CN112469750A

CN112469750A - Resin composition, prepreg using same, resin-containing film, resin-containing metal foil, metal-clad laminate, and wiring board

Info

Publication number: CN112469750A
Application number: CN201980048204.3A
Authority: CN
Inventors: 井之上裕辉; 阿部智之; 有泽达也
Original assignee: Panasonic Intellectual Property Management Co Ltd
Current assignee: Panasonic Intellectual Property Management Co Ltd
Priority date: 2018-09-19
Filing date: 2019-09-09
Publication date: 2021-03-09
Also published as: JPWO2020059562A1; TW202022017A; WO2020059562A1

Abstract

One aspect of the present invention relates to a resin composition comprising: a polyphenylene ether compound having a group represented by the following formula (1) at a molecular end; and a crosslinking agent having a carbon-carbon unsaturated double bond in the molecule, and curing the polyphenylene ether compound by reacting with the crosslinking agentWherein the amount of chloride ions in the polyphenylene ether compound is 250ppm or less,

in the formula (1), R₁R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms₂Represents an alkylene group having 1 to 10 carbon atoms.

Description

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

Technical Field

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

Background

In recent years, with an increase in the amount of information processing, various electronic devices have been rapidly developed in mounting technologies such as high integration of semiconductor devices mounted thereon, high density of wiring, and multilayering. A substrate material used for forming a printed wiring board substrate used in various electronic devices is required to have a low dielectric constant and a low dielectric loss tangent so as to increase a signal transmission speed and reduce a loss during signal transmission.

In response to this demand, resin compositions containing a polyphenylene ether (PPE) compound having a modified end are used as materials having excellent electrical characteristics (for example, patent documents 1 and 2). It has also been reported that: a wiring board or the like made of a resin composition containing a PPE compound has excellent transmission characteristics.

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

However, the resin composition described in patent document 1 is considered to have low dielectric characteristics, but the present inventors have studied and found that: due to the influence of the chloride ion residue used in the terminal modification (divinylbenzene-modified modification), there is a case where sufficient insulation reliability cannot be secured in the production of a printed wiring board using the resin composition. In particular, in a wiring board provided with a conductor circuit pattern having a small distance between conductor circuits, the influence is more significant.

On the other hand, when only the modified PPE used in patent document 2 is used, the reactivity is poor, and the Tg is lowered. A reaction initiator is required to solve this problem, but there is a difficulty that the electrical characteristics (low dielectric characteristics and transmission characteristics) are deteriorated by the influence of the initiator.

The present invention has been made in view of the above circumstances, and an object thereof is to: provided is a resin composition, wherein a cured product of the resin composition has low dielectric characteristics (low dielectric constant and dielectric dissipation factor), high Tg, and insulation reliability. Furthermore, it aims to: a prepreg, a film with a resin, a metal foil-clad laminate and a wiring board using the resin composition are provided.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2011-68713

Patent document 2: japanese patent laid-open publication No. 2004-511580

Disclosure of Invention

One aspect of the present invention relates to a resin composition comprising: a polyphenylene ether compound having a group represented by the following formula (1) at a molecular end; and a crosslinking agent having a carbon-carbon unsaturated double bond in the molecule and a crosslinking agent which reacts with the polyphenylene ether compound and cures the polyphenylene ether compound, wherein the amount of chloride ions in the polyphenylene ether compound is 250ppm or less.

[ in the formula (1), R₁R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms₂Represents an alkylene group having 1 to 10 carbon atoms.]

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided a resin composition comprising: a cured product of the resin composition has low dielectric characteristics, high Tg and excellent insulation reliability. Further, according to the present invention, by using the resin composition, a prepreg, a resin-attached film, a resin-attached metal foil, a metal-clad laminate, and a wiring board having excellent properties can also be provided.

Drawings

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

Fig. 2 is a schematic cross-sectional view showing the structure of a metal-clad laminate according to an embodiment of the present invention.

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

Fig. 4 is a schematic cross-sectional view showing a structure of a metal foil with resin according to an embodiment of the present invention.

Fig. 5 is a schematic cross-sectional view showing a structure of a resin film according to an embodiment of the present invention.

Fig. 6 is a schematic view showing a distance (interval) S between two adjacent wirings (conductor circuits) (L) on a substrate having a conductor circuit pattern according to an embodiment of the present invention.

Fig. 7 is a schematic diagram showing a comb pattern for evaluating insulation reliability in the example.

Detailed Description

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

Hereinafter, each component of the resin composition of the present embodiment will be specifically described.

(polyphenylene ether compound)

The polyphenylene ether compound used in the present embodiment is a compound having a group represented by the above formula (1) at a molecular end and a chloride (Cl)^-) The polyphenylene ether compound having an ionic content of 250ppm or less is not particularly limited. By using the polyphenylene ether compound, occurrence of ion migration can be suppressed, and excellent insulation reliability can be obtained. The polyphenylene ether compound of the present embodiment can react with a crosslinking agent described later without using a reaction initiator, and therefore is not affected by the reaction initiator. Thus, it is believed that: the resin composition of the present embodiment can obtain higher glass transition temperature (Tg) and adhesion while maintaining excellent insulation reliability and low dielectric constant and dielectric loss tangent.

As material characteristics, a material having a high Tg of a cured product may be one of factors for further improving heat resistance (solder heat resistance and the like). In addition, the cured product of the material with high Tg has the following advantages: the value of the thermal expansion coefficient of the material in the higher temperature region becomes smaller. The reason for this is that: generally, the thermal expansion becomes large rapidly at a temperature exceeding the glass transition temperature. That is, if the glass transition temperature is low, the thermal expansion coefficient becomes large 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, and for example, interlayer connection reliability (via hole wall cracking or the like) of the wiring board is deteriorated, and there is a possibility that the wiring board cannot function as a printed board. The reason is considered to be that: in the substrate, the difference in thermal expansion coefficient at high temperature between the insulating layer formed of a cured product of the resin composition and the material of the through hole formed of metal is large, and therefore, cracks are generated in the wall surface of the through hole formed of metal, and the connection reliability is deteriorated.

Cl in polyphenylene ether compound^-The amount of the ion (hereinafter, also simply referred to as Cl ion) is not particularly limited as long as it is 250ppm or less, and more preferably 200ppm or less. Although it is preferable that the amount of the Cl ion is smaller, the molecular end of the polyphenylene ether compound is inevitably mixed to some extent when the group represented by the formula (1) is used for modifying the molecular end, and therefore, there is a fear that the cost is increased in order to reduce the amount of the Cl ion. Therefore, from the viewpoint of cost, it is preferable that the amount of Cl ions in the polyphenylene ether compound is 5ppm or more. More preferably 10ppm or more, more preferably 15ppm or more, and still more preferably 30ppm or more.

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

The polyphenylene ether compound of the present embodiment may contain bromide ions (Br) in addition to the Cl ions described above^-) Nitrate ion (NO)₃ ^-) Sulfate ion (SO)₄ ^-) Nitrite ion (NO)₂ ^-) Phosphate radical ion (PO)₄ ^3-) Sodium ion (Na)⁺) Ammonium ion (NH)₄ ⁺) Plasma impurities. These impurities are not particularly limited, but preferably have as low a concentration as possible, and when these ionic impurities are contained, bromide ion (Br) is preferable^-) Nitrate ion (NO)₃ ^-) Sulfate ion (SO)₄ ^-) Nitrite ion (NO)₂ ^-) Phosphate radical ion (PO)₄ ^3-) Sodium ion (Na)⁺) Ammonium ion (NH)₄ ⁺) Each 50ppm or less.

In the above formula (1), R₁Represents 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 straight or branched. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, and hexyl groups. Among them, a hydrogen atom is preferable.

Further, in the above formula (1), R₂To representAn 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 examples thereof include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene groups. Among them, methylene is preferred.

The group represented by the above formula (1) is not particularly limited, and preferably has at least 1 vinylbenzyl (vinylbenzyl) group selected from p-vinylbenzyl, m-vinylbenzyl, and o-vinylbenzyl groups. It is more preferable to have at least two or more selected from p-vinylbenzyl, m-vinylbenzyl, and o-vinylbenzyl.

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

In the above formula (2), R₃～R₁₀Are independent respectively. Namely, R₃～R₁₀The groups may be the same or different from each other. In addition, R₃～R₁₀Represents 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, hydrogen atom and alkyl group are preferable.

With respect to as R₃～R₁₀Specific examples of the functional groups listed above include the following groups.

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 methyl, ethyl, propyl, hexyl and decyl groups.

The alkenyl group is not particularly limited, and 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 vinyl, allyl, and 3-butenyl groups.

The alkynyl group is not particularly limited, and 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 ethynyl and prop-2-yn-1-yl (propargyl).

The alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group, and 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 acetyl, propionyl, butyryl, isobutyryl, pivaloyl, hexanoyl, octanoyl, and cyclohexylcarbonyl.

The alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group, and 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 acryloyl, methacryloyl, and crotonyl groups.

The alkynyl carbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group, and for example, an alkynyl carbonyl group having 3 to 18 carbon atoms is preferable, and an alkynyl carbonyl group having 3 to 10 carbon atoms is more preferable. Specific examples thereof include propargyl and the like.

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

in the formulas (3) and (4), m and n of each repeating unit represent an integer of 0 to 20.

R₁₁～R₁₈Are independent respectively. Namely, R₁₁～R₁₈The groups may be the same or different from each other. In the present embodiment, R represents₁₁～R₁₈Is a hydrogen atom or an alkyl group.

In the formula (2), Y may be a linear, branched or cyclic hydrocarbon having 20 or less carbon atoms. More specifically, it has a structure represented by the following formula (5):

in the formula (5), R₁₉And R₂₀Each independently represents a hydrogen atom or an alkyl group. Examples of the alkyl group include a methyl group. Examples of the group represented by formula (5) include methylene, methylmethylene, and dimethylmethylene.

In the present embodiment, the weight average molecular weight (Mw) of the polyphenylene ether compound is not particularly limited, and is, for example, preferably 1000 to 5000, and more preferably 1000 to 4000. Here, the weight average molecular weight is a value measured by a general molecular weight measurement method, and specifically, a value measured by Gel Permeation Chromatography (GPC) or the like can be cited. In addition, in the case where the polyphenylene ether compound has repeating units (m, n) in the molecule, these repeating units are preferably numerical values such that the weight average molecular weight of the polyphenylene ether compound falls within the range.

When the weight average molecular weight of the polyphenylene ether compound is within this range, the polyphenylene ether compound has not only excellent low dielectric characteristics of the polyphenylene ether skeleton and excellent heat resistance of the cured product, but also excellent moldability. The reason is considered as follows. When the weight average molecular weight is within the above range, the molecular weight is low as compared with a general polyphenylene ether, and therefore the heat resistance of a cured product tends to be lowered. In this regard, it is believed that: the polyphenylene ether compound of the present embodiment has a structure represented by the above formula (1) at the end, and therefore has high reactivity and can give a cured product having sufficiently high heat resistance. In addition, it is considered that: when the weight average molecular weight of the polyphenylene ether compound is within this range, the molecular weight is higher than that of styrene or divinylbenzene, but the molecular weight is lower than that of a general polyphenylene ether, and therefore, the moldability is also excellent. Thus, it is believed that: by using the polyphenylene ether compound, a composition having not only excellent heat resistance of a cured product but also excellent moldability can be obtained.

The average number of the above-mentioned X substituents (the number of terminal functional groups) per 1 molecule of the modified polyphenylene ether in the polyphenylene ether compound used in the present embodiment is not particularly limited. Specifically, the number of the cells is preferably 1 to 5, and more preferably 1 to 3. If the number of terminal functional groups is too small, it tends to be difficult to obtain a cured product having sufficient heat resistance. If the number of terminal functional groups is too large, the reactivity may become too high, and there is a possibility that, for example, storage stability of the resin composition may be deteriorated or flowability of the resin composition may be deteriorated. That is, when the modified polyphenylene ether is used, there is a possibility that molding defects such as voids are generated at the time of multilayer molding due to insufficient fluidity or the like, for example, and it is difficult to obtain a highly reliable printed wiring board.

The number of terminal functional groups of the polyphenylene ether compound is as follows: a numerical value representing an average value of the above-mentioned substituents per 1 molecule of all polyphenylene ether compounds present in 1 mole of the polyphenylene ether compound, etc. 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 the amount of decrease in the number of hydroxyl groups compared with the polyphenylene ether before modification. The amount of decrease from the number of hydroxyl groups of the polyphenylene ether before modification is the number of terminal functional groups. The number of hydroxyl groups remaining in the polyphenylene ether compound can be determined by adding a quaternary ammonium salt (tetraethylammonium hydroxide) associated with hydroxyl groups to a solution of the polyphenylene ether compound and measuring the UV absorbance of the mixed solution.

The intrinsic viscosity of the polyphenylene ether compound used in the present embodiment is not particularly limited. Specifically, the concentration of the surfactant may be 0.03 to 0.12dl/g, preferably 0.04 to 0.11dl/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. When the intrinsic viscosity is too high, the viscosity becomes high, and sufficient fluidity cannot be obtained, so that the moldability of the cured product tends to be lowered. 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 achieved.

The intrinsic viscosity herein refers to the intrinsic viscosity measured in methylene chloride at 25 ℃, and more specifically, it may be measured, for example, by a viscometer on a 0.18g/45ml methylene chloride solution (liquid temperature 25 ℃). Examples of the viscometer include AVS500 Visco System manufactured by schottky (Schott) corporation.

The resin composition of the present embodiment may contain a thermosetting resin other than the polyphenylene ether compound as described above. Examples of other thermosetting resins that can be used include epoxy resins, phenol resins, amine resins, unsaturated polyester resins, thermosetting polyimide resins, and maleimide compounds. The maleimide compound may be a modified maleimide compound, and specifically, for example, a maleimide compound modified with an organosilicon compound at least in part of the molecule, a maleimide compound modified with an amine compound, or the like can be cited.

The method for synthesizing the polyphenylene ether compound preferably used in the present embodiment is not particularly limited as long as it is a method capable of synthesizing a modified polyphenylene ether compound which has been end-modified with the substituent X as described above and in which the amount of chloride ion of the obtained compound is 250ppm or less. Specifically, for example, a method of reacting a compound having a substituent X and a halogen atom bonded thereto with polyphenylene ether is exemplified.

In the substituent X represented by the above 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 to which the substituent X and the halogen atom are bonded, which is used in the above synthesis method, may be, for example, p-chloromethylstyrene, m-chloromethylstyrene, o-chloromethylstyrene, etc., and one of these compounds may be used alone, or 2 to 3 of these compounds may be used in combination. When two or more kinds of p-chloromethyl styrene, m-chloromethyl styrene, and o-chloromethyl styrene are used in combination, the use ratio (mass ratio) is not particularly limited, and when p-chloromethyl styrene and m-chloromethyl styrene are used in combination, the use ratio (mass ratio, the same applies hereinafter) is preferably about 5 to 95: 95 to 5 of p-chloromethyl styrene and m-chloromethyl styrene, as an example of use. When p-chloromethyl styrene and o-chloromethyl styrene are used in combination, the ratio of p-chloromethyl styrene to o-chloromethyl styrene is preferably about 5 to 95: 95 to 5; when the m-chloromethyl styrene and the o-chloromethyl styrene are used in combination, the use ratio thereof is preferably about 5 to 95: 95 to 5 of m-chloromethyl styrene to o-chloromethyl styrene. When 3 kinds of the compounds are used in combination, the ratio of p-chloromethylstyrene, m-chloromethylstyrene and o-chloromethylstyrene is preferably 20 to 90: 40 to 5.

When two or more of p-chloromethylstyrene, m-chloromethylstyrene and o-chloromethylstyrene are used in combination, it is preferable to use at least one of them as p-chloromethylstyrene. It is preferable to use 40% by weight or more of p-chloromethylstyrene, more preferably 50% by weight or more of p-chloromethylstyrene, and still more preferably 60% by weight or more of p-chloromethylstyrene, based on the total amount of chloromethylstyrene used.

Further, in the case of synthesizing a polyphenylene ether compound having a group represented by the formula (1) by using two or more selected from p-chloromethylstyrene, m-chloromethylstyrene and o-chloromethylstyrene in combination, and the formula (1) in the polyphenylene ether compound contains R₁Is a hydrogen atom and R₂In the case of a vinylbenzyl group which is an alkylene group having 1 carbon atom, the ratio of the p-vinylbenzyl group, the m-vinylbenzyl group, and the o-vinylbenzyl group in the polyphenylene ether compound having a substituent represented by formula (1) after synthesis is represented by the ratio of the average number of each group.

Specifically, when p-chloromethylstyrene and m-chloromethylstyrene are used in combination, the ratio of the average number of groups in the synthesized polyphenylene ether compound having the group represented by the formula (1) (average number ratio, the same applies hereinafter) is preferably about 5 to 95: 95 to 5, i.e., p-vinylbenzyl group and m-vinylbenzyl group. When p-chloromethylstyrene and o-chloromethylstyrene are used in combination, the ratio of the average number of the groups in the polyphenylene ether compound represented by the formula (1) is preferably about 5 to 95: 95 to 5 in terms of the ratio of p-vinylbenzyl group to o-vinylbenzyl group, and when m-chloromethylstyrene and o-chloromethylstyrene are used in combination, the ratio of the average number of the groups is preferably about 5 to 95: 95 to 5 in terms of the ratio of m-vinylbenzyl group to o-vinylbenzyl group. Further, when three kinds of p-chloromethylstyrene, m-chloromethylstyrene, and o-chloromethylstyrene are used in combination, the ratio of the average number of p-vinylbenzyl groups, m-vinylbenzyl groups, and o-vinylbenzyl groups in the polyphenylene ether compound having a group represented by the above formula (1) after synthesis is preferably p-vinylbenzyl groups: m-vinylbenzyl and o-vinylbenzyl are 20-90: 40-5: about 40-5. Further, when the polyphenylene ether compound having a group represented by the above formula (1) contains two or more of p-vinylbenzyl group, m-vinylbenzyl group and o-vinylbenzyl group, p-vinylbenzyl group is more preferably contained, and the proportion of p-vinylbenzyl group to the total number of vinylbenzyl groups contained in the polyphenylene ether compound having a group represented by the above formula (1) is preferably 40% or more, more preferably 50% or more, and still more preferably 60% or more.

The polyphenylene ether as a raw material is not particularly limited as long as a predetermined modified polyphenylene ether can be finally synthesized. Specific examples thereof include: polyphenylene ethers containing polyphenylene ether such as "2, 6-dimethylphenol" and "at least one of 2-functional phenol and 3-functional phenol", or polyphenylene ethers such as poly (2, 6-dimethyl-1, 4-phenylene ether) as a main component, and the like. The 2-functional phenol is a phenol compound having 2 phenolic hydroxyl groups in the molecule, and examples thereof include tetramethyl bisphenol a and the like. Further, the 3-functional phenol means a phenol compound having 3 phenolic hydroxyl groups in the molecule.

As an example of a method for synthesizing a polyphenylene ether compound, for example, when synthesizing a polyphenylene ether compound represented by the above formula (2), specifically, the polyphenylene ether and the compound having the substituent X and the halogen atom bonded thereto (the compound having the substituent X) as described above are dissolved in a solvent and stirred. Thus, the modified polyphenylene ether represented by the above formula (2) of the present embodiment can be obtained by reacting the polyphenylene ether with the compound having the substituent X.

When the reaction is carried out, it is preferably carried out in the presence of an alkali metal hydroxide. Consider that: thus, the reaction can be performed well. The reason is considered to be that: the alkali metal hydroxide functions as a dehydrohalogenation agent (specifically, as an acid desalting agent). Namely, it is considered that: the alkali metal hydroxide removes hydrogen halide from the phenol group of polyphenylene ether and the compound having substituent X, so that substituent X will bond to the oxygen atom of the phenol group instead of the hydrogen atom of the phenol group of polyphenylene ether.

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

The reaction conditions such as the reaction time and the reaction temperature are not particularly limited as long as they are different depending on the compound having the substituent X and the like and the reaction is favorably carried out. Specifically, the reaction temperature is preferably room temperature to 100 ℃, and more preferably 30 to 100 ℃. 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. Specifically, toluene and the like can be cited.

In addition, the above reaction is preferably: the reaction is carried out in the presence of not only the alkali metal hydroxide but also a phase transfer catalyst. Namely, the above reaction is preferably: the reaction is carried out in the presence of an alkali metal hydroxide and a phase transfer catalyst. Consider that: thus, the above reaction can be more preferably performed. The reason is considered as follows. Namely: this is achieved because the phase transfer catalyst has a function of supporting an alkali metal hydroxide, and is a catalyst which can be dissolved in both a polar solvent phase such as water and a nonpolar solvent phase such as an organic solvent and can move between these phases. Specifically, it is considered that: in the case of using an aqueous sodium hydroxide solution as the alkali metal hydroxide and using an organic solvent such as toluene, which is insoluble in water, as the solvent, even if the aqueous sodium hydroxide solution is added dropwise to the solvent for the reaction, the solvent and the aqueous sodium hydroxide solution are separated, and sodium hydroxide is less likely to migrate into the solvent. Thus, it is considered that: the aqueous sodium hydroxide solution added as the alkali metal hydroxide hardly contributes to the promotion of the reaction. In contrast, it is considered that: 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 supported on the phase transfer catalyst, and the aqueous sodium hydroxide solution easily contributes to the promotion of the reaction. Thus, it is believed that: if the reaction is carried out in the presence of an alkali metal hydroxide and a phase transfer catalyst, the above reaction proceeds more preferably.

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

After the reaction, an alcohol such as methanol is added to the reaction solution to reprecipitate the product, and the precipitate is obtained by filtration. The washing step is repeated several times (preferably 2 or more times), whereby the chloride ion content of the polyphenylene ether compound obtained can be 250ppm or less.

(crosslinking agent)

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

The crosslinking agent of the present embodiment is a compound having a carbon-carbon unsaturated double bond in the molecule or at least one or more functional groups in the molecule that contribute to the reaction with the polyphenylene ether compound, and therefore can efficiently react with the polyphenylene ether compound. Thus, it is believed that: the resin composition of the present embodiment can secure high Tg and adhesion.

The average number of carbon-carbon unsaturated bonds (the number of terminal double bonds) per 1 molecule of the crosslinking agent or the average number of functional groups (the number of functional groups) that contribute to the reaction with the compound (a) per 1 molecule of the crosslinking-type curing agent, which can be used in the present embodiment, differs depending on the weight average molecular weight of the crosslinking agent and the like. The number of terminal double bonds or functional groups is, for example, preferably 1 to 20, more preferably 2 to 18. If the number of terminal double bonds or the number of functional groups is too small, the heat resistance of the cured product tends to be insufficient. When the number of terminal double bonds or the number of functional groups is too large, the reactivity of the crosslinking agent becomes excessively high. Therefore, for example, storage stability of the resin composition is lowered, flowability of the resin composition is lowered, and the moldability of the obtained cured product may be lowered.

When the weight average molecular weight of the crosslinking agent is less than 500 (for example, 100 or more and less than 500), the number of terminal double bonds or the number of functional groups of the crosslinking agent is preferably 1 to 4. In addition, in the cross-linking agent weight average molecular weight of more than 500 (for example more than 500 and less than 5000) cases, the cross-linking agent terminal double bond number, or functional groups preferably 3 ~ 20. In each of the above cases, when 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 a cured product of the resin composition decreases, and the heat resistance or Tg may not be sufficiently improved. On the other hand, if 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 can be determined from the nominal value of the product of the crosslinking agent used. Specific examples of the number of terminal double bonds and the number of functional groups include a number representing the average of the number of double bonds and the number of functional groups per 1 molecule of all the crosslinking agents present in 1 mole of the crosslinking agent.

Specific examples of the crosslinking agent include compounds having 2 or more carbon-carbon double bonds in the molecule, such as styrene, styrene copolymers, and styrene derivatives, and include compounds having an acryloyl group in the molecule, compounds having a methacryloyl group in the molecule, compounds having a vinyl group in the molecule, compounds having an allyl group in the molecule, compounds having a maleimide group in the molecule, compounds having an acenaphthylene structure in the molecule, and isocyanurate compounds having an isocyanurate group in the molecule. Consider that: when these are used, crosslinking is more favorably 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 improved.

Examples of the styrene derivative include bromostyrene and dibromostyrene.

The compound having an acryloyl group in the molecule is an acrylate compound. Examples of the acrylate compound include a monofunctional acrylate compound having 1 acryloyl group in the molecule and a polyfunctional acrylate compound having 2 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 and the like.

The compound having a methacryloyl group in the molecule is a methacrylate compound. Examples of the methacrylate compound include a monofunctional methacrylate compound having 1 methacryloyl group in the molecule and a polyfunctional methacrylate compound having 2 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 and the like.

The compound having a vinyl group in the molecule is a vinyl compound. Examples of the vinyl compound include a monofunctional vinyl compound having 1 vinyl group in the molecule (monovinyl compound) and a polyfunctional vinyl compound having 2 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 copolymer having a structure derived from a polyfunctional aromatic vinyl compound, and a polymer or copolymer having a structure derived from a polyfunctional aliphatic vinyl compound, and examples thereof include divinylbenzene, a divinylbenzene copolymer, polybutadiene, and a butadiene copolymer.

The compound having an allyl group in the molecule is an allyl compound. Examples of the allyl compound include a monofunctional allyl compound having 1 allyl group in the molecule and a polyfunctional allyl compound having 2 or more allyl groups in the molecule. Examples of the polyfunctional allyl compound include diallyl phthalate (DAP).

The compound having a maleimide group in the molecule is a maleimide compound. Examples of the maleimide compound include a monofunctional maleimide compound having 1 maleimide group in the molecule and a polyfunctional maleimide compound having 2 or more maleimide groups in the molecule. The maleimide compound may be 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 an organosilicon compound, a modified maleimide compound in which a part of the molecule is modified with an amine compound and an organosilicon compound, or the like.

The compound having an acenaphthylene structure in a molecule is an acenaphthylene compound. Examples of the acenaphthylene compound include acenaphthylene, alkyl acenaphthylene, halogen acenaphthylene, and phenyl acenaphthylene. Examples of the alkyl acenaphthylene include 1-methyl acenaphthylene, 3-methyl acenaphthylene, 4-methyl acenaphthylene, 5-methyl acenaphthylene, 1-ethyl acenaphthylene, 3-ethyl acenaphthylene, 4-ethyl acenaphthylene, and 5-ethyl acenaphthylene. Examples of the halogenated acenaphthylene include 1-chloroacenaphthylene, 3-chloroacenaphthylene, 4-chloroacenaphthylene, 5-chloroacenaphthylene, 1-bromoacenaphthylene, 3-bromoacenaphthylene, 4-bromoacenaphthylene, and 5-bromoacenaphthylene. Examples of the phenyl acenaphthylene include 1-phenyl acenaphthylene, 3-phenyl acenaphthylene, 4-phenyl acenaphthylene, and 5-phenyl acenaphthylene. The acenaphthylene compound may be a monofunctional acenaphthylene compound having 1 acenaphthylene structure in the molecule as described above, or a polyfunctional acenaphthylene compound having 2 or more acenaphthylene structures in the molecule.

The compound having an isocyanurate group in the molecule is an isocyanurate compound. Examples of the isocyanurate compound include a compound having an alkenyl group in the molecule (alkenyl isocyanurate compound), and examples thereof include a triallyl isocyanurate (TAIC) and other triallyl isocyanurate compounds.

Among the above, the crosslinking agent is preferably, for example, a polyfunctional acrylate compound having 2 or more acryloyl groups in the molecule, a polyfunctional methacrylate compound having 2 or more methacryloyl groups in the molecule, a polyfunctional vinyl compound having 2 or more vinyl groups in the molecule, a styrene derivative, an allyl compound having allyl groups in the molecule, a maleimide compound having maleimide groups in the molecule, an acenaphthylene compound having an acenaphthylene structure in the molecule, and an isocyanurate compound having isocyanurate groups in the molecule.

The crosslinking agent may be used alone or in combination of two or more. In addition, as the crosslinking agent, a compound having 2 or more carbon-carbon unsaturated bonds in the molecule and a compound having 1 carbon-carbon unsaturated bond in the molecule may also be used in combination.

(content and 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. 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 90: 10 to 30: 70, and more preferably 90: 10 to 50: 50, in terms of mass ratio. When the polyphenylene ether and the crosslinking agent are contained in respective amounts satisfying the above ratio, the curing reaction of the modified polyphenylene ether and the crosslinking agent can be favorably carried out. Therefore, the resin composition can be a crosslinked product having more excellent heat resistance and flame retardancy.

(other Components)

The resin composition of the present embodiment is not particularly limited as long as it contains the polyphenylene ether compound and the crosslinking agent, and may further contain other components.

For example, the resin composition of the present embodiment may further contain a filler. The filler is not particularly limited, and may be added to improve the heat resistance and flame retardancy of a cured product of the resin composition. In addition, 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, titanium oxide, and mica; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; talc; aluminum borate; barium sulfate; and calcium carbonate, and the like. Among them, silica, mica and talc are preferable, and spherical silica is more preferable as the filler. Further, 1 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 surface-treated with an epoxy silane type, vinyl silane type, methacryl silane type or aminosilane type silane coupling agent. The silane coupling agent may be added not by a method of surface-treating the filler in advance but by a bulk blending method.

When the filler is contained, the content thereof is preferably 10 to 200 parts by mass, more preferably 30 to 150 parts by mass, based on 100 parts by mass of the total of the polyphenylene ether compound and the crosslinking agent.

The resin composition of the present embodiment may contain a flame retardant, and examples of the flame retardant include halogen flame retardants such as bromine flame retardants, phosphorus flame retardants, and the like. Specific examples of the halogen-based flame retardant include: brominated flame retardants such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, and hexabromocyclododecane; and chlorine-based flame retardants such as chlorinated paraffin. Specific examples of the phosphorus-based flame retardant include: phosphates such as condensed phosphates and cyclic phosphates; phosphazene compounds such as cyclic phosphazene compounds; phosphonate flame retardants such as metal phosphonates including aluminum dialkylphosphonate; melamine flame retardants such as melamine phosphate and melamine polyphosphate; phosphine oxide compounds having a diphenylphosphineoxide group, and the like. The flame retardants may be used alone or in combination of two or more.

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

The resin composition of the present embodiment may contain various additives in addition to the above components. Examples of the additives include defoamers such as silicone defoamers and acrylate defoamers, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes, pigments, lubricants, wetting dispersants, and the like.

(prepreg, film with resin, metal-clad laminate, wiring board, and metal foil with resin)

Next, a prepreg, a metal foil-clad laminate, a wiring board, and a resin-attached metal foil, each using the resin composition of the present embodiment, will be described. In the drawings described below, the symbols respectively represent the following meanings: 1 prepreg, 2 resin composition or semi-cured product of resin composition, 3 fibrous substrate, 11 metal-clad laminate, 12 insulating layer, 13 metal foil, 14 wiring, 21 wiring board, 31 resin-bearing metal foil, 32 and 42 resin layer, 41 resin-bearing film, 43 support film.

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

As shown in fig. 1, a prepreg 1 of the present embodiment includes: the above resin composition or the prepreg 2 of the above resin composition; and a fibrous substrate 3. The prepreg 1 may be a prepreg in which a fibrous substrate 3 is present in the resin composition or the prepreg 2 thereof. That is, the prepreg 1 includes: the above resin composition or a semi-cured product thereof; and a fibrous substrate 3 present in the above resin composition or the prepreg 2 thereof.

In the prepreg, the resin-attached film described later, and the resin-attached metal foil of the present embodiment, the amount of Cl ions in the resin composition or the semi-cured product of the resin composition is preferably about 0ppm to 40 ppm. From the viewpoint of cost, it is more preferably 1ppm to 40ppm, and still more preferably 2ppm 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 the method described in the examples below.

In the prepreg, the resin-attached film described later, and the resin-attached metal foil of the present embodiment, the resin composition or the semi-cured product of the resin composition may contain bromide ions (Br) in addition to the Cl ions described above^-) Nitrate ion (NO)₃ ^-) Sulfate ion (SO)₄ ^-) Nitrite ion (NO)₂ ^-) Phosphate radical ion (PO)₄ ^3-) Sodium ion (Na)⁺) Ammonium ion (NH)₄ ⁺) Calcium ion (Ca)²⁺) Plasma impurities. These ionic impurities are not particularly limited, but preferably have a concentration as low as possible, and for example, when ionic impurities are contained, bromide ion (Br) is preferable^-) Nitrate ion (NO)₃ ^-) Sulfate ion (SO)₄ ^-) Nitrite ion (NO)₂ ^-) Phosphate radical ion (PO)₄ ^3-) Sodium ion (Na)⁺) Ammonium ion (NH)₄ ⁺) Calcium ion (Ca)²⁺) Each of which is 30ppm or less.

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

[ in the formula (1), R₁R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms₂Represents an alkylene group having 1 to 10 carbon atoms.]And the amount of chloride ions in the resin composition or the semi-cured product of the resin composition is 40ppm or less.

In the present embodiment, the "prepreg" means: and a material which is obtained by curing the resin composition in the course of the curing to such an extent that the resin composition can be further cured. That is, the semi-cured product is a material in which the resin composition is in a semi-cured state (b-stage). For example, when the resin composition is heated, the viscosity gradually decreases at first, and then the curing starts, and the viscosity gradually increases. In this case, the semi-curing may be performed in a period from the start of viscosity increase to the time of complete curing.

The prepreg obtained using the resin composition of the present embodiment may be provided with a semi-cured product of the resin composition as described above, or may be provided with the resin composition itself that is not cured. That is, the prepreg may be a prepreg including a fibrous substrate and a prepreg of the resin composition (the resin composition of the second stage), or may be a prepreg including a fibrous substrate and the resin composition before curing (the resin composition of the first stage). Specific examples thereof include: the resin composition contains a prepreg of a fibrous substrate and the like. The resin composition or the prepreg thereof may be obtained by drying or heat-drying the resin composition.

The method for producing the prepreg 1 of the present embodiment using the varnish-like resin composition of the present embodiment includes, for example, a method in which the fibrous substrate 3 is impregnated with the varnish-like resin composition 2 and then dried.

Examples of the fibrous substrate used in the production of the prepreg include glass cloth, aramid cloth, polyester cloth, LCP (liquid crystal polymer) nonwoven cloth, glass nonwoven cloth, aramid nonwoven cloth, polyester nonwoven cloth, pulp paper, and cotton linter paper. When a glass cloth is used, a laminate having excellent mechanical strength can be obtained, and a glass cloth subjected to a leveling treatment is particularly preferable. The glass cloth used in the present embodiment is not particularly limited, and examples thereof include low dielectric constant glass cloths such as E glass, S glass, NE glass, Q glass, and L glass. As the uneven processing, specifically, the following processing can be performed: for example, the glass cloth is continuously pressed with a pressing roll at an appropriate pressure to compress the yarn to be flat. The thickness of the fibrous substrate is usually, for example, 0.01 to 0.3 mm.

Impregnation of the resin varnish (resin composition 2) into the fibrous base material 3 is performed by dipping, coating, or the like. This impregnation may be repeated as many times as necessary. In this case, the impregnation may be repeated using a plurality of resin varnishes having different compositions and concentrations, and the composition (content ratio) and the resin amount may be finally adjusted to desired values.

The fibrous substrate 3 impregnated with the resin varnish (resin composition 2) is heated under a desired heating condition, for example, 80 ℃ to 180 ℃ for 1 minute to 10 minutes. The solvent is evaporated from the varnish by heating to reduce or remove the solvent, thereby obtaining a prepreg 1 before curing (a stage a) or in a semi-cured state (a stage b).

As shown in fig. 4, the resin-coated metal foil 31 of the present embodiment has the following configuration: a structure in which the resin layer 32 containing the resin composition or the semi-cured product of the resin composition and the metal foil 13 are laminated. That is, the resin-bearing metal foil according to the present embodiment may be a resin-bearing metal foil including a resin layer containing the resin composition (the first-stage resin composition) before curing and a metal foil, or may be a resin-bearing metal foil including a resin layer containing a semi-cured product of the resin composition (the second-stage resin composition) and a metal foil.

Examples of the method for producing the resin-attached metal foil 31 include the following methods: a method of applying the resin composition in the form of a varnish to the surface of a metal foil 13 such as a copper foil and then drying the applied resin composition. Examples of the coating method include a bar coater, a comma coater, a die coater, a roll coater, and a gravure coater.

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

As shown in fig. 5, the resin-attached film 41 of the present embodiment has the following configuration: a structure in which a resin layer 42 containing the above resin composition or a semi-cured product of the above resin composition and a film supporting base 43 are laminated. That is, the resin-attached film of the present embodiment may be a resin-attached film including the resin composition before curing (the first-stage resin composition) and a film support base, or may be a resin-attached film including a semi-cured product of the resin composition (the second-stage resin composition) and a film support base.

As a method for producing the resin-attached film 41, for example, a resin-attached film before curing (a-stage) or in a semi-cured state (b-stage) can be obtained by applying the resin composition in the form of a resin varnish as described above to the surface of the film supporting substrate 43, and then evaporating the solvent from the varnish to reduce or remove the solvent.

Examples of the film support base include electrically insulating films such as a polyimide film, a PET (polyethylene terephthalate) film, a polyester film, a polyparacarboxylic acid film, a polyether ether ketone film, a polyphenylene sulfide film, an aramid film, a polycarbonate film, and a polyacrylate film.

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

The thicknesses of the metal foil 13 and the film support base 43 may be appropriately set according to the intended purpose. For example, about 0.2 to 70 μm can be used as the metal foil 13. In the case where the thickness of the metal foil is, for example, 10 μm or less, a copper foil with a carrier having a release layer and a carrier can be used for the purpose of improving the workability. The application of the resin varnish to the metal foil 13 and the film supporting base 43 is performed by coating or the like, and this operation may be repeated several times as needed. In this case, the composition (content ratio) and the resin amount may be finally adjusted to desired values by repeating the application of a plurality of resin varnishes having different compositions and concentrations.

The drying or heat drying conditions in the method for producing the resin-bearing metal foil 31 or the resin film 41 are not particularly limited, and the resin-bearing metal foil 31 or the resin film 41 before curing (a-stage) or in a semi-cured state (b-stage) can be obtained by applying a resin varnish-like resin composition to the metal foil 13 or the film support base 43, heating the composition at a desired heating condition, for example, at 80 to 170 ℃ for about 1 to 10 minutes, and volatilizing the solvent from the varnish to reduce or remove the solvent.

The metal foil 31 with resin and the resin film 41 may be provided with a cover film or the like as needed. By providing the cover film, it is possible to prevent the entry of foreign matter and the like. The cover film is not particularly limited as long as it can be peeled off without impairing the form of the resin composition, and examples thereof include a polyolefin film, a polyester film, a TPX film, a film formed by providing a release agent layer on the above films, and paper obtained by laminating the above films on a paper base.

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 resin composition or a cured product of the prepreg; and a metal foil 13. As the metal foil 13 used for the metal-clad laminate 11, the same metal foil as the metal foil 13 described above can be used.

The metal foil-clad laminate 13 of the present embodiment may be produced using the resin-attached metal foil 31 or the resin film 41 described above.

In the method for producing a metal foil-clad laminate using the prepreg 1, the resin-containing metal foil 31, and the resin film 41 obtained in the above manner, one or more sheets of the prepreg 1, the resin-containing metal foil 31, and the resin film 41 are stacked, and further, a metal foil 13 such as a copper foil is stacked on both surfaces or one surface of the upper and lower surfaces thereof, and is heated and pressed to be integrated, whereby a double-sided metal foil-clad laminate or a single-sided metal foil-clad laminate can be produced. The heating and pressurizing conditions may be suitably set according to the thickness of the laminate to be produced, the kind of the resin composition, and the like, and for example, the temperature may be set to 170 to 220 ℃, the pressure may be set to 1.5 to 5.0MPa, and the time may be set to 60 to 150 minutes.

The metal foil-clad laminate 11 may be produced by forming a film-like resin composition on the metal foil 13 and heating and pressing the film-like resin composition without using the prepreg 1 or the like.

As shown in fig. 3, the wiring board 21 of the present embodiment includes: an insulating layer 12 containing a cured product of the resin composition or a cured product of the prepreg; and a wiring 14.

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, it is preferably used as a material for an interlayer insulating layer of a multilayer wiring board having 10 or more, and further 15 or more circuit layers, for example.

In addition, as a material of the interlayer insulating layer, a plurality of insulating layers formed of the resin composition of the present embodiment are preferably used. Although not particularly limited, for example, 10 or more layers are preferably used. Accordingly, it is considered that: in a multilayer wiring board, the density of conductor circuit patterns can be further increased, and the lower dielectric characteristics of a plurality of interlayer insulating layers, the insulation reliability between conductor circuit patterns, and the insulation between interlayer circuits can be further improved. Further, effects are obtained that the transmission speed of signals in the multilayer wiring board can be increased and the loss at the time of signal transmission can be reduced.

As a method for manufacturing this wiring board 21, for example, a circuit (wiring) is formed by etching or the like the metal foil 13 on the surface of the metal-clad laminate 13 obtained as described above, and a wiring board 21 having a conductor pattern (wiring 14) as a circuit provided on the surface of the laminate can be obtained. Examples of the circuit forming method include, in addition to the above-described methods, forming a circuit by a Semi-Additive Process (SAP) or a Modified Semi-Additive Process (MSAP).

When the resin composition of the present embodiment is used, excellent insulation reliability can be secured even for a substrate on which circuits as described above are formed and which has a conductor circuit pattern with an inter-circuit distance of 150 μm or less. Here, as shown in fig. 6, the distance between circuits is: a distance (interval) S between two adjacent wirings (conductor circuits) (L). In the wiring board of the present embodiment, the distance between circuits does not need to be 150 μm or less in all, and at least a part of the wiring board may have a distance between circuits of 150 μm or less.

By thus forming a substrate having a conductor circuit pattern in the substrate and at least a part of the conductor circuit pattern including a portion where the distance between circuits is 150 μm or less, the density of the conductor circuit pattern in the substrate can be made higher, and the wiring board can be downsized. Further, by including a conductor circuit pattern having a conductor circuit width of 150 μm or less, the conductor circuit pattern can be further densified. Further, a part of the signal line of the conductor circuit pattern can be shortened, and lower transmission loss and higher-speed transmission can be realized.

By using the resin composition of the present embodiment, the resin composition of the present embodiment can exhibit the above-described effect (insulation reliability) even when the circuit distance is smaller. For example, insulation reliability can be exhibited even if the distance between conductor circuits is 150 μm or less, or 100 μm or less, or 75 μm or less, or even 50 μm or less. Thus, it is believed that: the resin composition of the present embodiment can be suitably used for a wiring (circuit) board having a narrow distance between wirings. In addition, in the wiring board, in the multilayer wiring board including the conductive through-hole and/or the conductive via hole, excellent insulation reliability can be obtained also between the conductive through-hole and/or the conductive via hole formed adjacent to each other in the insulating layer.

The prepreg, the resin-attached film, and the resin-attached metal foil obtained using the resin composition of the present embodiment are extremely useful in industrial applications because cured products thereof have low dielectric characteristics, high Tg, insulation reliability, and the like. Further, the metal-clad laminate and the wiring board including these also have low dielectric characteristics, high Tg, and excellent insulation reliability.

As described above, the present specification discloses the techniques according to the various embodiments, and its main techniques are summarized as follows.

According to this configuration, a resin composition having a cured product with low dielectric characteristics, high Tg and excellent insulation reliability can be provided.

Another aspect of the present invention relates to another resin composition comprising: a polyphenylene ether compound having a group represented by the following formula (1) at a molecular end; and a crosslinking agent having a carbon-carbon unsaturated double bond in the molecule and a crosslinking agent which reacts with the polyphenylene ether compound and cures the compound,

[ in the formula (1), R₁R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms₂Represents an alkylene group having 1 to 10 carbon atoms.]And, furthermore,

the amount of chloride ions in the resin composition or the semi-cured product of the resin composition is 40ppm or less.

According to this configuration, a resin composition having a cured product having both low dielectric characteristics, high Tg and excellent insulation reliability can be provided.

Further, it is preferable that: the crosslinking agent contains at least 1 selected from the group consisting of a triene isocyanurate compound, a polyfunctional acrylate compound having 2 or more acryloyl groups in the molecule, a polyfunctional methacrylate compound having 2 or more methacryloyl groups in the molecule, a polyfunctional vinyl compound having 2 or more vinyl groups in the molecule, an allyl compound, a maleimide compound, and an acenaphthylene compound.

Consider that: this allows better crosslinking by the curing reaction, and has an advantage that the heat resistance of the cured product of the resin composition used in the present embodiment can be further improved.

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

(in the formula (2), R₃～R₁₀Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. X 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 formulae (3) and (4), m and n each represent an integer of 0 to 20. R₁₁～R₁₄And R₁₅～R₁₈Each independently represents a hydrogen atom or an alkyl group. )

In the formula (2), Y is a structure represented by the following formula (5):

(in the formula (5), R₁₉And R₂₀Each independently represents a hydrogen atom or an alkyl group. )

Consider that: with this configuration, the above-described effects can be more reliably obtained.

Further, it is preferable that: the resin composition is used for a wiring board provided with a conductor circuit pattern having a distance between conductor circuits of 150 [ mu ] m or less at least in a part thereof. Consider that: in this application, the effects of the present invention can be further exhibited.

Another aspect of the invention relates to a prepreg comprising: the resin composition or a semi-cured product of the resin composition; and a fibrous substrate.

Another aspect of the invention relates to a resin-bearing film comprising: a resin layer comprising the resin composition or a semi-cured product of the resin composition; and a support film.

Another aspect of the present invention relates to a resin-coated metal foil, comprising: a resin layer comprising the resin composition or a semi-cured product of the resin composition; and a metal foil.

Another aspect of the present invention relates to a metal-clad laminate comprising: an insulating layer comprising a cured product of the resin composition or a cured product of the prepreg; and a metal foil.

Another aspect of the present invention relates to a wiring board, including: an insulating layer comprising a cured product of the resin composition or a cured product of the prepreg; and wiring.

According to the configuration described above, a prepreg, a resin-attached film, a resin-attached metal foil, a metal foil-clad laminate, a wiring board, and the like, which can obtain a substrate having low dielectric characteristics and high Tg and having excellent insulation reliability, can be provided.

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

Examples

First, the components used in the preparation of the resin composition in this example will be described.

< ingredient a: polyphenylene ether Compound >

Modified PPE-1: 2-functional 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 of polyphenylene ether per 1 molecule is represented as the number of terminal hydroxyl groups.

The polyphenylene ether was reacted with chloromethyl styrene to obtain modified polyphenylene ether 1 (modified PPE-1). Specifically, 200g of polyphenylene ether (SA 90, Intrinsic Viscosity (IV) 0.083dl/g, number of terminal hydroxyl groups 1.9, weight molecular weight Mw1700), 30g of a mixture of p-chloromethylstyrene and m-chloromethylstyrene at a mass ratio of 50: 50, 1.227g of tetra-n-butylammonium bromide as a phase transfer catalyst, and 400g of toluene were charged into a 1 liter 3-neck flask equipped with a temperature controller, a stirrer, a cooling device, and a dropping funnel, and stirred. Also, stirring was continued until polyphenylene ether, chloromethylstyrene and tetra-n-butylammonium bromide were dissolved in toluene. At this time, heating was slowly performed until the liquid temperature finally reached 75 ℃. Subsequently, an aqueous sodium hydroxide solution (sodium hydroxide 20 g/water 20g) as an alkali metal hydroxide was added dropwise to the solution over 20 minutes. Then, the mixture was further stirred at 75 ℃ for 4 hours. Next, after neutralizing the contents of the flask with 10 mass% hydrochloric acid, a large amount of methanol was added. By this operation, a precipitate was generated in the liquid in the flask. That is, the product contained in the reaction solution in the flask was precipitated again. Then, the precipitate was removed by filtration, and the residue was purified by filtration using a methanol-to-water mass ratio of 80: the mixture of 20 was washed 3 times and dried at 80 ℃ for 3 hours under reduced pressure.

Using the obtained solid¹H-NMR(400MHz、CDCl₃TMS) was analyzed. As a result of NMR measurement, a peak derived from vinylbenzyl group was observed 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 the molecular terminal. Specifically, it was confirmed that the polyphenylene ether was a vinylbenzylated polyphenylene ether.

In addition, the molecular weight distribution of the modified polyphenylene ether was measured by GPC. Then, the weight average molecular weight (Mw) was calculated from the obtained molecular weight distribution, and as a result, the Mw was 1900.

In addition, the number of terminal functions of the modified polyphenylene ether was measured as follows.

First, the modified polyphenylene ether was accurately weighed. The weight at this time was X (mg). Then, the weighed modified polyphenylene ether was dissolved in 25mL of methylene chloride, 100. mu.L of a 10 mass% ethanol solution of tetraethylammonium hydroxide (TEAH) (TEAH: ethanol (volume ratio): 15: 85) was added to the solution, and then the absorbance (Abs) at 318nm was measured using a UV spectrophotometer (UV-1600 manufactured by Shimadzu corporation). Then, based on the measurement results, the number of terminal hydroxyl groups of the modified polyphenylene ether was calculated using the following formula.

The residual OH amount (μmol/g) [ (25 × Abs)/(∈ × OPL × X) ] × 106

Here,. epsilon.represents an absorption coefficient of 4700L/mol. cm. The OPL is the unit optical path length and is 1 cm.

Then, since the residual OH amount (number of terminal hydroxyl groups) of the modified polyphenylene ether obtained by this calculation is almost zero, it is found that: the hydroxyl group of the polyphenylene ether before modification is almost modified. From this, it can be seen that: the amount of decrease in the number of terminal hydroxyl groups relative to the polyphenylene ether before modification was the number of terminal hydroxyl groups of the polyphenylene ether before modification. Namely, it can be seen that: the number of terminal hydroxyl groups of the polyphenylene ether before modification is the number of terminal functional groups of the modified polyphenylene ether. That is, the number of terminal functional groups is 2.

In addition, the amount of impurity ions in the modified polyphenylene ether compound was measured as follows. Namely: 15g of pure water was added to 0.75g of the sample (obtained modified PPE-1), and after extraction at 125 ℃ for 20 hours, the mixture was subjected to ion chromatography (using a column model of "ICS 1500", manufactured by Thermo Fisher Co., Ltd., separation column: Ionpac AS22, eluent: 4.5mm 1/LNa)₂CO₃/1.4mmol/L NaHCO₃Eluent flow rate: 1.5 mL/min). As a result, Cl was added in the amount of each impurity ion in the modified PPE-1 in terms of solid content^-The ion content was 1912 ppm. In addition, with respect to Cl^-Other than ionsFor other ions, Br^-Ion less than 2ppm, NO₃ ^-Ion 10ppm, SO₄ ^-Ion 2ppm, NO₂ ^-Ion less than 2ppm, PO₄ ^3-Ion content less than 2ppm, Na⁺Ion less than 2ppm, NH₄ ⁺The ion content was 12 ppm.

Modified PPE-2: 2-functional vinylbenzyl-modified PPE (Mw: 1900)

Modified PPE-2 was obtained in the same manner as in modified PPE-1 except that the step of adding methanol to precipitate the product in the reaction solution in the flask (i.e., the step of precipitating the product again in the reaction solution in the flask) and the step of obtaining the precipitate by filtration were repeated 3 times (3 times).

The amounts of various impurity ions in the obtained modified PPE-2 were measured in the same manner as in the modified PPE-1, and as a result, Cl was calculated as solid content^-Ion 42ppm, Br^-Ion less than 2ppm, NO₃ ^-Ion 29ppm, SO₄ ^-Ion 14ppm, NO₂ ^-Ion less than 2ppm, PO₄ ^3-Ion content less than 2ppm, Na⁺Ion less than 2ppm, NH₄ ⁺The ion content was 27 ppm.

Modified PPE-3: 2-functional vinylbenzyl-modified PPE (Mw: 1900)

Modified PPE-3 was obtained in the same manner as in modified PPE-1 except that the step of adding methanol to precipitate the product in the reaction mixture in the flask (i.e., the step of precipitating the product again in the reaction mixture in the flask) and the step of obtaining the precipitate by filtration were repeated 2 times (2 times).

The amounts of various impurity ions in the obtained modified PPE-3 were measured in the same manner as in the modified PPE-1, and as a result, Cl was calculated as solid content^-Ion 42ppm, Br^-Ion 2ppm, NO₃ ^-Ion 41ppm, SO₄ ^-Ion less than 2ppm, NO₂ ^-Ion less than 2ppm, PO₄ ^3-Ion less than 2ppm, Na ion⁺Is 8ppm, NH₄ ⁺The ion content was 20 ppm.

Modified PPE-4: 2-functional vinylbenzyl-modified PPE (Mw: 1900)

Modified PPE 4 was obtained in the same manner as in modified PPE-1 except that a mixture of o-chloromethylstyrene, p-chloromethylstyrene and m-chloromethylstyrene at a mass ratio of 20: 10: 70 was used in place of the mixture of p-chloromethylstyrene and m-chloromethylstyrene at a mass ratio of 50: 50, and that the step of precipitating the product contained in the reaction solution in the flask again by adding methanol and the step of obtaining the precipitate by filtration were repeated 3 times (3 times).

The amounts of various impurity ions in the obtained modified PPE-4 were measured in the same manner as in the modified PPE-1, and as a result, Cl was calculated as solid content^-The ion content was 31 ppm. In addition, as other ions, Br^-Ion less than 2ppm, NO₃ ^-Ion less than 2ppm, SO₄ ^-Ion less than 2ppm, NO₂ ^-Ion less than 2ppm, PO₄ ^3-Ion content less than 2ppm, Na⁺Ion 8ppm, NH₄ ⁺The ion content was 10 ppm.

SA-9000: 2-functional methacrylate-modified PPE (Mw: 1700, manufactured by Saber basic Innovative plastics Co., Ltd., Cl ion amount: less than 2ppm)

OPE-2St 2200: terminal vinylbenzyl-modified PPE (Mw: about 3600, manufactured by Mitsubishi gas chemical Co., Ltd., Cl ion content: 1350ppm)

< component B: crosslinking agent >

TAIC: triallyl isocyanurate, (manufactured by Nippon Kabushiki Kaisha)

DVB 810: divinyl benzene (Xinri iron Sunjin chemical Co., Ltd.)

DCP: dicyclopentadiene methacrylate (manufactured by Xinzhongcun chemical industry Co., Ltd.)

< other ingredients >

(inorganic Filler)

SC 2300-SVJ: methacryloylsilane surface-treated spherical silica (manufactured by Admatech Company Limited, Ltd.)

(flame retardant)

SAYTEX 8010: bromine flame retardant (manufactured by Albemarle Japan Corporation)

< examples 1 to 5 and comparative examples 1 to 3>

[ preparation method ] (resin varnish)

First, the components were added to toluene at the blending ratio (parts by mass) shown in table 1 and mixed so that the solid content concentration became about 60% by mass. This mixture was stirred at 30 ℃ for 60 minutes to obtain a varnish-like resin composition (varnish).

(preparation of prepreg)

Prepreg I

The resin varnishes of the examples and comparative examples were impregnated into glass cloth (manufactured by asahi chemicals corporation, # L2116), and then dried by heating at 130 ℃ for about 3 minutes to obtain prepregs. At this time, the content of the resin composition (resin content) was adjusted to be about 56 mass% with respect to the weight of the prepreg.

Prepreg II

The resin varnishes of the examples and comparative examples were impregnated into glass cloth (manufactured by asahi chemicals corporation, model # L1078), and then dried by heating at 130 ℃ for about 2 minutes to obtain prepregs. At this time, the content of the resin composition (resin content) was adjusted to be about 70 mass% with respect to the weight of the prepreg.

(production of copper clad laminate)

Copper clad laminate I

A6-piece prepreg was prepared by placing copper foils (GT-MP manufactured by Kogaku electric industries Co., Ltd.) having a thickness of 12 μm on both sides thereof to prepare a pressed body, and vacuum-pressing the pressed body at a temperature of 210 ℃ and a pressure of 30kgf/cm²The resultant was heated and pressed for 90 minutes under the conditions described above, to obtain a copper clad laminate having a copper foil bonded on both sides and having a thickness of about 0.75 mm.

Laminate II

2 sheets of the prepreg-II were stacked, and copper foils (FV-WS, manufactured by Kogaku electric industries Co., Ltd.) having a thickness of 18 μm were disposed on both sides of the stacked prepreg-II to prepare a pressed body, which was then pressed under vacuum at a temperature of 210 ℃ and a pressure of 30kgf/cm²The resultant was heated and pressed for 90 minutes under the conditions described above, to obtain a copper clad laminate-II' having a thickness of about 0.18mm, to which copper foil was bonded on both sides. The obtained laminate sheet-II' was exposed to light using a dry film so as to form a circuit pattern including a portion where the width of the conductor circuit became 100 μm, and copper was etched using an aqueous solution of copper chloride, thereby obtaining a laminate sheet-II "after the conductor circuit was fabricated. As the conductor circuit pattern, a comb pattern (number of lines: 15, line overlapping portion: 65mm) for evaluating insulation reliability was obtained, the comb pattern including, in an inner layer, L (conductor circuit width)/S (distance between conductor circuits) as shown in fig. 7: the circuit pattern of the conductor circuit 51 was formed to be 100 μm/100 μm. The prepreg-II was placed on both sides of the obtained laminate-II, FV-WS copper foil 18 μm thick was placed on both sides of the prepreg-II, and the laminate-II was placed under vacuum at a temperature of 210 ℃ and a pressure of 30kgf/cm²Was heated and pressed for 90 minutes under the conditions described above, to obtain a laminate II having a distance between conductor circuits of 100 μm.

< evaluation test >

[ dielectric characteristics (relative dielectric constant and dielectric loss tangent) ]

The relative dielectric constant and dielectric loss tangent of the evaluation substrate at 1GHz were measured using a material/impedance analyzer (HP 4291A and HP16453A manufactured by Hewlett packard Co.). As the evaluation substrate, a laminate obtained by removing the copper foil from the copper clad laminate I was used. The measurement was carried out by a method based on PC-TM-6502.5.5.9.

[ glass transition temperature (Tg) ]

The outer copper foil of the copper clad laminate I was etched on the entire surface, and the glass transition temperature (Tg) of the obtained sample was measured using a Differential Scanning Calorimeter (DSC). The determination was made based on the IPC-TM-6502.4.25 method.

[ insulation reliability ]

The laminate II was subjected to a voltage of 100V for 500 hours in an atmosphere of 85 ℃ and 85% humidity, and the resistance value was continuously measured every 1 hour. The sample was evaluated as acceptable (. smallcircle.) when the resistance value was not lost to 10^ 7. omega. after the application of 500 hours; then, the resistance loss was evaluated as not more than 10^7 Ω, and the value was found to be defective (X).

The above results are shown in table 1 below.

[ amount of impurity ions in prepreg ]

In addition, for examples 1-2 and comparative example 1, the amount of Cl ions in the prepreg was also measured. Specifically, 0.75g of the resin component of the prepreg I was prepared by sieving (100 mesh pass, 200 mesh pass) the resin component. Adding into 15g pure water, extracting at 125 deg.C for 20 hr, and subjecting to ion chromatography (using model number "ICS 1500", separation column of Saimer Feishale company: Ionpac AS22, eluent: 4.5mmol/L Na₂CO₃/1.4mmol/LNaHCO₃Eluent flow rate: 1.5 mL/min), the amount of various impurity ions was measured. The numerical limit of the amount of impurity ions detectable by the above ion chromatography apparatus is 2ppm, and impurity ions whose detected amount is less than this value are described as being less than 2 ppm.

As a result, the amounts of the respective impurity ions were as follows: in example 1, Cl^-The ion content was 7 ppm. In addition, with respect to Cl^-For ions other than ions, Br^-Ion less than 2ppm, NO₃ ^-Ion 17ppm, SO₄ ^-Ion 3ppm, NO₂ ^-Ion less than 2ppm, PO₄ ^3-Ion content less than 2ppm, Na⁺Ion less than 2ppm, NH₄ ⁺The ion content was 10ppm and the Ca ion content was 5 ppm.

In example 2, Cl^-The ion content was 29 ppm. In addition, with respect to Cl^-For ions other than ions, Br^-Ion less than 2ppm, NO₃ ^-Ion 7ppm, SO₄ ^-Ion 2ppm, NO₂ ^-Ion less than 2ppm, PO₄ ^3-Ion content less than 2ppm, Na⁺Ion less than 2ppm, NH₄ ⁺Ion 9ppm, Ca²⁺Ion is 5ppm。

In example 6, Cl^-The ion content was 4 ppm. In addition, with respect to Cl^-For ions other than ions, Br^-Ion less than 2ppm, NO₃ ^-Ion 7ppm, SO₄ ^-Ion 7ppm, NO₂ ^-Ion less than 2ppm, PO₄ ^3-Ion content less than 2ppm, Na⁺Ion 4ppm, NH₄ ⁺Ion 7ppm, Ca²⁺The ion content was 6 ppm. In comparative example 1, Cl^-Ion 75ppm, Br^-Ion less than 2ppm, NO₃ ^-Ion 15ppm, SO₄ ^-Ion less than 2ppm, NO₂ ^-Ion less than 2ppm, PO₄ ^3-Ion is less than²ppm，Na⁺Ion less than 2ppm, NH₄ ⁺Ion 7ppm, Ca²⁺The ion content is less than 2 ppm.

(examination)

From the results shown in table 1, it can be seen that: the present invention can provide a resin composition having both low dielectric characteristics (Dk: 3.3 or less, Df: 0.0015 or less) and high Tg and excellent insulation reliability.

On the other hand, in comparative examples 1 and 3 using a polyphenylene ether compound having a large amount of Cl ions, sufficient insulation reliability could not be obtained. In addition, comparative example 2 using a polyphenylene ether compound having no group represented by the above formula (1) at the molecular end showed the result of the difference in Tg.

The application is based on Japanese patent application laid-open at 9/19/2018, namely Japanese patent application laid-open at 2018 and 174980, and the content of the Japanese patent application is included in the application.

In order to describe the present invention, the present invention has been described in detail by way of embodiments with reference to specific examples and drawings, but it should be understood that modifications and/or improvements can be easily made to the embodiments by those skilled in the art. Therefore, a modified embodiment or an improved embodiment that a person skilled in the art carries out may be interpreted as being included in the scope of the claims as long as the modified embodiment or the improved embodiment does not depart from the scope of the claims described in the claims.

Industrial applicability

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

Claims

1. A resin composition characterized by comprising:

a polyphenylene ether compound having a group represented by the following formula (1) at a molecular end; and

at least one of a crosslinking agent having a carbon-carbon unsaturated double bond in the molecule and a crosslinking agent which reacts with the polyphenylene ether compound and cures the compound,

the amount of chloride ions in the polyphenylene ether compound is 250ppm or less,

2. A resin composition characterized by comprising:

in the formula (1), R₁R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms₂Represents an alkylene group having 1 to 10 carbon atoms,

3. The resin composition according to claim 1 or 2,

the crosslinking agent contains at least 1 selected from the group consisting of a triene isocyanurate compound, a polyfunctional acrylate compound having 2 or more acryloyl groups in the molecule, a polyfunctional methacrylate compound having 2 or more methacryloyl groups in the molecule, a polyfunctional vinyl compound having 2 or more vinyl groups in the molecule, an allyl compound, a maleimide compound, and an acenaphthylene compound.

4. The resin composition according to any one of claims 1 to 3,

the polyphenylene ether compound has a structure represented by the following formula (2),

in the formula (2), R₃～R₁₀Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group, X is a group represented by the formula (1),

in the formulas (3) and (4), m and n respectively represent an integer of 0-20, R₁₁～R₁₄And R₁₅～R₁₈Each independently represents a hydrogen atom or an alkyl group,

in the formula (2), Y is a structure represented by the following formula (5):

in the formula (5), R₁₉And R₂₀Each independently represents a hydrogen atom or an alkyl group.

5. The resin composition according to any one of claims 1 to 4,

used for a wiring board provided with a conductor circuit pattern having a distance between conductor circuits of 150 μm or less at least a part thereof.

6. A prepreg characterized by comprising:

the resin composition or the semi-cured product of the resin composition according to any one of claims 1 to 4; and

a fibrous substrate.

7. A resin-bearing film characterized by comprising:

a resin layer comprising the resin composition according to any one of claims 1 to 4 or a semi-cured product of the resin composition; and

and supporting the membrane.

8. A resin-bearing metal foil, characterized by comprising:

a metal foil.

9. A metal-clad laminate characterized by comprising:

an insulating layer comprising 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.

10. A wiring board characterized by comprising:

an insulating layer comprising a cured product of the resin composition according to any one of claims 1 to 5 or a cured product of the prepreg according to claim 6; and

and (6) wiring.