethylstyrene and o-chloromethylstyrene are used in combination, it is preferable to use p-chloromethylsulene as at least one of them. More preferably, p-chloromethylstyrene is used in an amount of at least 40% by weight, more preferably at least 50% by weight, and even more preferably at least 60% by weight, based on the total amount of chloromethylstyrene used. Is more preferred.

Further, a case where a polyphenylene ether compound having a group represented by the formula (1) is synthesized by using two or more kinds selected from p-chloromethylstyrene, m-chloromethylstyrene, and o-chloromethylstyrene in combination, When the formula (1) in the polyphenylene ether compound contains an ethenylbenzyl group in which R ₁ is a hydrogen atom and R ₂ is an alkylene group having 1 carbon atom, a substituent represented by the formula (1) after synthesis The ratio of the p-ethenylbenzyl group, the m-ethenylbenzyl group, and the o-ethenylbenzyl group in the polyphenylene ether compound having the formula (1) is represented by the ratio of each average number.

Specifically, when two kinds are used in combination, when p-chloromethylstyrene and m-chloromethylstyrene are used in combination, the average of each group in the polyphenylene ether compound having a group represented by the formula (1) after synthesis is used. The number ratio (average number ratio, hereinafter the same) is preferably about p-ethenylbenzyl group: m-ethenylbenzyl group = 5 to 95:95 to 5 or so. When p-chloromethylstyrene and o-chloromethylstyrene are used in combination, the ratio of the average number of each group in the polyphenylene ether compound represented by the above formula (1) is p-ethenylbenzyl group: o-ethenyl The benzyl group is preferably about 5 to 95:95 to 5. When m-chloromethylstyrene and o-chloromethylstyrene are used, the ratio of the average number of each group is m-ethenylbenzyl group: o -Ethenyl benzyl group = 5 to 95: preferably about 95 to 5. Further, when three of p-chloromethylstyrene, m-chloromethylstyrene, and o-chloromethylstyrene are used in combination, p-ethenyl in the polyphenylene ether compound having a group represented by the above formula (1) after synthesis is used. The ratio of the average number of benzyl groups, m-ethenylbenzyl groups and o-ethenylbenzyl groups is as follows: p-ethenylbenzyl group: m-ethenylbenzyl group: o-ethenylbenzyl group = 20 to 90:40 ５5: It is preferable to be about 40 ～ 5. When the polyphenylene ether compound having the group represented by the formula (1) contains two or more of p-ethenylbenzyl group, m-ethenylbenzyl group and o-ethenylbenzyl group, p-ethenylbenzyl More preferably, the ratio of the p-ethenylbenzyl group to the total number of ethenylbenzyl groups contained in the polyphenylene ether compound having the group represented by the formula (1) is 40% or more. It is more preferably at least 50%, and even more preferably at least 60%.

ポリ The raw material polyphenylene ether is not particularly limited as long as it can finally synthesize a predetermined modified polyphenylene ether. Specifically, a polyphenylene ether such as polyphenylene ether or poly (2,6-dimethyl-1,4-phenylene oxide) comprising 2,6-dimethylphenol and at least one of bifunctional phenol and trifunctional phenol is used. And the like as a main component. Further, the bifunctional phenol is a phenol compound having two phenolic hydroxyl groups in a molecule, for example, tetramethylbisphenol A and the like. The trifunctional phenol is a phenol compound having three phenolic hydroxyl groups in a molecule.

As an example of a method for synthesizing a polyphenylene ether compound, for example, in the case of a polyphenylene ether compound represented by the above formula (2), specifically, the above-described polyphenylene ether is bonded to a substituent X and a halogen atom. The obtained compound (compound having a substituent X) is dissolved in a solvent and stirred. By doing so, the polyphenylene ether reacts with the compound having the substituent X to obtain the modified polyphenylene ether of the present embodiment represented by the above formula (2).

It is preferable that this reaction is performed in the presence of an alkali metal hydroxide. By doing so, it is believed that this reaction proceeds favorably. This is presumably because the alkali metal hydroxide functions as a dehydrohalogenating agent, specifically, a dehydrochlorinating agent. That is, the alkali metal hydroxide removes the hydrogen halide from the phenol group of the polyphenylene ether and the compound having the substituent X, thereby replacing the hydrogen atom of the phenol group of the polyphenylene ether with a hydrogen atom. It is believed that group X is attached to the oxygen atom of the phenol group.

アルカリ Alkali metal hydroxide is not particularly limited as long as it can function as a dehalogenating agent, and examples thereof include sodium hydroxide. The alkali metal hydroxide is usually used in the form of an aqueous solution, and specifically, is used as an aqueous sodium hydroxide solution.

The reaction conditions such as the reaction time and the reaction temperature vary depending on the compound having the substituent X and the like, and are not particularly limited as long as the above-mentioned reaction proceeds suitably. Specifically, the reaction temperature is preferably from room temperature to 100 ° C., more preferably from 30 to 100 ° C. Further, the reaction time is preferably 0.5 to 20 hours, more preferably 0.5 to 10 hours.

The solvent used in the reaction is not particularly limited as long as it can dissolve the polyphenylene ether and the compound having the substituent X, and does not inhibit the reaction between the polyphenylene ether and the compound having the substituent X. . Specific examples include toluene.

In addition, the above reaction is preferably carried out in the presence of not only an alkali metal hydroxide but also a phase transfer catalyst. That is, the above reaction is preferably performed 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 suitably. This is thought to be due to the following. The phase transfer catalyst has a function of incorporating an 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. This is considered to be due to the fact that the catalyst is capable of transporting. Specifically, when an aqueous solution of sodium hydroxide is used as the alkali metal hydroxide and an organic solvent such as toluene that is incompatible with water is used as the solvent, the aqueous solution of sodium hydroxide is used for the reaction. It is considered that even when the solvent is dropped, the solvent and the aqueous solution of sodium hydroxide are separated, and the sodium hydroxide is hardly transferred to the solvent. In that case, it is considered that the aqueous sodium hydroxide solution added as the alkali metal hydroxide hardly contributes to the promotion of the reaction. On the other hand, when the reaction is performed in the presence of the alkali metal hydroxide and the phase transfer catalyst, the alkali metal hydroxide is transferred to the solvent with the alkali metal hydroxide being taken into the phase transfer catalyst, and the aqueous sodium hydroxide solution reacts. It is thought that it will be easier to contribute to promotion. Therefore, when the reaction is performed in the presence of the alkali metal hydroxide and the phase transfer catalyst, it is considered that the above reaction proceeds more suitably.

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

After the reaction is completed, alcohol such as methanol is added to the reaction solution to reprecipitate the product, and the precipitate is taken out by filtration. By repeating the washing step several times (preferably two or more times), the chloride ion content of the obtained polyphenylene ether compound can be reduced to 250 ppm or less.

(Crosslinking agent)
Next, the crosslinking agent used in the present embodiment will be described. The cross-linking agent used in the present embodiment is not particularly limited as long as it is a cross-linking agent having a carbon-carbon unsaturated double bond in the molecule or a cross-linking agent which reacts with the polyphenylene ether compound to be cured.

The crosslinking agent of the present embodiment is a compound having a carbon-carbon unsaturated double bond in the molecule or having at least one functional group in the molecule that contributes to the reaction with the polyphenylene ether compound. , And can efficiently react with the polyphenylene ether compound. Therefore, it is considered that the resin composition of the present embodiment can secure high Tg and adhesion.

The cross-linking agent that can be used in the present embodiment is an average number of carbon-carbon unsaturated bonds (number of terminal double bonds) per one molecule of the cross-linking agent, or a functional group that contributes to the reaction with the compound (A). The average number (number of functional groups) per molecule of the crosslinking type curing agent differs depending on the weight average molecular weight of the crosslinking agent and the like. The number of terminal double bonds and the number of functional groups are, for example, preferably from 1 to 20, more preferably from 2 to 18. If the number of terminal double bonds or the number of functional groups is too small, the cured product tends to have insufficient heat resistance. If the number of terminal double bonds or the number of functional groups is too large, the reactivity of the crosslinking agent becomes too high. For this reason, for example, 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, and the moldability of the obtained cured product may be reduced.

The number of terminal double bonds and the number of functional groups of the crosslinking agent are preferably 1 to 4 when the weight-average molecular weight of the crosslinking agent is less than 500 (for example, 100 or more and less than 500). Further, the number of terminal double bonds and the number of functional groups of the crosslinking agent are preferably 3 to 20 when the weight average molecular weight of the crosslinking agent is 500 or more (for example, 500 or more and 5000 or less). In each case, if the number of terminal double bonds or the number of functional groups is less than the lower limit of the above range, the reactivity of the crosslinking agent decreases, the crosslinking density of the cured product of the resin composition decreases, and the heat resistance and There is a possibility that Tg cannot be sufficiently improved. On the other hand, when the number of terminal double bonds or the number of functional groups is larger than the upper limit of the above range, the resin composition may be easily gelled.

The number of terminal double bonds and the number of functional groups here can be found from the standard value of the product of the crosslinking agent used. As the number of terminal double bonds and the number of functional groups, specifically, for example, the average value of the number of double bonds and the number of functional groups per molecule of all the cross-linking agents present in 1 mol of the cross-linking agent is shown. And the like.

As a specific crosslinking agent, a compound having two or more carbon-carbon double bonds in a molecule is preferable. For example, styrene, a styrene copolymer, a styrene derivative, a compound having an acryloyl group in a molecule, a molecule A compound having a methacryloyl group in the compound, a compound having a vinyl group in the molecule, a compound having an allyl group in the molecule, a compound having a maleimide group in the molecule, a compound having an acenaphthylene structure in the molecule, and an isocyanurate in the molecule And an isocyanurate compound having a group. When these are used, it is considered that crosslinking is more preferably formed by the curing reaction, and the heat resistance of the cured product of the resin composition used in the present embodiment can be further increased.

Examples of the styrene derivative include bromostyrene and dibromostyrene.

化合物 The compound having an acryloyl group in the molecule is an acrylate compound. Examples of the acrylate compound include a monofunctional acrylate compound having one acryloyl group in the molecule and a polyfunctional acrylate compound having two or more acryloyl groups in the molecule. Examples of the monofunctional acrylate compound include methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. Examples of the polyfunctional acrylate compound include tricyclodecane dimethanol diacrylate.

化合物 The compound having a methacryloyl group in the molecule is a methacrylate compound. Examples of the methacrylate compound include a monofunctional methacrylate compound having one methacryloyl group in the molecule and a polyfunctional methacrylate compound having two or more methacryloyl groups in the molecule. Examples of the monofunctional methacrylate compound include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. Examples of the polyfunctional methacrylate compound include tricyclodecane dimethanol dimethacrylate.

化合物 The compound having a vinyl group in the molecule is a vinyl compound. Examples of the vinyl compound include a monofunctional vinyl compound having one vinyl group in the molecule (monovinyl compound) and a polyfunctional vinyl compound having two or more vinyl groups in the molecule. Examples of the polyfunctional vinyl compound include a polyfunctional aromatic vinyl compound, a polyfunctional aliphatic vinyl compound, a polymer or a copolymer containing a structure derived from the polyfunctional aromatic vinyl compound, and a structure derived from the polyfunctional aliphatic vinyl compound. Examples thereof include polymers or copolymers containing divinylbenzene, divinylbenzene copolymer, polybutadiene, and butadiene copolymer.

化合物 The compound having an allyl group in the molecule is an allyl compound. Examples of the allyl compound include a monofunctional allyl compound having one allyl group in the molecule and a polyfunctional allyl compound having two or more allyl groups in the molecule. Examples of the polyfunctional allyl compound include diallyl phthalate (DAP).

化合物 The compound having a maleimide group in the molecule is a maleimide compound. Examples of the maleimide compound include a monofunctional maleimide compound having one maleimide group in a molecule and a polyfunctional maleimide compound having two or more maleimide groups in a molecule. Further, the maleimide compound is a modified maleimide compound in which a part of the molecule is modified with an amine compound, a modified maleimide compound in which a part of the molecule is modified with a silicone compound, and a part of the molecule is an amine compound or a silicone compound. And a modified maleimide compound modified with the above.

化合物 The compound having an acenaphthylene structure in the molecule is an acenaphthylene compound. Examples of the acenaphthylene compound include acenaphthylene, alkylacenaphthylenes, halogenated acenaphthylenes, and phenylacenaphthylenes. Examples of the alkyl acenaphthylenes include 1-methylacenaphthylene, 3-methylacenaphthylene, 4-methylacenaphthylene, 5-methylacenaphthylene, 1-ethylacenaphthylene, and 3-ethylacena Phthalene, 4-ethylacenaphthylene, 5-ethylacenaphthylene and the like. Examples of the halogenated acenaphthylenes include 1-chloroacenaphthylene, 3-chloroacenaphthylene, 4-chloroacenaphthylene, 5-chloroacenaphthylene, 1-bromoacenaphthylene, and 3-bromoacenaphthylene Len, 4-bromoacenaphthylene, 5-bromoacenaphthylene and the like. Examples of the phenylacenaphthylene include 1-phenylacenaphthylene, 3-phenylacenaphthylene, 4-phenylacenaphthylene, 5-phenylacenaphthylene and the like. The acenaphthylene compound may be a monofunctional acenaphthylene compound having one acenaphthylene structure in the molecule, or a polyfunctional acenaphthylene compound having two or more acenaphthylene structures in the molecule, as described above. .

化合物 The compound having an isocyanurate group in the molecule is an isocyanurate compound. Examples of the isocyanurate compound include a compound further having an alkenyl group in the molecule (alkenyl isocyanurate compound), and examples thereof include trialkenyl isocyanurate compounds such as triallyl isocyanurate (TAIC).

Examples of the crosslinking agent include, among the above, a polyfunctional acrylate compound having two or more acryloyl groups in the molecule, a polyfunctional methacrylate compound having two or more methacryloyl groups in the molecule, and two vinyl groups in the molecule. Polyfunctional vinyl compound having the above, a styrene derivative, an allyl compound having an allyl group in the molecule, a maleimide compound having a maleimide group in the molecule, an acenaphthylene compound having an acenaphthylene structure in the molecule, and an isocyanate having an isocyanurate group in the molecule Nurate compounds are preferred.

As the cross-linking agent, the above-mentioned cross-linking agents may be used alone or in combination of two or more. As the crosslinking agent, a compound having two or more carbon-carbon unsaturated bonds in a molecule and a compound having one carbon-carbon unsaturated bond in a molecule may be used in combination.

(Content / content ratio)
In the resin composition of the present embodiment, the content of the polyphenylene ether compound is preferably 30 to 90 parts by mass, and more preferably 50 to 90 parts by mass based on 100 parts by mass of the total of the polyphenylene ether compound and the crosslinking agent. Is more preferable. Further, the content of the crosslinking agent is preferably 10 to 70 parts by mass, more preferably 10 to 50 parts by mass, based on 100 parts by mass of the total of the polyphenylene ether compound and the crosslinking agent. That is, the content ratio of the polyphenylene ether compound to the crosslinking agent is preferably from 90:10 to 30:70 by mass, and more preferably from 90:10 to 50:50. If the respective contents of the polyphenylene ether and the crosslinking agent satisfy the above ratio, the curing reaction between the modified polyphenylene ether and the crosslinking agent proceeds suitably. Therefore, the resin composition becomes more excellent in heat resistance and flame retardancy of the crosslinked product.

(Other components)
The resin composition according to the present embodiment is not particularly limited as long as it contains the polyphenylene ether compound and the crosslinking agent, but may further contain other components.

For example, the resin composition according to the present embodiment may further contain a filler. Examples of the filler include, but are not particularly limited to, those added to the cured product of the resin composition to enhance heat resistance and flame retardancy. In addition, by including a filler, heat resistance, flame retardancy, and the like can be further increased. Specific examples of the filler include silica such as spherical silica, metal oxides such as alumina, titanium oxide and mica, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, talc, aluminum borate, and sulfuric acid. Barium, calcium carbonate, and the like. As the filler, silica, mica, and talc are preferable, and spherical silica is more preferable. Further, one kind of the filler may be used alone, or two or more kinds may be used in combination. The filler may be used as it is, or may be one that has been surface-treated with a silane coupling agent of an epoxy silane type, a vinyl silane type, a methacryl silane type, or an amino silane type. The silane coupling agent may be added by an integral blend method instead of a method of preliminarily surface-treating the filler.

When a filler is contained, the content is preferably 10 to 200 parts by mass, and more preferably 30 to 150 parts by mass with respect to 100 parts by mass of the total of the polyphenylene ether compound and the crosslinking agent. More preferred.

Furthermore, the resin composition of the present embodiment may contain a flame retardant. Examples of the flame retardant include a halogen-based flame retardant such as a bromine-based flame retardant and a phosphorus-based flame retardant. Specific examples of the halogen-based flame retardants include, for example, brominated flame retardants such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, hexabromocyclododecane, and chlorinated flame retardants such as chlorinated paraffin. And the like. Specific examples of the phosphorus-based flame retardant include, for example, condensed phosphates, phosphates such as cyclic phosphates, phosphazene compounds such as cyclic phosphazene compounds, metal phosphinates such as aluminum dialkylphosphinates, and the like. Examples include phosphinate-based flame retardants, melamine-based flame retardants such as melamine phosphate and melamine polyphosphate, and phosphine oxide compounds having a diphenylphosphine oxide group. As the flame retardant, each exemplified flame retardant may be used alone, or two or more flame retardants may be used in combination.

When a flame retardant is contained, the content is preferably from 10 to 40 parts by mass, and more preferably from 15 to 30 parts by mass, based on 100 parts by mass of the total of the polyphenylene ether compound and the crosslinking agent. More preferred.

Furthermore, the resin composition according to the present embodiment may contain various additives in addition to the above. Examples of additives include antifoaming agents such as silicone-based antifoaming agents and acrylate-based antifoaming agents, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes and pigments, lubricants, and dispersants such as wetting dispersants. Agents and the like.

(Prepreg, film with resin, metal-clad laminate, wiring board, and metal foil with resin)
Next, a prepreg, a metal-clad laminate, a wiring board, and a resin-attached metal foil using the resin composition of the present embodiment will be described. Reference numerals in the drawings described below denote 1 prepreg, 2 semi-cured resin composition or resin composition, 3 fibrous base material, 11 metal-clad laminate, 12 insulating layer, 13 metal foil, 14 wiring , 21 wiring board, 31 metal foil with resin, 32 and 42 resin layer, 41 film with resin, 43 support film, respectively.

FIG. 1 is a schematic sectional view showing an example of the prepreg 1 according to the embodiment of the present invention.

プリ The prepreg 1 according to the present embodiment includes the resin composition or a semi-cured product 2 of the resin composition and a fibrous base material 3 as shown in FIG. Examples of the prepreg 1 include a resin composition or a semi-cured product 2 in which a fibrous base material 3 is present. That is, the prepreg 1 includes the resin composition or the semi-cured product thereof, and the fibrous base material 3 existing in the resin composition or the semi-cured product 2 thereof.

Ｃｌ The amount of Cl ions in the resin composition or the semi-cured product of the resin composition in the prepreg of the present embodiment, the resin-attached film and the resin-attached metal foil described below is preferably about 0 ppm to 40 ppm. From the viewpoint of cost, the content is more preferably 1 ppm to 40 ppm, further preferably 2 ppm to 40 ppm. The amount of Cl ions in the resin composition or the semi-cured product of the resin composition can be measured by a method described in Examples described later.

Furthermore, in addition to the above-mentioned Cl ion, bromide ion (Br ⁻ ) nitrate ion is contained in the prepreg of the present embodiment, the resin composition or the semi-cured product of the resin composition in the resin-added film and the resin-added metal foil described below. (NO ₃ ⁻ ), sulfate ion (SO ₄ ⁻ ), nitrite ion (NO ₂ ⁻ ), phosphate ion (PO ₄ ³⁻ ), sodium ion (Na ⁺ ), ammonium ion (NH ₄ ⁺ ), calcium ion In some cases, ionic impurities such as (Ca ²⁺ ) are also contained. These ionic impurities are not particularly limited, but are preferably as low as possible. For example, when ionic impurities are contained, bromide ion (Br ⁻ ) nitrate ion (NO ₃ ⁻ ), sulfate ion (SO ₃ ⁻ ) ₄ ⁻ ), nitrite ion (NO ₂ ⁻ ), phosphate ion (PO ₄ ³⁻ ), sodium ion (Na ⁺ ), ammonium ion (NH ₄ ⁺ ), and calcium ion (Ca ²⁺ ) are 30 ppm or less, respectively. Preferably, there is.

Accordingly, the present invention includes a polyphenylene ether compound having a group represented by the following formula (1) at a molecular terminal, and a crosslinking agent having a carbon-carbon unsaturated double bond in the molecule;

[In the formula (1), R ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ₂ represents an alkylene group having 1 to 10 carbon atoms. ]
A resin composition characterized in that the amount of chloride ions in the resin composition or the semi-cured product of the resin composition is 40 ppm or less.

In the present embodiment, the “semi-cured material” is a resin composition in which the resin composition has been cured halfway so that it can be further cured. That is, the semi-cured product is a semi-cured resin composition (B-staged). For example, when heated, the viscosity of the resin composition first decreases gradually, and thereafter, the curing starts, and the viscosity gradually increases. In such a case, the semi-cured state includes a state after the viscosity starts to increase and before complete curing.

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 may include the resin composition that is not cured. It may be provided with itself. That is, a prepreg including a semi-cured product of the resin composition (the B-stage resin composition) and a fibrous base material may be used, or the resin composition before curing (the A-stage resin composition) ) And a prepreg comprising a fibrous base material. Specifically, for example, a resin composition in which a fibrous base material exists in the resin composition may be used. In addition, the resin composition or the semi-cured product thereof may be obtained by drying or heating and drying the resin composition.

As a method for producing the prepreg 1 of the present embodiment using the varnish-like resin composition of the present embodiment, for example, a resin varnish-like resin composition 2 is impregnated into a fibrous base material 3 and then dried. Method.

Specific examples of the fibrous base material used in producing the prepreg include, for example, glass cloth, aramid cloth, polyester cloth, LCP (liquid crystal polymer) nonwoven cloth, glass nonwoven cloth, aramid nonwoven cloth, polyester nonwoven cloth, pulp paper, And linter paper. When a glass cloth is used, a laminate having excellent mechanical strength can be obtained, and particularly, a flattened glass cloth is preferable. The glass cloth used in the present embodiment is not particularly limited, and examples thereof include E glass, S glass, NE glass, low dielectric glass cloth such as Q glass and L glass. Specifically, for example, the flattening treatment can be performed by continuously pressing the glass cloth with an appropriate pressure with a press roll to compress the yarn flatly. As the thickness of the fibrous base material, for example, a thickness of 0.01 to 0.3 mm can be generally used.

繊維 The impregnation of the fibrous base material 3 with the resin varnish (resin composition 2) is performed by dipping and coating. This impregnation can be repeated a plurality of times as necessary. At this time, it is also possible to repeat the impregnation using a plurality of resin varnishes having different compositions and concentrations to finally adjust the composition (content ratio) and the desired resin amount to the desired values.

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

As shown in FIG. 4, the resin-attached metal foil 31 of the present embodiment has a configuration in which the resin layer 32 containing the above-described resin composition or a semi-cured product of the resin composition and the metal foil 13 are laminated. Having. That is, the resin-attached metal foil of the present embodiment may be a resin-attached metal foil including the resin layer containing the resin composition before curing (the A-stage resin composition) and a metal foil, It may be a resin-attached metal foil including a resin layer containing a semi-cured product of the resin composition (the B-stage resin composition) and a metal foil.

方法 As a method of manufacturing such a resin-attached metal foil 31, for example, a method of applying the resin varnish-like resin composition as described above to the surface of the metal foil 13 such as a copper foil, followed by drying. Examples of the coating method include a bar coater, a comma coater, a die coater, a roll coater, and a gravure coater.

、 As the metal foil 13, a metal foil used for a metal-clad laminate, a wiring board, or the like can be used without limitation, and examples thereof include a copper foil and an aluminum foil.

Further, as shown in FIG. 5, the resin-attached film 41 of the present embodiment has a resin layer 42 containing the above-described resin composition or a semi-cured product of the resin composition, and a film supporting substrate 43 laminated thereon. Having a configuration. That is, the resin-attached film of the present embodiment may be a resin-attached film including the resin composition before curing (the A-stage resin composition) and a film supporting substrate, or may be a resin-attached film. And a resin-attached film comprising a semi-cured product of the above (B-stage resin composition) and a film supporting substrate.

As a method for manufacturing such a resin-attached film 41, for example, after applying the resin varnish-like resin composition as described above to the surface of the film supporting base material 43, the solvent is volatilized from the varnish to reduce the solvent. By causing the solvent or removing the solvent, a resin-coated film before curing (A stage) or in a semi-cured state (B stage) can be obtained.

Examples of the film supporting substrate include electrical insulating films such as polyimide films, PET (polyethylene terephthalate) films, polyester films, polyparabanic acid films, polyetheretherketone films, polyphenylene sulfide films, aramid films, polycarbonate films, and polyarylate films. And the like.

In the resin-attached film and the resin-attached metal foil of the present embodiment, the resin composition or the semi-cured product thereof may be obtained by drying or heating and drying the resin composition, as in the case of the prepreg described above.

厚み The thickness and the like of the metal foil 13 and the film support base 43 can be appropriately set according to a desired purpose. For example, a metal foil 13 having a thickness of about 0.2 to 70 μm can be used. When the thickness of the metal foil is, for example, 10 μm or less, a copper foil with a carrier provided with a release layer and a carrier may be used to improve the handleability. The application of the resin varnish to the metal foil 13 and the film support base 43 is performed by coating or the like, but this can be repeated a plurality of times as necessary. Further, at this time, it is also possible to repeatedly apply by using a plurality of resin varnishes having different compositions and concentrations to finally adjust the composition (content ratio) and the amount of the resin to the desired values.

The drying or heating and drying conditions in the method for producing the resin-attached metal foil 31 and the resin film 41 are not particularly limited, but after applying the resin varnish-like resin composition to the metal foil 13 or the film supporting base material 43, By heating at 80 to 170 ° C. for about 1 to 10 minutes to evaporate the solvent from the varnish and reduce or remove the solvent, a pre-curing (A stage) or semi-curing state (B stage) The resin-coated metal foil 31 and the resin film 41 are obtained.

金属 The resin-attached metal foil 31 and the resin film 41 may be provided with a cover film or the like as necessary. The provision of the cover film can prevent foreign substances from being mixed. The cover film is not particularly limited as long as it can be peeled off without damaging the form of the resin composition. For example, a polyolefin film, a polyester film, a TPX film, and a release agent Films formed by providing layers, and paper or the like obtained by laminating these films on a paper substrate can be used.

As shown in FIG. 2, the metal-clad laminate 11 of the present embodiment includes an insulating layer 12 containing a cured product of the above-described resin composition or a cured product of the above-described prepreg, and a metal foil 13. I do. In addition, as the metal foil 13 used in the metal-clad laminate 11, the same metal foil 13 as described above can be used.

金属 Moreover, the metal-clad laminate 13 of this embodiment can also be produced using the above-mentioned resin-attached metal foil 31 or resin film 41.

As a method of manufacturing a metal-clad laminate using the prepreg 1, the resin-coated metal foil 31 or the resin film 41 obtained as described above, the prepreg 1, the resin-coated metal foil 31 or the resin film 41 may be used as one sheet or By laminating a plurality of sheets, further stacking a metal foil 13 such as a copper foil on both upper and lower surfaces or one surface thereof, forming the laminate by heating and pressing, and forming a double-sided metal foil-clad or single-sided metal foil-clad laminate. It can be produced. The heating and pressing conditions can be appropriately set depending on the thickness of the laminate to be manufactured, the type of the resin composition, and the like. For example, the temperature is 170 to 220 ° C., the pressure is 1.5 to 5.0 MPa, and the time is 60. It can be up to 150 minutes.

金属 Moreover, the metal-clad laminate 11 may be produced by forming a film-shaped resin composition on the metal foil 13 without using the prepreg 1 or the like, and applying heat and pressure.

Then, as shown in FIG. 3, the wiring board 21 of the present embodiment includes the insulating layer 12 including the cured product of the above-described resin composition or the cured product of the above-described prepreg, and the wiring 14.

樹脂 The resin composition of the present embodiment is preferably used as a material for an interlayer insulating layer of a wiring board. Although not particularly limited, for example, it is preferably used as a material of an interlayer insulating layer of a multilayer wiring board having 10 or more circuit layers, and more preferably 15 or more layers.

復 As a material of the interlayer insulating layer, it is preferable to use a plurality of insulating layers made of the resin composition of the present embodiment. Although not particularly limited, for example, it is preferable to use 10 or more layers. As a result, in the multilayer wiring board, the density of the conductive circuit patterns can be further increased, and the lower dielectric properties of the plurality of interlayer insulating layers, the insulation reliability between the conductive circuit patterns, and the insulating property between the interlayer circuits can be improved. It can be improved. Further, effects such as an increase in signal transmission speed in the multilayer wiring board and a reduction in signal transmission loss can be obtained.

As a method for manufacturing such a wiring board 21, for example, a circuit (wiring) is formed by etching the metal foil 13 on the surface of the metal-clad laminate 13 obtained above to form a circuit (wiring). A wiring board 21 provided with a conductor pattern (wiring 14) as a circuit can be obtained. As a method of forming a circuit, in addition to the method described above, for example, a circuit formation by a semi-additive method (SAP: Semi @ Additive @ Process) or a modified semi-additive method (MSAP: Modified @ Semi @ Additive @ Process) may be mentioned.

By using the resin composition of the present embodiment, excellent insulation reliability can be obtained even on a wiring board on which a circuit as described above is formed, and a substrate having a conductive circuit pattern in which the distance between circuits is 150 μm or less. Can be secured. Here, the distance between circuits means a distance (space) S between two adjacent wirings (conductor circuits) (L), as shown in FIG. Further, in the wiring board of the present embodiment, the distance between the circuits does not need to be all 150 μm or less, and it is sufficient that at least a part has a distance between the circuits of 150 μm or less.

By providing a substrate having a conductor circuit pattern including at least a portion where the distance between circuits is 150 μm or less in the substrate in this way, the conductor circuit pattern in the substrate can be further increased in density, and The substrate can be made smaller. In addition, by including a conductor circuit pattern having a conductor circuit width of 150 μm or less, the density of the conductor circuit pattern can be further increased. Furthermore, a part of the signal line of the conductor circuit pattern can be shortened, so that transmission loss can be further reduced and high-speed transmission can be performed.

により By using the resin composition of the present embodiment, even when the circuit distance is small, the resin composition of the present embodiment can exhibit the above-described effects (insulation reliability). For example, insulation reliability can be exhibited even when the distance between the conductor circuits is 150 μm or less, or 100 μm or less, 75 μm or less, and even 50 μm or less. Therefore, it is considered that the resin composition of the present embodiment is suitably used for a wiring (circuit) substrate having a small distance between wirings. Still further, in a wiring board, in a multilayer wiring board having a conductive through hole or / and a conductive via, between adjacent conductive through holes formed in an insulating layer and / or between conductive vias. Excellent insulation reliability is obtained.

The prepreg, film with resin, and metal foil with resin obtained by using the resin composition of the present embodiment have low dielectric properties, high Tg, insulation reliability, and the like in the cured product. Useful for The metal-clad laminates and wiring boards containing them also have low dielectric properties, high Tg, and excellent insulation reliability.

This specification discloses various aspects of the technology as described above, and the main technologies are summarized below.

[In the formula (1), R ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ₂ represents an alkylene group having 1 to 10 carbon atoms. ]
According to such a configuration, a resin composition having low dielectric properties, high Tg, and excellent insulation reliability in a cured product can be provided.

A resin composition according to another embodiment of the present invention comprises a polyphenylene ether compound having a group represented by the following formula (1) at a molecular terminal, a crosslinking agent having a carbon-carbon unsaturated double bond in a molecule, Including at least one of a crosslinking agent that reacts with the polyphenylene ether compound and cures,

[In the formula (1), R ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ₂ represents an alkylene group having 1 to 10 carbon atoms. ], And
The resin composition or the semi-cured resin composition has a chloride ion content of 40 ppm or less.

も Even with such a configuration, it is possible to provide a resin composition having low dielectric properties, high Tg, and excellent insulation reliability in a cured product.

The crosslinking agent may be a trialkenyl isocyanurate compound, a polyfunctional acrylate compound having two or more acryl groups in the molecule, a polyfunctional methacrylate compound having two or more methacryl groups in the molecule, or a vinyl compound having two or more vinyl groups in the molecule. It is preferable to include at least one selected from the group consisting of a polyfunctional vinyl compound having at least one compound, an allyl compound, a maleimide compound, and an acenaphthylene compound.

Thereby, it is considered that crosslinking is more preferably formed by the curing reaction, and there is an advantage that the heat resistance of the cured product of the resin composition used in the present embodiment can be further increased.

Furthermore, it is preferable that the polyphenylene ether compound has a structure represented by the following formula (2).

(In the formula (2), R ₃ to R ₁₀ each 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. Is a group represented by the formula (1).)

中 In the formula (2), A and B are structures represented by the following formulas (3) and (4), respectively:

(In the formulas (3) and (4), m and n each represent an integer of 0 to 20. R ₁₁ to R ₁₄ and R ₁₅ to R ₁₈ each independently represent a hydrogen atom or an alkyl group. )
Further, in the formula (2), Y is a structure represented by the following formula (5):

(In the formula (5), R ₁₉ and R ₂₀ each independently represent a hydrogen atom or an alkyl group.)

効果 With such a configuration, it is considered that the above-described effects can be obtained more reliably.

樹脂 Further, it is preferable that the resin composition is for a wiring board provided with a conductor circuit pattern in which the distance between conductor circuits is at least partially 100 μm or less. In such an application, it is considered that the effect of the present invention is more exhibited.

プリ A prepreg according to still another aspect of the present invention includes the above resin composition or a semi-cured product of the resin composition and a fibrous base material.

樹脂 A resin-attached film according to still another aspect of the present invention is characterized by having a resin film containing the above-described resin composition or a semi-cured product of the resin composition, and a support film.

樹脂 A resin-attached metal foil according to still another aspect of the present invention includes a resin layer containing the above-described resin composition or a semi-cured product of the resin composition, and a metal foil.

金属 A metal-clad laminate according to still another aspect of the present invention is characterized by having an insulating layer containing a cured product of the above resin composition or a cured product of the above prepreg, and a metal foil.

配線 Further, a wiring board according to still another aspect of the present invention is characterized by having an insulating layer containing a cured product of the above-described resin composition or a cured product of the above-described prepreg, and wiring.

According to the configuration described above, a prepreg, a film with a resin, a metal foil with a resin, a metal-clad laminate, and a wiring, which can obtain a substrate having low dielectric properties and high Tg and further having excellent insulation reliability, can be obtained. A substrate or the like can be obtained.

The present invention will be described more specifically with reference to the following examples, but the scope of the present invention is not limited thereto.

First, in this example, components used when preparing a resin composition will be described.

<A component: polyphenylene ether compound>
-Modified PPE-1: Bifunctional vinylbenzyl-modified PPE (Mw: 1900)
First, a modified polyphenylene ether (modified PPE-1) was synthesized. The average number of phenolic hydroxyl groups at the molecular terminals per molecule of polyphenylene ether is indicated as the number of terminal hydroxyl groups.

(Iv) Polyphenylene ether was reacted with chloromethylstyrene to obtain modified polyphenylene ether 1 (modified PPE-1). Specifically, first, a polyphenylene ether (SA90, manufactured by SABIC Innovative Plastics Co., Ltd .; 0.083 dl / g, number of terminal hydroxyl groups: 1.9, weight molecular weight Mw: 1700) 200 g, 30 g of a mixture of p-chloromethylstyrene and m-chloromethylstyrene in a mass ratio of 50:50, tetra-n as a phase transfer catalyst 1.227 g of -butylammonium bromide and 400 g of toluene were charged and stirred. Then, the mixture was stirred until the polyphenylene ether, chloromethylstyrene, and tetra-n-butylammonium bromide were dissolved in toluene. At that time, the mixture was gradually heated and finally heated until the liquid temperature reached 75 ° C. Then, an aqueous solution of sodium hydroxide (20 g of sodium hydroxide / 20 g of water) as an alkali metal hydroxide was added dropwise to the solution over 20 minutes. Thereafter, the mixture was further stirred at 75 ° C. for 4 hours. Next, after neutralizing the contents of the flask with 10% by mass of hydrochloric acid, a large amount of methanol was added. Doing so caused a precipitate in the liquid in the flask. That is, the product contained in the reaction solution in the flask was reprecipitated. The precipitate was taken out by filtration, washed three times with a mixed solution of methanol and water at a mass ratio of 80:20, and dried under reduced pressure at 80 ° C. for 3 hours.

The obtained solid was analyzed by ¹ H-NMR (400 MHz, CDCl ₃ , TMS). As a result of NMR measurement, a peak derived from a vinylbenzyl group was confirmed at 5 to 7 ppm. Thus, it was confirmed that the obtained solid was a modified polyphenylene ether having a group represented by the formula (1) at a molecular terminal. Specifically, it was confirmed that the polyphenylene ether was vinylbenzylated.

(4) The molecular weight distribution of the modified polyphenylene ether was measured using GPC. The weight average molecular weight (Mw) was calculated from the obtained molecular weight distribution, and as a result, Mw was 1,900.

{Circle around (2)} The number of terminal functional groups of the modified polyphenylene ether was measured as follows.

First, the modified polyphenylene ether was accurately weighed. The weight at that time is defined as X (mg). Then, the weighed modified polyphenylene ether was dissolved in 25 mL of methylene chloride, and an ethanol solution of 10% by mass of tetraethylammonium hydroxide (TEAH) (TEAH: ethanol (volume ratio) = 15: 85) was added to the solution. After adding 100 μL, the absorbance (Abs) at 318 nm was measured using a UV spectrophotometer (UV-1600 manufactured by Shimadzu Corporation). Then, from the measurement results, the number of terminal hydroxyl groups of the modified polyphenylene ether was calculated using the following equation.

Residual OH amount (μmol / g) = [(25 × Abs) / (ε × OPL × X)] × 106
Here, ε indicates the extinction coefficient, which is 4700 L / mol · cm. OPL is the cell optical path length, which is 1 cm.

The calculated residual OH content (the number of terminal hydroxyl groups) of the modified polyphenylene ether was almost zero, indicating that the hydroxyl groups of the polyphenylene ether before modification were substantially modified. From this, it was found that the decrease from the number of terminal hydroxyl groups of the polyphenylene ether before modification was the number of terminal hydroxyl groups of the polyphenylene ether before modification. That is, it was found that the number of terminal hydroxyl groups of the polyphenylene ether before modification was the number of terminal functional groups of the modified polyphenylene ether. That is, the number of terminal functional groups was two.

The amount of impurity ions in the modified polyphenylene ether compound was determined by adding 15 g of pure water to 0.75 g of the sample (obtained modified PPE-1), extracting the mixture at 125 ° C. for 20 hours, and then performing ion chromatography (using model “ICS1500”). "Thermo Fisher Co., separation column: IonPac AS 22, _{_{eluent: 4.5mmol / L Na 2 CO 3}} /1.4mmol/L NaHCO 3, eluent flow rate was measured by 1.5 mL / min). As a result, the amount of various impurity ions in the modified PPE-1 was 1912 ppm of Cl ⁻ ions in terms of solid content. As other ions other than Cl ⁻ ions, Br ⁻ ions are less than 2 ppm, NO ₃ ⁻ ions are 10 ppm, SO ₄ ⁻ ions are 2 ppm, NO ₂ ⁻ ions are less than 2 ppm, PO ₄ ³⁻ ions are less than 2 ppm, and Na ⁺ The ions were less than 2 ppm and the NH ₄ ⁺ ions were 12 ppm.

-Modified PPE-2: Bifunctional vinylbenzyl-modified PPE (Mw: 1900)
The step of introducing methanol to form a precipitate in the liquid in the flask, that is, the step of reprecipitating the product contained in the reaction solution in the flask, and the step of removing the precipitate by filtration are performed three times ( 3 sets) A modified PPE-2 was obtained in the same manner as the modified PPE-1, except that this was repeated.

The amounts of various impurity ions in the obtained modified PPE-2 were measured in the same manner as in the modified PPE-1. As a result, Cl ⁻ ion was 42 ppm, Br ⁻ ion was less than 2 ppm, and NO ₃ ⁻ ion was 29 ppm in terms of solid content. , SO ₄ ^- ion was less than ₂ ppm, NO ₂ ^- ion was less than 2 ppm, PO ₄ ^3- ion was less than 2 ppm, Na ⁺ ion was less than 2 ppm, and NH ₄ ⁺ ion was 27 ppm.

-Modified PPE-3: Bifunctional vinylbenzyl-modified PPE (Mw: 1900)
The step of introducing methanol to form a precipitate in the liquid in the flask, that is, the step of reprecipitating the product contained in the reaction solution in the flask, and the step of removing the precipitate by filtration are performed twice ( Modified PPE-3 was obtained in the same manner as Modified PPE-1, except for repeating 2 sets).

The amount of various impurity ions in the obtained modified PPE-3 was measured in the same manner as in the modified PPE-1, and as a result, Cl ^- ion was 42 ppm, Br ^- ion was 2 ppm, NO ₃ ^- ion was 41 ppm, and SO ₄ ^- ions were less than 2 ppm, NO ₂ ^- ions were less than 2 ppm, PO ₄ ^3- ions were less than 2 ppm, Na ions ⁺ were 8 ppm, and NH ₄ ⁺ ions were 20 ppm.

-Modified PPE-4: Bifunctional vinylbenzyl-modified PPE (Mw: 1900)
Instead of a mixture of p-chloromethylstyrene and m-chloromethylstyrene at a mass ratio of 50:50 in the modified PPE synthesis process, o-chloromethylstyrene, p-chloromethylstyrene, m-chloromethylstyrene and Using a mixture having a mass ratio of 20:10:70 and adding methanol to form a precipitate in the liquid in the flask, that is, a step of reprecipitating the product contained in the reaction solution in the flask A modified PPE-4 was obtained in the same manner as the modified PPE-1, except that the step of removing the precipitate by filtration was repeated three times (three sets).

The amount of various impurity ions in the obtained modified PPE-4 was measured in the same manner as in the modified PPE-1, and as a result, Cl ^- ion was 31 ppm in terms of solid content. The other ions are less than 2 ppm of Br ^- ion, less than 2 ppm of NO ₃ ^- ion, less than 2 ppm of SO ₄ ^- ion, less than 2 ppm of NO ₂ ^- ion, less than 2 ppm of PO ₄ ^3- ion, and less than 2 ppm of Na ⁺ ion. 8 ppm and 10 ppm of NH ₄ ⁺ ions.

SA-9000: bifunctional methacrylate-modified PPE (Mw: 1700, manufactured by SABIC, Cl ion amount: less than 2 ppm)
OPE-2St 2200: PPE modified with vinyl vinyl terminal (Mw: about 3600, manufactured by Mitsubishi Gas Chemical Company, Inc., Cl ion amount: 1350 ppm)

<Component B: crosslinking agent>
・ TAIC: triallyl isocyanurate, (Nippon Kasei Co., Ltd.)
・ DVB810: divinylbenzene (Nippon Steel & Sumikin Chemical Co., Ltd.)
・ DCP: dicyclopentadiene type methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

<Other ingredients>
(Inorganic filler)
・ SC2300-SVJ: Methacrylsilane surface-treated spherical silica (manufactured by Admatechs Co., Ltd.)
(Flame retardants)
・ SAYTEX8010: Brominated flame retardant (Albemarle Japan Co., Ltd.)

<Examples 1 to 5, Comparative Examples 1 to 3>
[Preparation method]
(Resin varnish)
First, each component was added to toluene and mixed at a mixing ratio (parts by mass) shown in Table 1 so that the solid content concentration was about 60% by mass. The mixture was stirred at 30 ° C. for 60 minutes to obtain a varnish-like resin composition (varnish).

(Preparation of prepreg)
・ Prepreg I
The resin varnish of each Example and Comparative Example was impregnated in a glass cloth (L2116 type, manufactured by Asahi Kasei Corporation), and then heated and dried at 130 ° C. for about 3 minutes to obtain a prepreg. At that time, the content of the resin composition (resin content) with respect to the weight of the prepreg was adjusted to be about 56% by mass.

・ Prepreg II
The resin varnish of each Example and Comparative Example was impregnated into a glass cloth (L1078 type, manufactured by Asahi Kasei Corporation), and then heated and dried at 130 ° C. for about 2 minutes to obtain a prepreg. At that time, the content of the resin composition (resin content) with respect to the weight of the prepreg was adjusted to be about 70% by mass.

(Production of copper-clad laminate)
・ Copper clad laminate I
Six prepregs each having copper foil (GT-MP manufactured by Furukawa Electric Co., Ltd.) placed on both sides of each of the six prepregs to form a pressure-receiving body under a vacuum condition at a temperature of 210 ° C. and a pressure of 30 kgf / cm ² . The mixture was heated and pressed under the conditions for 90 minutes to obtain a copper-clad laminate having a thickness of about 0.75 mm and a copper foil bonded to both sides.

・ Laminated plate II
Two sheets of the prepreg-II are stacked, and a copper foil (FV-WS, manufactured by Furukawa Electric Co., Ltd.) having a thickness of 18 μm is arranged on both sides of the prepreg-II to form a pressure-receiving body. The temperature is 210 ° C., the pressure is 30 kgf / cm. Heating and pressing were performed for 90 minutes under the conditions of ² to obtain a copper-clad laminate-II 'having a thickness of about 0.18 mm and a copper foil bonded to both sides. The obtained laminated plate-II ′ is exposed to a circuit pattern including a portion having a conductor circuit width of 100 μm using a dry film, and copper is etched with a copper chloride aqueous solution. To obtain a laminated plate-II ″. The conductor circuit pattern includes a circuit pattern in which a conductor circuit 51 is formed in an inner layer such that L (conductor circuit width) / S (distance between conductor circuits): 100 μm / 100 μm as shown in FIG. A comb-shaped pattern (number of lines: 15; line overlapping portion: 65 mm) for evaluating insulation reliability was obtained. The prepreg-II was placed on both sides of the obtained laminate-II ″, and FV-WS copper foil having a thickness of 18 μm was placed on both outer sides thereof. The temperature was 210 ° C. and the pressure was 30 kgf under vacuum conditions. / Cm ² for 90 minutes to obtain a laminate II having a distance between conductor circuits of 100 μm.

<Evaluation test>
[Dielectric properties (relative permittivity and dielectric loss tangent)]
The relative permittivity and the dielectric loss tangent of the evaluation board at 1 GHz were measured using a material / impedance analyzer (HP4291A and HP16453A manufactured by Hewlett-Packard Co.). As the evaluation board, a laminate obtained by removing the copper foil from the copper-clad laminate I was used. The measurement was performed by a method based on PC-TM-650 2.5.5.9.

[Glass transition temperature (Tg)]
The outer copper foil of the copper-clad laminate I was entirely etched, and the glass transition point (Tg) of the obtained sample was measured using a differential scanning calorimeter (DSC). The measurement was performed by a method based on IPC-TM-650 2.4.25.

[Insulation reliability]
Using the laminated plate II, a voltage of 100 V was applied for 500 hours in an environment of 85 ° C. and a humidity of 85%, and the resistance value was continuously measured every hour. A sample whose resistance value did not deteriorate to 10 ＾ 7Ω or less even after 500 hours of application was evaluated as pass (合格), and a sample whose resistance deteriorated to 10 ＾ 7Ω or less was rejected (×).

The above results are shown in Table 1 below.

[Amount of impurity ions in prepreg]
Further, in Example 1-2 and Comparative Example 1, the amount of Cl ions in the prepreg was also measured. Specifically, the resin component of the prepreg I was sieved (100 mesh under, 200 mesh up) to prepare 0.75 g. After adding it to 15 g of pure water and extracting at 125 ° C. for 20 hours, ion chromatography (used model “ICS1500” manufactured by Thermo Fisher, separation column: Ionpac AS22, eluent: 4.5 mmol / L Na ₂ CO ₃₎ /1.4 mmol / L NaHCO ₃ , eluent flow rate: 1.5 mL / min) to measure the amounts of various impurity ions. The limit of the amount of impurity ions that can be detected using the above-described ion chromatography apparatus is up to 2 ppm, and the amount of impurity ions having a lower detection amount is less than 2 ppm.

As a result, the amount of each impurity ion in Example 1 was 7 ppm for Cl ⁻ ions. As other ions other than Cl ^- ions, Br ^- ions are less than 2 ppm, NO ₃ ^- ions are 17 ppm, SO ₄ ^- ions are 3 ppm, NO ₂ ^- ions are less than 2 ppm, PO ₄ ^3- ions are less than 2 ppm, Na is less than 2 ppm. ⁺ Ions were less than 2 ppm, NH ₄ ⁺ ions were 10 ppm, and Ca ions were 5 ppm.

In Example 2, Cl ⁻ ion was 29 ppm. As other ions other than Cl ^- ions, Br ^- ions are less than 2 ppm, NO ₃ ^- ions are 7 ppm, SO ₄ ^- ions are 2 ppm, NO ₂ ^- ions are less than 2 ppm, PO ₄ ^3- ions are less than 2 ppm, Na is less than 2 ppm. ⁺ Ions were less than 2 ppm, NH ₄ ⁺ ions were 9 ppm, and Ca ²⁺ ions were 5 ppm.

In Example 6, Cl ⁻ ion was 4 ppm. As other ions other than Cl ⁻ ions, Br ⁻ ions are less than 2 ppm, NO ₃ ⁻ ions are 7 ppm, SO ₄ ⁻ ions are 7 ppm, NO ₂ ⁻ ions are less than 2 ppm, PO ₄ ³⁻ ions are less than 2 ppm, Na is less than 2 ppm. ⁺ Ion was 4 ppm, NH ₄ ⁺ ion was 7 ppm, and Ca ²⁺ ion was 6 ppm. Then, in Comparative Example 1 Cl ^- ions 75 ppm, Br ^- ions is less than 2ppm, NO ₃ ^- ions 15 ppm, SO ₄ ^- ions is less than 2ppm, NO ₂ ^ions is less than 2ppm, _PO ^{4 3-} ions 2ppm , Less than 2 ppm of Na ⁺ ion, less than 7 ppm of NH ₄ ⁺ ion, and less than 2 ppm of Ca ²⁺ ion.

(Discussion)
As is clear from the results shown in Table 1, according to the present invention, a resin composition having excellent insulation reliability in addition to low dielectric properties (Dk: 3.3 or less, Df: 0.0015 or less) and high Tg. It was shown that things could be provided.

On the other hand, in Comparative Examples 1 and 3, in which a polyphenylene ether compound having a large amount of Cl ions was used, sufficient insulation reliability could not be obtained. In Comparative Example 2 using a polyphenylene ether compound having no group represented by the above formula (1) at the molecular end, the result was inferior to Tg.

This application is based on Japanese Patent Application No. 2018-174980 filed on Sep. 19, 2018, the contents of which are included in the present application.

In order to express the present invention, the present invention has been described above appropriately and sufficiently through the embodiments with reference to specific examples and drawings. However, those skilled in the art may modify and / or improve the above-described embodiments. It should be recognized that is easy to do. Therefore, unless a modification or improvement performed by a person skilled in the art is at a level that departs from the scope of the claims set forth in the claims, the modification or the improvement shall not cover the scope of the claims. Is interpreted as being included in

The present invention has wide industrial applicability in the technical field related to electronic materials and various devices using the same.

Claims

A polyphenylene ether compound having a group represented by the following formula (1) at a molecular terminal:
A cross-linking agent having a carbon-carbon unsaturated double bond in the molecule or at least one of a cross-linking agent which is cured by reacting with the polyphenylene ether compound,
A resin composition, wherein the amount of chloride ions in the polyphenylene ether compound is 250 ppm or less.

[In the formula (1), R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 2 represents an alkylene group having 1 to 10 carbon atoms. ]
A polyphenylene ether compound having a group represented by the following formula (1) at a molecular terminal:
Including at least one of a cross-linking agent having a carbon-carbon unsaturated double bond in the molecule or a cross-linking agent which is cured by reacting with the polyphenylene ether compound;

[In the formula (1), R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 2 represents an alkylene group having 1 to 10 carbon atoms. ], And
The resin composition, wherein the amount of chloride ions in the resin composition or the semi-cured product of the resin composition is 40 ppm or less.
The crosslinking agent is a trialkenyl isocyanurate compound, a polyfunctional acrylate compound having two or more acryl groups in a molecule, a polyfunctional methacrylate compound having two or more methacryl groups in a molecule, two or more vinyl groups in a molecule. The resin composition according to claim 1, further comprising at least one selected from the group consisting of a polyfunctional vinyl compound, an allyl compound, a maleimide compound, and an acenaphthylene compound.
4. The resin composition according to claim 1, wherein the polyphenylene ether compound has a structure represented by the following formula (2).

(In the formula (2), R 3 to R 10 each 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. Is a group represented by the formula (1).)
In the formula (2), A and B are structures represented by the following formulas (3) and (4), respectively:

(In the formulas (3) and (4), m and n each represent an integer of 0 to 20. R 11 to R 14 and R 15 to R 18 each independently represent a hydrogen atom or an alkyl group. )
Further, in the formula (2), Y is a structure represented by the following formula (5):

(In the formula (5), R 19 and R 20 each independently represent a hydrogen atom or an alkyl group.)
(5) The resin composition according to any one of (1) to (4), which is used for a wiring board provided with a conductor circuit pattern in which the distance between conductor circuits is at least partially 150 μm or less.
A prepreg comprising the resin composition according to any one of claims 1 to 4, 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 claim 1 or a semi-cured product of the resin composition; and a support film.
(5) A resin-attached metal foil, comprising: a resin layer containing the resin composition according to claim 1 or a semi-cured product of the resin composition; and a metal foil.
[4] A metal-clad laminate having an insulating layer containing a cured product of the resin composition according to any one of claims 1 to 4 or a cured product of the prepreg according to claim 6, and a metal foil.
(4) A wiring substrate, comprising: an insulating layer containing the cured product of the resin composition according to any one of claims 1 to 5 or the cured product of the prepreg according to claim 6; and a wiring.