TW202348646A - Resin composition, cured product, prepreg, metal-foil-clad laminate, resin composite sheet, printed circuit board, and semiconductor device - Google Patents

Abstract

Provided are: a resin composition having excellent moisture absorption heat resistance while maintaining excellent low dielectric properties (Dk and/or Df); a cured product; a prepreg; a metal foil-clad laminate; a resin composite sheet; a printed circuit board; and a semiconductor device. The resin composition comprises a compound (M) represented by formula (M), a polymer (V) having a constituent unit represented by formula (V), and a compound (M1) represented by formula (M1). In formula (V), Ar represents an aromatic hydrocarbon linking group.

Description

Resin compositions, cured products, prepregs, metal foil-clad laminates, resin composite sheets, printed wiring boards, and semiconductor devices

The present invention relates to a resin composition, a cured product, a prepreg, a metal foil-clad laminate, a resin composite sheet, a printed wiring board, and a semiconductor device.

In recent years, semiconductor devices used in electronic equipment, communication equipment, etc., represented by portable terminals, have become highly integrated and miniaturized. Along with this, technologies that enable high-density mounting of semiconductor elements are being sought, and improvements are also being sought on printed wiring boards that occupy an important position. On the other hand, the uses of electronic equipment and the like are diversifying and expanding. Therefore, the various properties required for printed wiring boards, metal foil-clad laminates, prepregs, etc. used therefor are also diversifying and becoming more stringent. In order to obtain a printed wiring board that is improved in consideration of such required characteristics, various materials and processing methods have been proposed. One of them is the improvement and development of resin materials constituting prepregs and resin composite sheets.

Furthermore, Patent Document 1 discloses a maleimide resin as shown below as a maleimide resin suitable for electronic material applications. In addition, Patent Document 1 discloses a curable resin composition blended with an epoxy resin or the like, which has excellent dielectric properties. Furthermore, Patent Document 2 also describes the following compounds. [Chemical 1] [Prior art documents] [Patent documents]

[Patent Document 1] International Publication No. 2020/054601 [Patent Document 2] International Publication No. 2021/182360

[Problem to be solved by the invention]

As mentioned above, the uses of electronic devices and the like are diversifying and expanding, and new materials are being sought for resin materials constituting prepregs and the like. In particular, further material development is sought for a resin composition that maintains excellent low dielectric properties (Dk and/or Df) and has excellent moisture absorption and heat resistance. In order to solve the above-mentioned problems, the object of the present invention is to provide a resin composition that maintains excellent low dielectric properties (Dk and/or Df) and has excellent moisture absorption and heat resistance, and to provide a cured product, a prepreg, and a metal foil-clad laminate. , resin composite sheets, printed wiring boards, and semiconductor devices. [Means to solve the problem]

Based on the above-mentioned problems, the inventors of the present invention conducted research and found that the above-mentioned problems can be solved by using a predetermined maleimide compound and a predetermined polyfunctional vinyl aromatic polymer in combination. Specifically, the above-mentioned problems were solved using the following means. <1> A resin composition containing: a compound (M) represented by formula (M), a polymer (V) having a structural unit represented by formula (V), and a compound (M1) represented by formula (M1). [Chemicalization 2] In the formula (M), R each independently represents a hydrocarbon group with 1 to 10 carbon atoms that may be substituted by a halogen atom, R ^mx each independently represents a methylene group, an ethylene group, or a 2,2-propylene group, and R ^my is a base selected from the following group (A). m represents an integer from 0 to 3, n is the average of repeated numbers, and represents 1.00≦n≦20.00. (Group (A)) [Chemicalization 3] In group (A), R ^y is each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may have a substituent, and ny is each independently an alkyl group having 0 to 3 carbon atoms. Integer, * is the bonding position with R ^mx . [Chemical 4] In formula (V), Ar represents an aromatic hydrocarbon connecting group. *Indicates bonding position. [Chemistry 5] In formula (M1), R ^M1 , R ^M2 , R ^M3 and R ^M4 each independently represent a hydrogen atom or an organic group. R ^M5 and R ^M6 each independently represent a hydrogen atom or an alkyl group. Ar ^M represents a divalent aromatic group. A is an alicyclic group with 4 to 6 members. R ^M7 and R ^M8 are each independently an alkyl group. mx is 1 or 2, lx is 0 or 1. R ^M9 and R ^M10 each independently represent a hydrogen atom or an alkyl group. ^RM11 , ^RM12 , ^RM13 and ^RM14 each independently represent a hydrogen atom or an organic group. R ^M15 independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl group having 6 carbon atoms. An aryloxy group with ∼10 carbon atoms, an arylthio group with 6 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group. px represents an integer from 0 to 3. nx represents an integer from 1 to 20. <2> The resin composition according to <1>, wherein the content of the compound (M) represented by the formula (M) is 5 to 50 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. <3> The resin composition according to <1> or <2>, wherein the polymer (V) having the structural unit represented by formula (V) is 100 parts by mass of the resin solid content in the resin composition. The content is 5 to 50 parts by mass. <4> The resin composition according to any one of <1> to <3>, wherein the compound (M1) represented by the formula (M1) is 100 parts by mass of the resin solid content in the resin composition. The content is 5 to 50 parts by mass. <5> The resin composition according to any one of <1> to <4>, wherein n is 1.05≦n≦20.00 in the compound (M) represented by the formula (M). <6> The resin composition according to any one of <1> to <5>, wherein the compound (M) represented by the formula (M) includes a compound represented by the formula (M-1). [Chemical 6] In the formula (M-1), R each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a halogen atom. m represents an integer from 0 to 3, n is the average of repeated numbers, and represents 1.00≦n≦20.00. <7> The resin composition according to any one of <1> to <6>, wherein the compound (M) represented by the formula (M) includes the compound represented by the formula (M-2). [Chemical 7] In formula (M-2), ^Rz each independently represents a hydrocarbon group having 1 to 10 carbon atoms. m represents an integer from 0 to 3, n is the average of repeated numbers, and represents 1.00≦n≦20.00. <8> The resin composition according to any one of <1> to <7>, wherein the weight average molecular weight of the polymer (V) having the structural unit represented by the formula (V) is 3,000 to 130,000. <9> The resin composition according to any one of <1> to <8>, wherein the weight average molecular weight of the polymer (V) having the structural unit represented by the formula (V) is 10,000 to 130,000. <10> The resin composition according to any one of <1> to <9>, further containing a compound (M) selected from the compound (M) represented by the aforementioned formula (M) and a compound (M1) represented by the aforementioned formula (M1). Maleimide compounds, epoxy compounds, phenolic compounds, oxetane resins, benzodiazepine compounds, compounds containing (meth)allyl groups (preferably alkenyl nadicide imine compounds) , and one or more other thermosetting compounds (C) in the group consisting of polyphenylene ether compounds containing two or more carbon-carbon unsaturated double bonds. <11> The resin composition according to <10>, wherein the content of the other thermosetting compound (C) is 1 to 50 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. <12> The resin composition according to any one of <1> to <11>, further containing a filler (D). <13> The resin composition according to <12>, wherein the content of the filler (D) in the resin composition is 10 to 1,600 parts by mass relative to 100 parts by mass of the resin solid content. <14> The resin composition according to any one of <1> to <13>, further containing a thermoplastic elastomer. <15> The resin composition according to any one of <1> to <14>, wherein the compound (M) represented by the formula (M) is 100 parts by mass of the resin solid content in the resin composition. The content is 5 to 50 parts by mass, and the content of the polymer (V) having the structural unit represented by formula (V) is 5 to 50 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition, and the aforementioned formula (V) is 5 to 50 parts by mass. The content of the compound (M1) represented by M1) is 5 to 50 parts by mass relative to 100 parts by mass of the resin solid content in the aforementioned resin composition, and the compound (M) represented by the aforementioned formula (M) includes the compound represented by the formula (M-1) The compound, and n is 1.05≦n≦20.00, and the weight average molecular weight of the polymer (V) having the structural unit represented by the formula (V) is 3,000 to 130,000. [Chemical 8] In the formula (M-1), R each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a halogen atom. m represents an integer from 0 to 3, n is the average of repeated numbers, and represents 1.00≦n≦20.00. <16> A cured product is a cured product of the resin composition according to any one of <1> to <15>. <17> A prepreg composed of a base material and the resin composition according to any one of <1> to <15>. <18> A metal foil-clad laminate comprising: at least one layer made of the prepreg according to <17>, and a single-sided or double-sided metal foil disposed on the layer made of the prepreg. . <19> A resin composite sheet including: a support, and a layer formed of the resin composition according to any one of <1> to <15> arranged on the surface of the support. <20> A printed wiring board including an insulating layer and a conductor layer disposed on the surface of the insulating layer, the insulating layer including a layer made of the resin composition according to any one of <1> to <15> At least one. <21> A semiconductor device including the printed wiring board according to <20>. [Effects of the invention]

According to the present invention, it is possible to provide a resin composition that maintains excellent low dielectric properties (Dk and/or Df) and has excellent moisture absorption and heat resistance, and to provide cured products, prepregs, metal foil-clad laminates, and resins. Composite sheets, printed wiring boards, and semiconductor devices.

Hereinafter, a mode for implementing the present invention (hereinafter referred to as "this embodiment") will be described in detail. In addition, the following embodiment is an illustration for explaining the present invention, and the present invention is not limited to only this embodiment. In addition, "～" in this specification is used in the meaning including the numerical value described before and after it as a lower limit value and an upper limit value. In this specification, various physical property values and characteristic values are assumed to be at 23°C unless otherwise stated. In the indications of groups (atomic groups) in this specification, indications that do not describe substitution or unsubstitution include groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In this specification, there is no indication of substitution or non-substitution, and the non-substitution is preferred. In this specification, the relative dielectric constant indicates the ratio of the dielectric constant of a substance to its dielectric constant in a vacuum. In addition, in this specification, the relative dielectric constant may be simply referred to as "dielectric constant". In this specification, "(meth)acrylic acid group" means both or any one of an acrylic acid group and a methacrylic acid group. "(Meth)allyl" represents both or any one of allyl and metallyl. The standards illustrated in this manual may have different measurement methods depending on the year. Unless otherwise stated, they are based on the standards as of January 1, 2022.

In this specification, the maleimide group refers to the group represented below. [Chemical 9] In the formula, A is independently a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. * is the bonding position with other parts. A From the viewpoint of ideal hardening, it is more ideal that both are hydrogen atoms. The number of carbon atoms in the alkyl group is preferably 1 to 3, more preferably 1 to 2, from the viewpoint of ideal hardening.

In this specification, the resin solid content refers to the component excluding fillers and solvents, and contains the compound (M) represented by the formula (M), the polymer (V) having the structural unit represented by the formula (V), and the formula (M1 ) represents the concept of the compound (M1), as well as other thermosetting compounds (C) and other resin additive components (additives such as flame retardants, etc.) that are blended as necessary.

The resin composition of this embodiment is characterized by containing a compound (M) represented by formula (M), a polymer (V) having a structural unit represented by formula (V), and a compound (M1) represented by formula (M1). . [Chemical 10] In the formula (M), R each independently represents a hydrocarbon group with 1 to 10 carbon atoms that may be substituted by a halogen atom, R ^mx each independently represents a methylene group, an ethylene group, or a 2,2-propylene group, and R ^my is a base selected from the following group (A). m represents an integer from 0 to 3, n is the average of repeated numbers, and represents 1.00≦n≦20.00. (Group (A)) [Chemicalization 11] In group (A), R ^y is each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may have a substituent, and ny is each independently an alkyl group having 0 to 3 carbon atoms. Integer, * is the bonding position with R ^mx . [Chemical 12] In formula (V), Ar represents an aromatic hydrocarbon connecting group. *Indicates bonding position. [Chemical 13] In formula (M1), R ^M1 , R ^M2 , R ^M3 and R ^M4 each independently represent a hydrogen atom or an organic group. R ^M5 and R ^M6 each independently represent a hydrogen atom or an alkyl group. Ar ^M represents a divalent aromatic group. A is an alicyclic group with 4 to 6 members. R ^M7 and R ^M8 are each independently an alkyl group. mx is 1 or 2, lx is 0 or 1. R ^M9 and R ^M10 each independently represent a hydrogen atom or an alkyl group. ^RM11 , ^RM12 , ^RM13 and ^RM14 each independently represent a hydrogen atom or an organic group. R ^M15 independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl group having 6 carbon atoms. An aryloxy group with ∼10 carbon atoms, an arylthio group with 6 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group. px represents an integer from 0 to 3. nx represents an integer from 1 to 20.

By adopting such a structure, it is possible to obtain a resin composition that is excellent in moisture absorption and heat resistance while maintaining excellent low dielectric properties (Dk and/or Df). The mechanism is not limited to this. It is speculated that in the compound (M) represented by the formula (M), R ^mxy is a methylene group, an ethylene group, or a 2,2-propylene group, and two R ^mx are bonded to one The benzene ring thus becomes a denser structure, so it is less likely to become rigid even if the cross-linking reaction proceeds, and it becomes easier to be compatible with other resin components. In particular, it is presumed that low dielectric properties (low relative dielectric constant, low dielectric constant) will be achieved by combining the compound (M) represented by the formula (M) and the polymer (V) having the structural unit represented by the formula (V). Electrical loss tangent (especially low dielectric loss tangent)). Furthermore, it is presumed that the compound (M1) represented by the formula (M1) and the polymer (V) having the structural unit represented by the formula (V) are represented by the formula (M) by making the hardening reaction temperature higher than that of these compounds. Compounding the compound (M) will control the progress of the hardening reaction in a well-balanced manner, and as a result, the moisture absorption and heat resistance will be improved. In addition, the resin composition of this embodiment can be made to have high heat resistance. Furthermore, the resin composition of this embodiment can be made to have high peel strength. In addition, the resin composition of this embodiment can be made to have excellent smear removal resistance.

<Compound (M) represented by formula (M)> The resin composition of this embodiment contains the compound (M) represented by formula (M). By containing the compound (M) represented by the formula (M), the low dielectric properties (Dk and/or Df) of the obtained resin composition can be effectively achieved. [Chemical 14] In the formula (M), R each independently represents a hydrocarbon group with 1 to 10 carbon atoms that may be substituted by a halogen atom, R ^mx each independently represents a methylene group, an ethylene group, or a 2,2-propylene group, and R ^my is a base selected from the following group (A). m represents an integer from 0 to 3, n is the average of repeated numbers, and represents 1.00≦n≦20.00. (Group (A)) [Chemical 15] In group (A), R ^y is each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may have a substituent, and ny is each independently an alkyl group having 0 to 3 carbon atoms. Integer, * is the bonding position with R ^mx .

In the formula (M), R each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a halogen atom, preferably an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen atom, or a halogen atom. The substituted phenyl group is selected from methyl, ethyl, propyl (preferably isopropyl), butyl (preferably secondary butyl, tertiary butyl), and phenyl which may also be substituted by a halogen atom. At least one of the groups is preferred. The aforementioned halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom or a chlorine atom. In this embodiment, R is preferably a hydrocarbon group having 1 to 10 carbon atoms that is not substituted by a halogen atom.

In the formula (M), m represents an integer from 0 to 3, preferably an integer from 0 to 2, more preferably 0 or 1, more preferably 0.

In formula (M), R ^mx are each independently a methylene group, an ethylene group, or a 2,2-propylene group. It is speculated that by using methylene, ethylene, or 2,2-propylene, R ^mx has lower dielectric properties (Dk and/or Df) and a soft structure than an aromatic ring, so even if it is crossed It is not easy to become rigid even when the coupling reaction is going on, and it is easy to be compatible with other resin components. R ^mx is preferably each independently an ethylene group or a 2,2-propylene group, and is more preferably a 2,2-propylene group.

In formula (M), ^Rmy is a base selected from group (A). In this way, by having a structure that is bonded to two adjacent R ^mx via one benzene ring, the structure does not become more rigid than necessary and becomes easily compatible with other resin components.

In group (A), R ^y is each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may have a substituent, and is preferably selected from methyl and ethyl groups. At least one of the group consisting of , propyl, methoxy, ethoxy, and phenyl. ny is independently an integer from 0 to 3, preferably an integer from 0 to 2, more preferably 0 or 1, even more preferably 0.

In this embodiment, in group (A), [Chemical 16] More ideal.

In addition, in the formula (M), n is the average of the repeated numbers, and represents 1.00≦n≦20.00. n is preferably 1.05 or more (1.05≦n), more preferably 1.10 or more (1.10≦n), more preferably 1.20 or more (1.20≦n), more preferably 1.25 or more (1.25≦n), more preferably 1.30 or more ( 1.30≦n) is even better, and above 1.50 (1.50≦n) is even better. By being above the aforementioned lower limit, the low dielectric properties (Dk and/or Df) of the compound (M) represented by the formula (M) tend to be improved, and the resin composition using the compound (M) and even the obtained cured product tend to have low dielectric properties. The dielectric properties (Dk and/or Df) also tend to improve. In particular, by setting 1.00≦n, the crystallinity of the compound (M) represented by the formula (M) decreases, so the solvent solubility tends to improve. In addition, n is preferably 10.00 or less (n≦10.00), more preferably 5.00 or less (n≦5.00), more preferably 3.00 or less (n≦3.00), and 2.75 or less (n≦2.75), still more preferably 2.50 The following (n≦2.50) is even better. By being below the aforementioned upper limit, the viscosity of the resin composition containing the compound (M) represented by the formula (M) will be reduced, the impregnation property will be improved, and the moldability will tend to be excellent. The value of n can be, for example, the number average molecular weight obtained by measuring the compound (M) represented by the formula (M) by gel permeation chromatography (GPC, detector: RI) or the area ratio of each separated peak. Come and ask for it.

In this embodiment, the compound (M) represented by the formula (M) preferably includes the compound represented by the formula (M-1). [Chemical 17] In the formula (M-1), R each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a halogen atom. m represents an integer from 0 to 3, n is the average of repeated numbers, and represents 1.00≦n≦20.00.

In formula (M-1), R, m and n are synonymous with R, m and n in formula (M) respectively, and the ideal range is also the same.

In this embodiment, it is more preferable that the compound (M) represented by the formula (M) contains the compound represented by the formula (M-2). [Chemical 18] In formula (M-2), ^Rz each independently represents a hydrocarbon group having 1 to 10 carbon atoms. m represents an integer from 0 to 3, n is the average of repeated numbers, and represents 1.00≦n≦20.00.

In the formula (M-2), m and n are synonymous with m and n in the formula (M), respectively, and the ideal range is also the same. R ^z is a hydrocarbon group with 1 to 10 carbon atoms, preferably an alkyl group or phenyl group with 1 to 10 carbon atoms, and is selected from methyl, ethyl, and propyl groups (preferably isopropyl) which may also be substituted by a halogen atom. , butyl (preferably secondary butyl, tertiary butyl), and at least one of the group consisting of phenyl is more preferred.

In this embodiment, the compound (M) represented by the formula (M) (preferably in the n=1 form contained in the compound (M) represented by the formula (M)) preferably contains two terminal maleimide groups and The nearest R ^mx to the aforementioned maleimide group (preferably 2,2-propylene) is located in one of the two terminal maleimide groups of the compound (MA) in the para position relative to the benzene ring. The one and the R ^mx (preferably 2,2-propylene) closest to the aforementioned maleimide group are located in the meta or ortho position relative to the benzene ring, and the other maleimide group is in the meta or ortho position with respect to the aforementioned maleimide group. The nearest R ^mx of the maleimide group (preferably 2,2-propylene) is located in a compound (MB) in the para position relative to the benzene ring, and the two terminal maleimide groups are far away from the aforementioned maleyl group. The nearest R ^mx of the imine group (preferably 2,2-propylene) is located in a compound (MC) in the meta or ortho position relative to the benzene ring. In this way, by mixing the compound (MA) with the compound (MB) and the compound (MC) with a high degree of rotational freedom of the phenylenemaleimide moiety in the molecule, there is a possibility of a hardening reaction. The degree of freedom in the distribution of cross-linking reaction points in the resin composition becomes higher, and a cured resin product with a stronger network tends to be formed. As a result, the heat resistance (such as glass transition temperature) and low thermal expansion of the resulting cured product tend to be further improved. Among the above compounds (MB) and compound (MC), it is preferable that the terminal maleimide group and R ^mx (preferably 2,2-propylene group) are located in the ortho position relative to the benzene ring.

In this embodiment, during HPLC analysis, the proportion of the compound (MA) in the compound (M) represented by the formula (M) is preferably 90 area % or less, more preferably 80 area % or less, and further preferably 70 area % or less. Better, it can also be less than 50 area% or less than 30 area%. By setting it below the upper limit, the crystallinity is reduced, so the solvent solubility tends to be improved. Moreover, the proportion of the compound (MA) may be 0 area %, more preferably 2 area % or more, still more preferably 5 area % or more, or 10 area % or more. By setting the ratio of the compound (MA) to 2 area % or more, there is a tendency that the decrease in reactivity can be effectively suppressed. When the proportion of the above compound (MA) in the formula (M) is 1.00≦n≦5.00, it should conform to the above range. When it is 1.00≦n≦3.00, it is better to conform to the above range. When n=1, it conforms to the above range. Even better. In addition, when the compound (MA) contains the following compound as a main component (for example, the proportion of the compound (M) represented by the formula (M) is 2 area % or more), it is preferably within the above range. [Chemical 19] In this embodiment, during HPLC analysis, the proportion of the compound (MB) in the compound (M) represented by the formula (M) is preferably less than 60 area %, and more preferably less than 55 area %. By setting it below the upper limit, the production cost of the compound (M) represented by the formula (M) and the reduction of industrial waste tend to be achieved. Moreover, the ratio of the compound (MB) is preferably 30 area % or more, more preferably 35 area % or more, and still more preferably 40 area % or more. When the proportion of the compound (MB) having an asymmetric structure is 30 area % or more, in addition to improving the solvent solubility, the low dielectric properties (Dk and/or Df) of the obtained hardened material tend to be improved. . As mentioned above, when the ratio of compound (MB) in formula (M) is 1.00≦n≦5.00, it should be within the above range, and when 1.00≦n≦3.00, it is more preferably within the above range. In addition, when the compound (MB) contains the following compound as a main component (for example, the proportion of the compound (M) represented by the formula (M) is 30% by mass or more), it is preferably within the above range. [Chemistry 20]

In this embodiment, during HPLC analysis, the proportion of the compound (MC) in the compound (M) represented by the formula (M) is preferably less than 60 area %, and more preferably less than 50 area %. Moreover, the ratio of the compound (MC) is preferably 15 area % or more, more preferably 25 area % or more. When the proportion of the compound (MC) is 15 area % or more, the low dielectric properties (Dk and/or Df) are better. When it is less than 60 area %, the hardening and adhesion are good, and the substrate can be effectively suppressed. Wait for defects in production. As mentioned above, when the ratio of the compound (MC) in the formula (M) is 1.00≦n≦5.00, it should be within the above range, and when 1.00≦n≦3.00, it is more preferably within the above range. In addition, when the compound (MC) contains the following compound as a main component (for example, the proportion of the compound represented by the formula (M) is 15% by mass or more), it is preferably within the above range. [Chemistry 21]

In addition, since the compound (M-A) has a large influence on the problem of crystallinity and deterioration of electrical characteristics, the total ratio of the compound (M-B) and the compound (M-C) in the compound (M) represented by the formula (M), The total amount of compound (M-A), compound (M-B), and compound (M-C) is preferably 50 area % or more, more preferably 60 area % or more, particularly preferably 70 area % or more. The upper limit is, for example, 100 area % or less, and may be 99 area % or less. In particular, in formula (M), when 1.00≦n≦5.00, it is preferably within the above range, and when 1.00≦n≦3.00, it is more preferably within the above range.

The softening point of the compound (M) represented by the formula (M) measured according to the method of JIS K-7234 is preferably 50°C or higher, more preferably 80°C or higher, more preferably 90°C or higher, particularly 95°C or higher. good. The softening point is preferably 150°C or lower, more preferably 140°C or lower, more preferably 130°C or lower, still more preferably 120°C or lower, and may also be 110°C or lower, or 100°C or lower.

The acid value of the compound (M) represented by the formula (M) is preferably 30 mgKOH/g or less, more preferably 1 to 15 mgKOH/g. If the acid value is high, there will be many molecules that have not been imidized by maleyl, and there will be an excess of carboxylic acid structures, which will affect the electrical properties and water resistance.

The weight average molecular weight (Mw) of the compound (M) represented by the formula (M) is preferably 500 or more, and may be 600 or more or 700 or more. By setting it to above the lower limit, the low dielectric properties (Dk and/or Df) and low water absorption of the obtained cured product tend to be further improved. The upper limit of the weight average molecular weight (Mw) of the compound (M) represented by the formula (M) is preferably 10,000 or less, more preferably 9,000 or less, still more preferably 7,000 or less, more preferably 5,000 or less, still more preferably 3,000 or less , preferably below 1,000. By setting it below the aforementioned upper limit, the heat resistance and workability of the obtained cured product tend to be further improved.

For the synthesis method of compound (M) represented by formula (M), please refer to the records of International Publication No. 2020-054601 and International Publication No. 2021-182360, and these contents are incorporated into this specification. When the compound (M) represented by the formula (M) is synthesized by the method described in these publications, the compound (M) represented by the formula (M) can be obtained as a mixture of the compound (M-A), the compound (M-B) and the compound (M-C). ). In addition, a commercially available product may be used as the compound (M) represented by the formula (M). For example, MIR-5000 (a compound in the formula (M-2) in which m=0) manufactured by Nippon Kayaku Co., Ltd. can be used. MIR-5000 can also be synthesized by the method described in the above-mentioned publication.

In the resin composition of this embodiment, when the resin solid content in the resin composition is 100 parts by mass, the content of the compound (M) represented by the formula (M) is preferably 5 to 50 parts by mass. The lower limit of the content of the compound (M) represented by the formula (M) is preferably 5 parts by mass or more, more preferably 7 parts by mass or more, and 10 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. More preferably, it is more than 15 parts by mass, still more preferably 18 parts by mass or more. When the content of the compound (M) represented by the formula (M) is 5 parts by mass or more, the obtained hardened material will have low dielectric properties (Dk and/or Df, especially low dielectric loss tangent) and metal foil peeling. Tendency to improve strength. Moreover, the upper limit of the content of the compound (M) represented by the formula (M) is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition. It is more preferably not more than 30 parts by mass, more preferably not more than 35 parts by mass. It may be 30 parts by mass or less, or it may be 25 parts by mass or less. When the content of the compound (M) represented by the formula (M) is 50 parts by mass or less, the heat resistance and moisture absorption heat resistance of the obtained cured product tend to be further improved. The resin composition in this embodiment may contain only one type of compound (M) represented by formula (M), or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

<Polymer (V) having a structural unit represented by formula (V)> The resin composition of this embodiment contains a polymer (V) having a structural unit represented by formula (V). By containing the polymer (V) having the structural unit represented by the formula (V), a resin composition excellent in low dielectric properties (low dielectric constant, low dielectric loss tangent) can be obtained. In particular, when used in combination with the compound (M) represented by the formula (M), a cured resin with a strong network is formed, so it is presumed to have excellent low dielectric properties (Dk and/or Df) and low thermal expansion. The coefficient (low CTE) is also excellent. [Chemistry 22] In formula (V), Ar represents an aromatic hydrocarbon connecting group. *Indicates bonding position.

The aromatic hydrocarbon connecting group may be a group consisting only of an aromatic hydrocarbon which may have a substituent, or a group consisting of a combination of an aromatic hydrocarbon which may have a substituent and other connecting groups. The aromatic hydrocarbon linking group is preferably a group consisting only of aromatic hydrocarbons which may have a substituent. In addition, the substituent that the aromatic hydrocarbon may have includes substituent Z (for example, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, an alkynyl group with 2 to 6 carbon atoms, an alkyl group with 1 to 6 carbon atoms, etc.). 6 alkoxy group, hydroxyl group, amine group, carboxyl group, halogen atom, etc.). Moreover, it is preferable that the above-mentioned aromatic hydrocarbon has no substituent. The aromatic hydrocarbon linking group is usually a divalent linking group.

Specific examples of the aromatic hydrocarbon linking group include phenylene group, naphthalenediyl group, anthracenediyl group, phenanthrenediyl group, biphenyldiyl group, and quinediyl group which may have a substituent. Among them, an optionally substituted phenylene group is preferred. phenyl. The substituent is exemplified by the above-mentioned substituent Z. However, the above-mentioned groups such as phenylene group are preferably unsubstituted.

It is more preferable that the structural unit represented by formula (V) contains at least one kind of the structural unit represented by the following formula (V1), the structural unit represented by the following formula (V2), and the structural unit represented by the following formula (V3). In addition, * in the following formula represents a bonding position. In addition, below, the structural units represented by Formulas (V1) to (V3) may be collectively referred to as "structural units (a)".

[Chemistry 23] In the formulas (V1) to (V3), L ¹ is an aromatic hydrocarbon linking group (preferably it has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, more preferably 6 to 10 carbon atoms). Specific examples thereof include phenylene group, naphthalenediyl, anthracenediyl, phenanthrenediyl, biphenyldiyl, and fendiyl which may have a substituent. Among these, a phenylene group which may have a substituent is preferred. The substituent is exemplified by the above-mentioned substituent Z. However, the above-mentioned groups such as phenylene group are preferably unsubstituted. The compound forming the structural unit (a) is preferably a divinyl aromatic compound, and examples thereof include: divinylbenzene, bis(1-methylvinyl)benzene, divinylnaphthalene, divinylanthracene, divinylbiphenyl, divinylbiphenyl, Vinphenanthrene etc. Among them, divinylbenzene is particularly preferred. One type of these divinyl aromatic compounds may be used, or two or more types may be used as needed.

The polymer (V) having the structural unit represented by the formula (V) may be a homopolymer of the structural unit (a) as described above, or a copolymer with a structural unit derived from another monomer. When the polymer (V) having the structural unit represented by the formula (V) is a copolymer, the copolymerization ratio of the structural unit (a) is preferably 3 mol% or more, more preferably 5 mol% or more. , more preferably 10 mol% or more, and may also be 15 mol% or more. The upper limit value is preferably 90 mol% or less, more preferably 85 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, and even more preferably 60 mol% or less. It is more preferably 50 mol% or less, more preferably 40 mol% or less, particularly preferably 30 mol% or less. In addition, it may be 25 mol% or less or 20 mol% or less.

As for the structural unit derived from another monomer, a structural unit (b) derived from an aromatic compound having one vinyl group (monovinyl aromatic compound) is exemplified.

The structural unit (b) derived from the monovinyl aromatic compound is preferably a structural unit represented by the following formula (V4).

[Chemistry 24] In the formula (V4), L ² is an aromatic hydrocarbon linking group. Preferable specific examples include the above-mentioned L ¹ . R ^V1 is a hydrogen atom or a hydrocarbon group with 1 to 12 carbon atoms (preferably an alkyl group). When R ^V1 is a hydrocarbon group, its carbon number is preferably 1 to 6, more preferably 1 to 3. R ^V1 and L ² may have the substituent Z mentioned above.

When the polymer (V) having a structural unit represented by formula (V) is a copolymer containing a structural unit (b) derived from a monovinyl aromatic compound, examples of the monovinyl aromatic compound include: Styrene, vinyl naphthalene, vinyl biphenyl and other vinyl aromatic compounds; o-methylstyrene, m-methylstyrene, p-methylstyrene, o-, p-dimethylstyrene, o-ethylvinylbenzene, m- Nuclear alkyl-substituted vinyl aromatic compounds such as ethylvinylbenzene, p-ethylvinylbenzene, methylvinylbiphenyl, ethylvinylbiphenyl, etc. The monovinyl aromatic compound exemplified here may also have the above-mentioned substituent Z as appropriate. Moreover, these monovinyl aromatic compounds may be used 1 type or 2 or more types may be used.

When the polymer (V) having the structural unit represented by the formula (V) is a copolymer containing the structural unit (b), the copolymerization ratio of the structural unit (b) is preferably 10 mol% or more and 15 mol% or more. More preferably, it may also be 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, or 75 mol% or more. . The upper limit is preferably 98 mol% or less, more preferably 90 mol% or less, and still more preferably 85 mol% or less.

The polymer (V) having the structural unit represented by the formula (V) may have other structural units other than the structural unit (a) and the structural unit (b). Examples of other structural units include structural units (c) derived from cycloolefin compounds. Examples of cycloolefin compounds include hydrocarbons having a double bond in the ring structure. Specific examples include monocyclic cyclic olefins such as cyclobutene, cyclopentene, cyclohexene, and cyclooctene. In addition, examples include norbornene, dicyclopentadiene, and the like having a norbornene ring. Compounds of structure; cyclic olefin compounds formed by the condensation of aromatic rings such as indene and acenaphthene. Examples of norbornene compounds include those described in paragraphs 0037 to 0043 of Japanese Patent Application Laid-Open No. 2018-39995, and the content is incorporated into this specification. In addition, the cycloolefin compound illustrated here may further have the above-mentioned substituent Z.

When the polymer (V) having the structural unit represented by the formula (V) is a copolymer containing the structural unit (c), the copolymerization ratio of the structural unit (c) is preferably 10 mol% or more and 20 mol% or more. More preferably, it is 30 mol% or more, still more preferably. The upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, 50 mol% or less, or 30 mol% or less.

The polymer (V) having the structural unit represented by the formula (V) may further contain a structural unit (d) derived from a different polymerizable compound (hereinafter also referred to as other polymerizable compound). Examples of other polymerizable compounds (monomers) include compounds containing three vinyl groups. Specific examples include: 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, and 1,2,4-trivinylcyclohexane. Or examples include: ethylene glycol diacrylate, butadiene, etc. The copolymerization ratio of the structural unit (d) derived from other polymerizable compounds is preferably 30 mol% or less, more preferably 20 mol% or less, and still more preferably 10 mol% or less.

An embodiment of the polymer (V) having the structural unit represented by the formula (V) includes the structural unit (a) as an essential component and contains at least one of the structural units (b) to (d). of polymers. In addition, an aspect in which the total of the structural units (a) to (d) accounts for more than 95 mol% of all the structural units is exemplified, and an aspect in which the total of the structural units (a) to (d) accounts for more than 98 mol% is exemplified. In another embodiment of the polymer (V) having the structural unit represented by the formula (V), it is preferable that the structural unit (a) is an essential component, and all the structural units except the terminal ones contain an aromatic ring. The structural unit is 90 mol% or more, preferably 95 mol% or more, and may also be 100 mol%. In addition, when calculating mol% of all structural units per unit, one structural unit is defined as the monomer used in the production of the polymer (V) derived from one molecule having the structural unit represented by the formula (V). (For example, divinyl aromatic compounds, monovinyl aromatic compounds, etc.).

The method for producing the polymer (V) having the structural unit represented by the formula (V) is not particularly limited and may be based on a common method. For example, a raw material containing a divinyl aromatic compound (monoethylene may be used if necessary). Aromatic compounds, cycloolefin compounds, etc. coexist), and polymerization is performed in the presence of Lewis acid catalyst. As a Lewis acid catalyst, metal fluorides such as boron trifluoride or complexes thereof can be used.

The structure of the chain end of the polymer (V) having the structural unit represented by the formula (V) is not particularly limited. If the group derived from the above-mentioned divinyl aromatic compound is explained, the following formula (E1) can be cited structure. In addition, L ¹ in the formula (E1) is the same as that defined in the above formula (V1). *Indicates bonding position. *-CH=CH-L ¹ -CH=CH ₂ (E1)

When a group derived from a monovinyl aromatic compound serves as a chain terminal, a structure adopting the following formula (E2) can be cited. L ² and R ^V1 in the formula are respectively synonymous with those defined in the aforementioned formula (V4). *Indicates bonding position. *-CH=CH-L ² -R ^V1 (E2)

The molecular weight of the polymer (V) having the structural unit represented by the formula (V) is preferably 300 or more in terms of number average molecular weight Mn, more preferably 500 or more, more preferably 1,000 or more, still more preferably 1,500 or more. The upper limit is preferably below 130,000, preferably below 120,000, preferably below 110,000, and preferably below 100,000. The molecular weight of the polymer (V) having the structural unit represented by the formula (V) is preferably at least 3,000, more preferably at least 5,000, more preferably at least 10,000 in terms of weight average molecular weight Mw. By setting the value to be not less than the aforementioned lower limit, the excellent low dielectric properties (Dk and/or Df), especially Df, the dielectric properties after moisture absorption are effectively exerted. The upper limit is preferably below 130,000, preferably below 100,000, preferably below 80,000, and preferably below 50,000. By setting it below the above-mentioned upper limit, there is a tendency that filling defects are less likely to occur when the prepreg or resin sheet is laminated on a circuit forming substrate. The monodispersity (Mw/Mn) expressed as the ratio of the weight average molecular weight Mw and the number average molecular weight Mn is preferably 100 or less, more preferably 50 or less, and still more preferably 20 or less. It is more practical for the lower limit value to be 1.1 or more, preferably 5 or more, more preferably 7 or more, and even more preferably 10 or more. The above-mentioned Mw and Mn were measured according to the description of the Examples mentioned later. When the resin composition of the present embodiment contains two or more types of polymers (V) having structural units represented by formula (V), the Mw, Mn and Mw/Mn of the mixture are preferably within the above ranges.

The equivalent weight of the vinyl group of the polymer (V) having the structural unit represented by the formula (V) is preferably 200 g/eq. or more, more preferably 230 g/eq. or more, and still more preferably 250 g/eq. or more. In addition, the vinyl equivalent weight is preferably 1200 g/eq. or less, more preferably 1000 g/eq. or less. In addition, it may be 800 g/eq. or less, 600 g/eq. or less, 400 g/eq. the following. By setting it to the above lower limit value or more, the storage stability of the resin composition will tend to be improved, and the fluidity of the resin composition will tend to be improved. Therefore, the formability is improved, and voids are less likely to occur during the formation of prepregs and the like, and a printed wiring board with higher reliability tends to be obtained. On the other hand, by setting it below the above-mentioned upper limit, the heat resistance of the obtained hardened material tends to be improved.

Regarding the polymer (V) having the structural unit represented by the formula (V) in this specification, reference can be made to the compounds and their synthesis reaction conditions described in International Publication No. 2017/115813, paragraphs 0029 to 0058, Japanese Patent Application Laid-Open No. 2018- The compounds described in paragraphs 0013 to 0058 of Japanese Patent Application Publication No. 039995 and their synthesis reaction conditions, etc., the compounds and their synthesis reaction conditions, etc. described in paragraphs 0008 to 0043 of Japanese Patent Application Laid-Open No. 2018-168347, and their synthesis reaction conditions, etc., Japanese Patent Application Laid-Open No. 2006-070136 The compounds described in paragraphs 0014 to 0042 of the publication and their synthesis reaction conditions, etc., the compounds and their synthesis reaction conditions, etc. described in paragraphs 0014 to 0061 of Japanese Patent Application Laid-Open No. 2006-089683, the compounds and their synthesis reaction conditions, etc., described in Japanese Patent Application Laid-Open No. 2008-248001 The compounds and their synthesis reaction conditions described in paragraphs 0008 to 0036 are incorporated into this specification.

In the resin composition of this embodiment, when the resin solid content in the resin composition is 100 parts by mass, the content of the polymer (V) having the structural unit represented by formula (V) is preferably 5 to 50 parts by mass.

The lower limit of the content of the polymer (V) having the structural unit represented by the formula (V) is 7 parts by mass or more, more preferably 9 parts by mass, when the resin solid content in the resin composition is 100 parts by mass. More preferably, it is more than 10 parts by mass, still more preferably 15 parts by mass or more. On the other hand, the upper limit of the content of the polymer (V) having the structural unit represented by the formula (V) is more preferably 45 parts by mass or less when the resin solid content in the resin composition is 100 parts by mass. It is more preferably 40 parts by mass or less, more preferably 35 parts by mass or less. It may be 30 parts by mass or less, or it may be 25 parts by mass or less. By setting the content of the polymer (V) having the structural unit represented by the formula (V) to be equal to or higher than the above lower limit, the cured product obtained will have low dielectric properties (Dk and/or Df) and good desmear properties. The tendency to have excellent patience. Moreover, by making it below the said upper limit, the metal foil peeling strength and moisture absorption heat resistance of the obtained hardened material can be effectively improved.

In addition, the lower limit of the content of the polymer (V) having the structural unit represented by the formula (V) is preferably 20 parts by mass or more and 30 parts by mass per 100 parts by mass of the compound (M) represented by the formula (M). The above is more preferably 40 parts by mass or more, still more preferably 50 parts by mass or more. In addition, it is preferably 60 parts by mass or more, 70 parts by mass or more, 75 parts by mass or more, or 80 parts by mass or more, depending on the use. It may be 85 parts by mass or more, 90 parts by mass or more, or 95 parts by mass or more. On the other hand, the upper limit of the content of the polymer (V) having the structural unit represented by the formula (V) is preferably 600 parts by mass or less and 500 parts by mass per 100 parts by mass of the compound (M) represented by the formula (M). Parts by mass or less are more preferred, parts by mass or less is still more preferred, parts by mass or less is still more preferred, and parts by mass or less are preferably 200 parts by mass or less, 170 parts by mass or less, 150 parts by mass or less, 140 parts by mass or less, and 130 parts by mass or less. Parts by mass or less, 125 parts by mass or less, depending on the use, etc., may be 120 parts by mass or less, 115 parts by mass or less, 110 parts by mass or less, or 105 parts by mass or less. By adjusting the content range of the polymer (V) having the structural unit represented by the formula (V) to the above range, there will be low dielectric properties (Dk and/or Df, especially low dielectric loss tangent) and metal foil peeling. Tends to have excellent strength, slag removal resistance, and moisture absorption and heat resistance. The resin composition may contain only one type of polymer (V) having a structural unit represented by formula (V), or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

<Compound (M1) represented by formula (M1)> The resin composition of this embodiment contains the compound (M1) represented by formula (M1). By using it in combination with the compound (M) represented by the above formula (M), the curing reaction proceeds appropriately, and the heat resistance and moisture absorption heat resistance of the obtained resin composition and even the cured product are improved. [Chemical 25] In formula (M1), R ^M1 , R ^M2 , R ^M3 and R ^M4 each independently represent a hydrogen atom or an organic group. R ^M5 and R ^M6 each independently represent a hydrogen atom or an alkyl group. Ar ^M represents a divalent aromatic group. A is an alicyclic group with 4 to 6 members. R ^M7 and R ^M8 are each independently an alkyl group. mx is 1 or 2, lx is 0 or 1. R ^M9 and R ^M10 each independently represent a hydrogen atom or an alkyl group. ^RM11 , ^RM12 , ^RM13 and ^RM14 each independently represent a hydrogen atom or an organic group. R ^M15 independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl group having 6 carbon atoms. An aryloxy group with ∼10 carbon atoms, an arylthio group with 6 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group. px represents an integer from 0 to 3. nx represents an integer from 1 to 20.

^RM1 , ^RM2 , ^RM3 and ^RM4 in the formula each independently represent a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl, ethyl, propyl or butyl group. , of which methyl is particularly preferred. R ^M1 and R ^M3 are preferably each independently an alkyl group, and R ^M2 and R ^M4 are preferably hydrogen atoms. R ^M5 and R ^M6 respectively independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. . Ar ^M represents a divalent aromatic group, and is preferably a phenylene group, naphthalenediyl, phenanthrenediyl, or anthracenediyl group, more preferably a phenylene group, and even more preferably a m-phenylene group. Ar ^M may also have a substituent, and the substituent is preferably an alkyl group, preferably an alkyl group with 1 to 12 carbon atoms, and even more preferably an alkyl group with 1 to 6 carbon atoms, such as methyl, ethyl, propyl, Butyl is more preferred, and methyl is particularly preferred. However, Ar ^M is preferably unsubstituted. A is a 4- to 6-membered alicyclic group, preferably a 5-membered alicyclic group (preferably a group that combines with a benzene ring to form an indene ring). R ^M7 and R ^M8 are each independently an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group. mx is 1 or 2, preferably 2. lx is 0 or 1, preferably 1. R ^M9 and R ^M10 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl, ethyl, propyl, or butyl group, of which methyl is particularly good. ^RM11 , ^RM12 , ^RM13 and ^RM14 each independently represent a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl, ethyl, propyl or butyl group. , among which, methyl is particularly preferred. R ^M12 and R ^M13 are each independently preferably an alkyl group, and R ^M11 and R ^M14 are preferably hydrogen atoms. R ^M15 independently represents an alkyl group with 1 to 10 carbon atoms, an alkyloxy group with 1 to 10 carbon atoms, an alkylthio group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, and an aryl group with 6 to 10 carbon atoms. The aryloxy group of 10, the arylthio group with 6 to 10 carbon atoms, the halogen atom, the hydroxyl group or the mercapto group is preferably an alkyl group with 1 to 4 carbon atoms, a cycloalkyl group with 3 to 6 carbon atoms, or 6 carbon atoms. ~10 of the aryl group. px represents an integer from 0 to 3, preferably an integer from 0 to 2, preferably 0 or 1, and even more preferably 0. nx represents an integer from 1 to 20. nx can also be an integer below 10. In addition, the resin composition of this embodiment may contain only one type of compound (M1) represented by formula (M1) and which have at least different values of nx, or may contain two or more types. When two or more types are contained, the average value (average number of repeating units) n of nx in the compound (M1) represented by the formula (M1) in the resin composition is used to obtain a low melting point (low softening point) and low melt viscosity. For excellent operability, it should be 0.92 or more, more preferably 0.95 or more, more preferably 1.0 or more, still more preferably 1.1 or more. In addition, n is preferably 10.0 or less, more preferably 8.0 or less, more preferably 7.0 or less, more preferably 6.0 or less, or 5.0 or less. The same applies to the following formula (M1-2) and the like.

The compound (M1) represented by the formula (M1) is preferably a compound represented by the following formula (M1-1). [Chemical 26] In formula (M1-1), ^RM21 , ^RM22 , ^RM23 , and ^RM24 each independently represent a hydrogen atom or an organic group. R ^M25 and R ^M26 each independently represent a hydrogen atom or an alkyl group. ^RM27 , ^RM28 , ^RM29 , and ^RM30 each independently represent a hydrogen atom or an organic group. R ^M31 and R ^M32 each independently represent a hydrogen atom or an alkyl group. ^RM33 , ^RM34 , ^RM35 , and ^RM36 each independently represent a hydrogen atom or an organic group. ^RM37 , ^RM38 , and ^RM39 each independently represent a hydrogen atom or an alkyl group. nx represents an integer from 1 to 20.

^RM21 , ^RM22 , ^RM23 , and ^RM24 in the formula each independently represent a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl, ethyl, propyl or butyl group. , which is particularly good for methyl. R ^M21 and R ^M23 are preferably alkyl groups, and R ^M22 and R ^M24 are preferably hydrogen atoms. R ^M25 and R ^M26 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl, ethyl, propyl, or butyl group, of which methyl is particularly good. ^RM27 , ^RM28 , ^RM29 , and ^RM30 each independently represent a hydrogen atom or an organic group, and are preferably a hydrogen atom. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl, ethyl, propyl or butyl group. , which is particularly good for methyl. R ^M31 and R ^M32 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl, ethyl, propyl, or butyl group, of which methyl is particularly good. ^RM33 , ^RM34 , ^RM35 , and ^RM36 each independently represent a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl, ethyl, propyl or butyl group. , which is particularly good for methyl. R ^M33 and R ^M36 are preferably hydrogen atoms, and R ^M34 and R ^M35 are preferably alkyl groups. ^RM37 , ^RM38 , and ^RM39 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl, ethyl, propyl, or butyl group, of which methyl is particularly good. nx represents an integer from 1 to 20. nx can also be an integer below 10.

The compound represented by formula (M1-1) is preferably a compound represented by the following formula (M1-2). [Chemical 27] In formula (M1-2), ^RM21 , ^RM22 , ^RM23 , and ^RM24 each independently represent a hydrogen atom or an organic group. R ^M25 and R ^M26 each independently represent a hydrogen atom or an alkyl group. ^RM27 , ^RM28 , ^RM29 , and ^RM30 each independently represent a hydrogen atom or an organic group. R ^M31 and R ^M32 each independently represent a hydrogen atom or an alkyl group. ^RM33 , ^RM34 , ^RM35 , and ^RM36 each independently represent a hydrogen atom or an organic group. ^RM37 , ^RM38 , and ^RM39 each independently represent a hydrogen atom or an alkyl group. nx represents an integer from 1 to 20.

In formula (M1-2), ^RM21 , ^RM22 , ^RM23 , ^RM24 , ^RM25 , ^RM26 , ^RM27 , ^RM28 , ^RM29 , ^RM30 , ^RM31 , ^RM32 , ^RM33 , ^RM34 , ^RM35 , ^RM36 , ^RM37 , ^RM38 , ^RM39 , and nx are respectively the same as ^RM21 , ^RM22 , RM23, ^RM24 , ^RM25 , ^RM26 , ^RM27 , ^RM28 in formula ( ^M1-1 ) , ^RM29 , ^RM30 , ^RM31 , ^RM32 , ^{RM33 , RM34} , ^RM35 , ^RM36 , RM37, ^RM38 , ^RM39 , and nx are synonymous, and the ideal range is also the same.

The compound represented by formula (M1-1) is preferably a compound represented by the following formula (M1-3), and more preferably a compound represented by the following formula (M1-4). [Chemical 28] In Formula (M1-3), nx represents an integer from 1 to 20. nx can also be an integer below 10. [Chemical 29] In Formula (M1-4), nx represents an integer from 1 to 20. nx can also be an integer below 10.

The molecular weight of the compound (M1) represented by the formula (M1) is preferably 500 or more, more preferably 600 or more, and still more preferably 700 or more. By setting it to above the lower limit, the low dielectric properties (Dk and/or Df) and low water absorption of the obtained cured product tend to be further improved. Furthermore, the molecular weight of the compound (M1) represented by the formula (M1) is preferably 10,000 or less, more preferably 9,000 or less, still more preferably 7,000 or less, more preferably 5,000 or less, still more preferably 4,000 or less. By setting it below the aforementioned upper limit, the heat resistance and workability of the obtained cured product tend to be further improved.

In the resin composition of this embodiment, when the resin solid content in the resin composition is 100 parts by mass, the content of the compound (M1) represented by the formula (M1) is preferably 5 to 50 parts by mass. The lower limit of the content of the compound (M1) represented by the formula (M1) is preferably 5 parts by mass or more, more preferably 7 parts by mass or more, and is 9 when the resin solid content in the resin composition is 100 parts by mass. It is more preferably not less than 10 parts by mass, and more preferably not less than 15 parts by mass. On the other hand, the upper limit of the content of the compound (M1) represented by the formula (M1) is preferably 50 parts by mass or less, and more preferably 40 parts by mass or less when the resin solid content in the resin composition is 100 parts by mass. Preferably, it is 35 parts by mass or less, even more preferably, it may be 30 parts by mass or less, or it may be 25 parts by mass or less. By setting the compound (M1) represented by the formula (M1) to be equal to or more than the above lower limit, the obtained cured product tends to be excellent in heat resistance and moisture absorption heat resistance. Moreover, by setting it below the said upper limit value, the metal foil peeling strength and the desmear resistance of the hardened material obtained can be effectively adjusted to a favorable range.

Moreover, the lower limit value of the content of the compound (M1) represented by the formula (M1) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more per 100 parts by mass of the compound (M) represented by the formula (M), and is More preferably 30 parts by mass or more, more preferably 60 parts by mass or more, more preferably 70 parts by mass or more, more than 80 parts by mass still more preferably, 85 parts by mass or more, particularly 90 parts by mass or more Preferably, it can also be more than 95 parts by mass. On the other hand, the upper limit of the content of the compound (M1) represented by the formula (M1) is preferably 600 parts by mass or less, and more preferably 500 parts by mass or less per 100 parts by mass of the compound (M) represented by the formula (M). , more preferably not more than 400 parts by mass, more preferably not more than 300 parts by mass, and preferably not more than 200 parts by mass, not more than 170 parts by mass, not more than 150 parts by mass, not more than 140 parts by mass, not more than 130 parts by mass, and not more than 125 parts by mass Parts or less may be 120 parts by mass or less, 115 parts by mass or less, 110 parts by mass or less, or 105 parts by mass or less depending on the use. By adjusting the content range of the compound (M1) represented by the formula (M1) to the above range, there will be low dielectric properties (Dk and/or Df, especially low dielectric loss tangent), metal foil peeling strength, and desmear removal. Tends to have excellent resistance to moisture absorption and heat resistance. The resin composition may contain only one type of compound (M1) represented by formula (M1) or two or more types. When two or more types are contained, the total amount is preferably within the above range.

In the resin composition of this embodiment, the content of the compound (M) represented by the formula (M), the polymer (V) having the structural unit represented by the formula (V), and the compound (M1) represented by the formula (M1) is In terms of mass ratio, the ratio of the polymer (V) having the structural unit represented by the formula (V) and the compound (M1) represented by the formula (M1) relative to 100 parts by mass of the compound (M) represented by the formula (M) is suitable. 30 to 130: 90 to 400, 40 to 130: 90 to 300 is better, 70 to 130: 90 to 140 is better, 70 to 110: 90 to 110 is even better, 90 to 105:90 ~105 is even better. By adjusting their blending ratio, the hardening of the resin composition can be progressed favorably, Df can be further reduced, and the desmear resistance can be further improved. Furthermore, in the resin composition of this embodiment, the ratio expressed by the content of the compound (M1) represented by the formula (M1)/the content of the polymer (V) having the structural unit represented by the formula (V) is preferably 3.0 or less. , is preferably 2.5 or less, more preferably 2.0 or less, more preferably 1.8 or less, and preferably 0.5 or more, more preferably 0.8 or more. By adjusting such a blending ratio, hardening of the resin composition can be progressed favorably, Df can be further reduced, and desmear resistance can be further improved.

<Other thermosetting compounds (C)> The resin composition of this embodiment may further contain a maleimide compound, an epoxy compound, a phenol compound selected from other than the compound (M) represented by the formula (M) and the compound (M1) represented by the formula (M1). Oxetane resins, benzodiazepine compounds, compounds containing (meth)allyl groups (preferably alkenyl nadic acid imine compounds) and polymers containing more than 2 carbon-carbon unsaturated double bonds One or more other thermosetting compounds (C) from the group consisting of phenylene ether compounds. By containing such components, the performance required by the printed wiring board can be exerted more effectively.

<<Maleimide compounds other than the compound (M) represented by the formula (M) and the compound (M1) represented by the formula (M1) >> The resin composition of this embodiment may also contain the compound represented by the formula (M) Maleimide compounds other than compound (M) and compound (M1) represented by formula (M1). In the resin composition of this embodiment, if there are more than 1 in 1 molecule (preferably 2 to 12, more preferably 2 to 6, more preferably 2 to 4, more preferably 2 or 3, The maleimide-based compound (2 or more preferably) is not particularly limited, and compounds commonly used in the field of printed wiring boards can be widely used. In this embodiment, the maleimide compound other than the compound (M) represented by the formula (M) and the compound (M1) represented by the formula (M1) preferably includes a compound selected from the compound represented by the formula (M2), the compound represented by the formula (M3) ), a compound represented by formula (M4), and a maleimide compound (M6), including one selected from the group consisting of a compound represented by formula (M2), a compound represented by formula (M3) More preferably, one or more types from the group consisting of a compound and a compound represented by formula (M4). [Chemical 30] In the formula (M2), R ⁵⁴ each independently represents a hydrogen atom or a methyl group, and n ₄ represents an integer of 1 or more. n ₄ is preferably an integer from 1 to 10, more preferably an integer from 1 to 5, even more preferably an integer from 1 to 3, even more preferably 1 or 2. The compound represented by formula (M2) may also be a mixture of n ₄ different compounds, and is preferably a mixture. [Chemical 31] In the formula (M3), R ⁵⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n ₅ represents an integer from 1 to 10. R ⁵⁵ is preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl, phenyl, and is one of hydrogen atom and methyl Even better, it is a hydrogen atom. n ₅ is preferably an integer from 1 to 5, more preferably an integer from 1 to 3, more preferably 1 or 2. The compound represented by formula (M3) may also be a mixture of compounds with n ₅ different compounds, and is preferably a mixture. [Chemical 32] In the formula (M4), R ⁵⁶ each independently represents a hydrogen atom, a methyl group or an ethyl group, and R ⁵⁷ each independently represents a hydrogen atom or a methyl group.

The maleimide compound (M6) is a compound having a structural unit represented by the formula (M6) and maleimide groups at both ends of the molecular chain. [Chemical 33] In formula (M6), R ⁶¹ represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. R ⁶² represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. R ⁶³ each independently represents a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. n each independently represents an integer from 0 to 10. For details of the maleimide compound (M6) and its production method, please refer to the descriptions in paragraphs 0061 to 0066 of International Publication No. 2020/262577, and the contents are incorporated into this specification.

Maleimide compounds other than the compound (M) represented by the formula (M) and the compound (M1) represented by the formula (M1) can be produced by a known method, and commercial products can also be used. Examples of commercially available products include: "BMI-2300" manufactured by Yamato Chemical Industry Co., Ltd. as the compound represented by the formula (M2), "MIR-3000" manufactured by Nippon Kayaku Co., Ltd. as the compound represented by the formula (M3), The compound represented by formula (M4) is "BMI-70" manufactured by K･I Chemical Co., Ltd., and the maleimide compound (M6) is "MIZ-001" manufactured by Nippon Kayaku Co., Ltd.

Examples of maleimide compounds other than those mentioned above include compounds having two or more maleimide groups. Specific examples include: isophenyl bismaleimide, 2,2-bis(4-(4 -Maleimidophenoxy)-phenyl)propane, 4-methyl-1,3-phenylbismaleimide, 1,6-bismaleimino-(2 ,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl ester bismaleimide, 1,3-bis( 3-maleiminophenoxy)benzene, 1,3-bis(4-maleiminophenoxy)benzene, and their prepolymers, and the combinations of these maleimides and amines Prepolymers, etc.

When a maleimide compound other than the compound (M) represented by the formula (M) and the compound (M1) represented by the formula (M1) is contained, the lower limit of the content shall be based on 100 mass of the resin solid content in the resin composition. Parts are preferably 1 part by mass or more, more preferably 5 parts by mass or more, more preferably 10 parts by mass or more, 20 parts by mass or more, or 25 parts by mass or more. When the content of the maleimide compound other than the compound (M) represented by the formula (M) and the compound (M1) represented by the formula (M1) is 1 part by mass or more, the flame resistance of the obtained cured product will be improved. tendency. Moreover, the upper limit of the content of the maleimide compound other than the compound (M) represented by the formula (M) and the compound (M1) represented by the formula (M1) is based on 100 parts by mass of the resin solid content in the resin composition. , preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and may also be 30 parts by mass or less. When the content of the maleimide compound other than the compound (M) represented by the formula (M) and the compound (M1) represented by the formula (M1) is 50 parts by mass or less, the metal foil peeling of the obtained cured product will be improved. Strength and low water absorption tendency. The resin composition in this embodiment may contain only one type of maleimide compound other than the compound (M) represented by the formula (M) and the compound (M1) represented by the formula (M1), or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range. Moreover, the resin composition in this embodiment may have a structure which does not substantially contain the maleimide compound other than the compound (M) represented by formula (M) and the compound (M1) represented by formula (M1). Substantially free of maleimide compounds other than the compound (M) represented by the formula (M) and the compound (M1) represented by the formula (M1), relative to 100 parts by mass of the resin solid content in the resin composition. Less than 1 part by mass, preferably less than 0.1 part by mass, more preferably less than 0.01 part by mass.

＜＜Epoxy compounds＞＞ The resin composition of this embodiment may contain an epoxy compound. If the epoxy compound has one or more rings per molecule (preferably 2 to 12, more preferably 2 to 6, more preferably 2 to 4, more preferably 2 or 3, more preferably 2), The oxygen-based compound or resin is not particularly limited, and compounds commonly used in the field of printed wiring boards can be widely used. Examples of the epoxy compound include: bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, bisphenol A Novolak type epoxy resin, glycidyl ester type epoxy resin, aralkyl novolak type epoxy resin, biphenyl aralkyl type epoxy resin, naphthyl ether type epoxy resin, cresol novolac type type epoxy resin, multifunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthalene skeleton modified novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene epoxy resin, biphenyl epoxy resin, cycloaliphatic epoxy resin, polyol epoxy resin, phosphorus-containing epoxy resin, epoxypropylamine, epoxy Propyl ester, compounds obtained by epoxidizing the double bonds of butadiene, etc., compounds obtained by the reaction of hydroxyl-containing silicone resins and epichlorohydrin, etc. By using them, the formability and adhesion of the resin composition will be improved. Among them, from the viewpoint of further improving flame retardancy and heat resistance, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, multifunctional phenol type epoxy resin, naphthalene type epoxy resin, and naphthalene type epoxy resin are suitable. Oxygen resin, preferably biphenyl aralkyl epoxy resin.

The resin composition of this embodiment preferably contains an epoxy compound within a range that does not impair the effects of the present invention. When the resin composition of this embodiment contains an epoxy compound, its content is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and more preferably 2 parts by mass or more based on 100 parts by mass of the resin solid content in the resin composition. Better. When the content of the epoxy compound is 0.1 parts by mass or more, the metal foil peeling strength and toughness of the obtained hardened material tend to be improved. When the resin composition of the present embodiment contains an epoxy compound, the upper limit of the content of the epoxy compound is preferably 50 parts by mass or less and 30 parts by mass or less based on 100 parts by mass of the resin solid content in the resin composition. More preferably, it is 20 parts by mass or less, still more preferably 10 parts by mass or less, and it may be 8 parts by mass or less, or 5 parts by mass or less. When the content of the epoxy compound is 50 parts by mass or less, the electrical characteristics of the obtained cured product tend to be improved. The resin composition in this embodiment may contain only one type of epoxy compound, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range. Moreover, the resin composition in this embodiment may have a structure which does not substantially contain an epoxy compound. Substantially free means that the content of the epoxy compound is less than 0.1 parts by mass, preferably less than 0.01 parts by mass, and may be less than 0.001 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

＜＜Phenolic compounds＞＞ The resin composition of this embodiment may contain a phenol compound. If the phenolic compound has 1 or more (preferably 2 to 12, more preferably 2 to 6, more preferably 2 to 4, more preferably 2 or 3, more preferably 2) phenolic properties per molecule The hydroxyl phenolic compound is not particularly limited, and compounds commonly used in the field of printed wiring boards can be widely used. Examples of the phenolic compound include bisphenol A phenolic resin, bisphenol E phenolic resin, bisphenol F phenolic resin, bisphenol S phenolic resin, phenol novolak resin, bisphenol A novolak type phenolic resin, and epoxy. Propyl ester type phenolic resin, aralkyl novolac phenolic resin, biphenyl aralkyl type phenolic resin, cresol novolak type phenolic resin, multifunctional phenolic resin, naphthol resin, naphthol novolak resin, multifunctional naphthalene Phenolic resin, anthracene type phenolic resin, naphthalene skeleton modified novolac type phenolic resin, phenol aralkyl type phenolic resin, naphthol aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin, lipid Cyclic phenolic resin, polyol-type phenolic resin, phosphorus-containing phenolic resin, hydroxyl-containing polysiloxane resin, etc. Among them, from the viewpoint of further improving the flame resistance of the obtained hardened material, it is preferable to select one selected from the group consisting of biphenyl aralkyl type phenolic resin, naphthol aralkyl type phenolic resin, phosphorus-containing phenolic resin, and hydroxyl-containing phenolic resin. At least one of the group consisting of polysiloxane resins.

The resin composition of this embodiment preferably contains a phenolic compound within a range that does not impair the effects of the present invention. When the resin composition of this embodiment contains a phenolic compound, its content is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and more preferably 2 parts by mass or more based on 100 parts by mass of the resin solid content in the resin composition. good. Moreover, it is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, more preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and may be 5 parts by mass or less. The resin composition in this embodiment may contain only one type of phenolic compound, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range. Furthermore, the resin composition in this embodiment may be configured to contain substantially no phenol compound. Substantially free means that the content of the phenolic compound is less than 0.1 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

＜＜Oxetane resin＞＞ The resin composition of this embodiment may contain an oxetane resin. If the oxetane resin has more than 1 (preferably 2 to 12, more preferably 2 to 6, more preferably 2 to 4, more preferably 2 or 3, more preferably 2) oxygen The heterocyclobutyl compound is not particularly limited, and compounds commonly used in the field of printed wiring boards can be widely used. Examples of the oxetane resin include: oxetane, alkyloxetane (for example, 2-methyloxetane, 2,2-dimethyloxetane, 3- Methyl oxetane, 3,3-dimethyloxetane, etc.), 3-methyl-3-methoxymethyloxetane, 3,3-bis(trifluoromethyl base) oxetane, 2-chloromethyl oxetane, 3,3-bis(chloromethyl) oxetane, biphenyl oxetane, OXT-101 (East Asia Synthetic Co., Ltd.), OXT-121 (manufactured by Toa Gosei Co., Ltd.), etc.

The resin composition of this embodiment preferably contains an oxetane resin within a range that does not impair the effects of the present invention. When the resin composition of this embodiment contains an oxetane resin, its content is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and 2 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. More than one portion is better. When the content of the oxetane resin is 0.1 parts by mass or more, the metal foil peeling strength and toughness of the obtained cured product tend to be improved. The upper limit of the content of the oxetane resin is preferably 50 parts by mass or less based on 100 parts by mass of the resin solid content in the resin composition when the resin composition of the present embodiment contains the oxetane resin. , it is more preferably 30 parts by mass or less, more preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and it may be 5 parts by mass or less. When the content of the oxetane resin is 50 parts by mass or less, the electrical characteristics of the obtained cured product tend to be improved. The resin composition in this embodiment may contain only one type of oxetane resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range. Furthermore, the resin composition in this embodiment may be substantially free of oxetane resin. Substantially free means that the content of the oxetane resin is less than 0.1 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

＜＜Benzodiazepine compounds＞＞ The resin composition of this embodiment may contain a benzene compound. If the benzene compound has 2 or more in 1 molecule (preferably 2 to 12, more preferably 2 to 6, more preferably 2 to 4, more preferably 2 or 3, more preferably 2) The compound of the dihydrobenzoic acid ring is not particularly limited, and compounds commonly used in the field of printed wiring boards can be widely used. Examples of benzophenone compounds include: bisphenol A type benzoyl BA-BXZ (manufactured by Konishi Chemical Co., Ltd.), bisphenol F type benzophenone BF-BXZ (manufactured by Konishi Chemical Co., Ltd.), bisphenol S type benzene Also available are BS-BXZ (manufactured by Konishi Chemical Co., Ltd.), etc.

The resin composition of this embodiment preferably contains a benzene compound within a range that does not impair the effects of the present invention. When the resin composition of this embodiment contains a benzene compound, its content is preferably 0.1 parts by mass or more and more preferably 50 parts by mass or less based on 100 parts by mass of the resin solid content in the resin composition. The resin composition in this embodiment may contain only one type of benzodiazepine compound, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range. Moreover, the resin composition in this embodiment may be substantially free of benzene compounds. Substantially free means that the content of the benzophenone compound is less than 0.1 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

＜＜Compounds containing (meth)allyl＞＞ The resin composition of this embodiment preferably contains a (meth)allyl-containing compound, and more preferably contains an allyl-containing compound. Furthermore, the compound containing a (meth)allyl group is preferably a compound containing two or more (meth)allyl groups, and a compound containing two or more allyl groups is more preferred. The compound containing a (meth)allyl group preferably includes an allyl isocyanurate compound, an allyl-substituted nadicamide compound, an allyl compound having a glycoluril structure, and diallyl benzene. At least one of the group consisting of dicarboxylic acid esters, including an allyl isocyanurate compound, an allyl-substituted nadicamide compound, and an allyl compound having a glycoluril structure. More preferably, it is at least one of the group, more preferably it contains an allyl-substituted nadicide imine compound, and still more preferably it is an alkenyl nadicide imine compound.

When the resin composition of this embodiment contains a (meth)allyl group-containing compound, its molecular weight is preferably 195 or more, more preferably 300 or more, more preferably 400 or more, still more preferably 500 or more. By setting it to the lower limit value or more, the low dielectric property and heat resistance of the obtained hardened material tend to be further improved. The molecular weight of the (meth)allyl-containing compound is also preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less, still more preferably 800 or less. By setting it below the above-mentioned upper limit, the low thermal expansion property of the obtained hardened material tends to be further improved.

When the resin composition of this embodiment contains a (meth)allyl group-containing compound, its content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, based on 100 parts by mass of the resin solid content in the resin composition. , more preferably 5 parts by mass or more, and may be 10 parts by mass or more. By setting the content of the (meth)allyl group-containing compound to be equal to or more than the above lower limit, the moldability of the resin composition will be excellent, and the heat resistance of the resulting cured product will tend to be further improved. In addition, the upper limit of the content of the (meth)allyl group-containing compound is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and 20 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. A portion or less is better. By setting the content of the (meth)allyl group-containing compound below the above upper limit, the low thermal expansion property of the obtained cured product tends to be further improved. The resin composition of this embodiment may contain only one type of (meth)allyl-containing compound, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range. Moreover, the resin composition in this embodiment may have a structure which does not substantially contain the compound containing a (meth)allyl group. Substantially free means that the content of the (meth)allyl-containing compound is less than 0.1 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

＜＜＜Allyl isocyanurate compound＞＞＞ The allyl isocyanurate compound must be a compound having two or more allyl groups and an isocyanurate ring (uric acid ester skeleton) , then there is no particular restriction, and it is preferably a compound represented by formula (TA). Formula (TA) [Chemical 34] In formula (TA), R ^A represents a substituent.

In the formula (TA), R ^A represents a substituent, preferably a substituent with a chemical formula weight of 15 to 500.

The first example of ^RA is an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms. By using an allyl compound having an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, it is possible to provide a resin composition capable of obtaining a cured product having excellent crosslinkability and high toughness. Thereby, even if the resin composition does not contain a base material such as glass cloth, damage during etching processing, etc. can be suppressed. The number of carbon atoms in the alkyl group and/or alkenyl group is preferably 3 or more, more preferably 8 or more, and may be 12 or more and preferably 18 or less from the viewpoint of improving operability. It is thought that the resin fluidity of the resin composition will be improved by this, and the circuit embedding property when using the resin composition of this embodiment to produce a multilayer circuit board or the like can be improved.

The second example of R ^A is a group containing an allyl isocyanurate group. When R ^A contains an allyl isocyanurate group, the compound represented by formula (TA) is preferably a compound represented by formula (TA-1). Formula (TA-1) [Chemical 35] In formula (TA-1), R ^A2 is a divalent linking group.

In the formula (TA-1), R ^A2 is preferably a divalent linking group with a chemical formula weight of 54 to 250, more preferably a divalent linking group with a chemical formula weight of 54 to 250 and carbon atoms at both ends, and a carbon number of 2 to 250. The aliphatic hydrocarbon group of 20 is even better (however, the aliphatic hydrocarbon group may also contain an ether group and may also contain a hydroxyl group). More specifically, R ^A2 is preferably a group represented by any one of the following formulas (i) to (iii). [Chemical 36] In the formulas (i) to (iii), p ^c1 represents the number of repeating units of the methylene group, and is an integer from 2 to 18. p ^c2 represents the number of repeating units of oxyethylene group, and is 0 or 1. * is the bonding part. The aforementioned p ^c1 is preferably an integer from 2 to 10, more preferably an integer from 3 to 8, and even more preferably an integer from 3 to 5. The aforementioned p ^c2 may also be 0 or 1, preferably 1.

R ^A2 should be the first example.

In this embodiment, the reactive group (allyl) equivalent of the compound represented by formula (TA) is preferably 1,000 or less. It is considered that if the equivalent is 1,000 or less, high Tg can be obtained more reliably. The alkyl group having 1 to 22 carbon atoms can be a linear or branched alkyl group, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl. Base, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, behenyl, etc. Examples of the alkenyl group having 2 to 22 carbon atoms include allyl group, decene group, and the like.

Specific examples of the compound represented by formula (TA) include triallyl isocyanurate, 5-octyl-1,3-diallyl isocyanurate, and 5-dodecyl- 1,3-diallylisocyanurate, 5-tetradecyl-1,3-diallylisocyanurate, 5-hexadecyl-1,3-diallyl Isocyanurate, 5-octadecyl-1,3-diallylisocyanurate, 5-eicosyl-1,3-diallylisocyanurate, 5- Behenyl-1,3-diallyl isocyanurate, 5-decenyl-1,3-diallyl isocyanurate, etc. These may be used alone or in combination of two or more types, and may be used in the form of a prepolymer.

The method of producing the compound represented by the formula (TA) is not particularly limited. For example, diallylisocyanurate and an alkyl halide can be produced in an aprotic compound such as N,N'-dimethylformamide. It is obtained by reacting in a polar solvent at a temperature of about 60°C to 150°C in the presence of alkaline substances such as sodium hydroxide, potassium carbonate, and triethylamine.

In addition, a commercially available compound represented by formula (TA) can also be used. There are no particular restrictions on commercial sellers, and examples thereof include L-DAIC manufactured by Shikoku Chemical Industry Co., Ltd. Examples of triallyl isocyanurate include TAIC manufactured by Mitsubishi Chemical Co., Ltd. Examples of the compound represented by the formula (TA-1) include DD-1 manufactured by Shikoku Chemical Industry Co., Ltd.

The molecular weight of the allyl isocyanurate compound (preferably the compound represented by formula (TA)) is preferably 200 or more, more preferably 300 or more, more preferably 400 or more, still more preferably 500 or more. By setting the molecular weight to be equal to or higher than the lower limit, the low dielectric properties and heat resistance of the obtained cured product tend to be further improved. Furthermore, the molecular weight of the allyl isocyanurate compound (preferably the compound represented by formula (TA)) is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less, still more preferably 800 or less. By setting the molecular weight to be equal to or less than the upper limit, the low thermal expansion property of the obtained cured product tends to be further improved.

When the resin composition of this embodiment contains an allyl isocyanurate compound, its content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, based on 100 parts by mass of the resin solid content in the resin composition. More preferably, it is 5 parts by mass or more, and it may be 10 parts by mass or more. By setting the content of the allyl isocyanurate compound to not less than the above lower limit, the moldability of the resin composition is excellent, and the heat resistance of the obtained cured product tends to be further improved. In addition, the upper limit of the content of the allyl isocyanurate compound is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and 20 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. The following is even better. By setting the content of the allyl isocyanurate compound below the above upper limit, the low thermal expansion property of the obtained cured product tends to be further improved. The resin composition of this embodiment may contain only one type of allyl isocyanurate, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

＜＜＜Allyl-substituted nadicide imine compound＞＞ If the allyl-substituted nadicide imine compound is a compound with more than one allyl-substituted nadicide imine group in the molecule (preferably There are no particular restrictions on compounds having one or more nadicidoimine groups substituted by alkenyl groups in the molecule (alkenyl nadicidoimine compounds). Specific examples thereof include compounds represented by the following formula (AN). Formula (AN) [Chemistry 38] In the formula (AN), R ₁ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₂ represents an alkylene group, phenylene group, biphenylene group, or naphthylene group having 1 to 6 carbon atoms. , or the base represented by formula (AN-2) or (AN-3). Formula (AN-2) [Chemical 40] In the formula (AN-2), R ₃ represents a methylene group, an isopropylene group, a group represented by -C(=O)-, -O-, -S-, or -S(=O) ₂ -. Formula (AN-3) [Chemical 42] In formula (AN-3), R ₄ each independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.

In addition, a commercially available compound represented by formula (AN) can also be used. Commercially available compounds are not particularly limited, and examples include compounds represented by formula (AN-4) (BANI-M (manufactured by Maruzen Petrochemical Co., Ltd.)), compounds represented by formula (AN-5) (BANI-X ( Maruzen Petrochemical Co., Ltd.), etc. These can be used 1 type or in combination of 2 or more types. Formula (AN-4) [Chemistry 55] Formula (AN-5) [Chemistry 56]

The molecular weight of the allyl-substituted nadicamide compound (preferably the compound represented by formula (AN)) is preferably 400 or more, more preferably 500 or more, and may also be 550 or more. By setting the molecular weight of the allyl-substituted nadic acid imine compound to be equal to or higher than the above lower limit, the low dielectric property, low thermal expansion property, and heat resistance of the obtained cured product tend to be further improved. The molecular weight of the allyl-substituted nadicamide compound (preferably a compound represented by formula (AN)) is also preferably 1,500 or less, more preferably 1,000 or less, still more preferably 800 or less, and may also be 700 or less or 600 or less. . By setting the molecular weight of the allyl-substituted nadicide imine compound to less than the above upper limit, the moldability of the resin composition and the peel strength of the obtained cured product tend to be further improved.

When the resin composition of this embodiment contains an allyl-substituted nadicamide compound (preferably a compound represented by formula (AN)), its content is preferably 0.1 with respect to 100 parts by mass of the resin solid content in the resin composition. The amount is more than 1 part by mass, more preferably not less than 1 part by mass, and even more preferably not less than 2 parts by mass. Moreover, it is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, more preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and may be 5 parts by mass or less. By setting the content of the allyl-substituted nadicamide compound below the above upper limit, the formability of the resin composition and the peel strength of the obtained cured product tend to be further improved. The resin composition of this embodiment may contain only one type of allyl-substituted nadicamide compound, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range. Moreover, the resin composition in this embodiment may be a structure which does not substantially contain an allyl-substituted nadic acid imine compound. Substantially free means that the content of the allyl-substituted nadicamide compound is less than 0.1 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

＜＜＜Allyl compound having glycoluril structure>>＞ If the allyl compound having glycoluril structure is a compound containing two or more glycoluril structures and allyl groups, there is no particular limitation, and it is preferably of the formula ( Compounds represented by GU). Formula (GU) [Chemical 44] In formula (GU), R is each independently a hydrogen atom or a substituent, and at least 2 of R are groups containing allyl groups. In the formula (GU), R is preferably a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or an alkenyl group with 2 to 5 carbon atoms, more preferably an alkenyl group with 2 to 5 carbon atoms, and is allyl. Even better. In the formula (GU), R is preferably a group having 3 or 4 R's containing allyl groups, more preferably 4 R's containing allyl groups.

Specific examples of the compound represented by the formula (GU) include 1,3,4,6-tetraallyl glycoluril (a compound in which all R in the formula (GU) are allyl groups).

In addition, a commercially available compound represented by formula (GU) can also be used. Commercially available ones are not particularly limited, and examples thereof include TA-G manufactured by Shikoku Chemical Industry Co., Ltd.

The molecular weight of the allyl compound having a glycoluril structure (preferably a compound represented by formula (GU)) is preferably 195 or more, more preferably 220 or more, more preferably 250 or more, and may also be 300 or more or 400 or more. By setting the molecular weight of the allyl compound having a glycoluril structure to the above lower limit value or more, the low dielectric property and heat resistance of the obtained cured product tend to be further improved. The molecular weight of the allyl compound having a glycoluril structure (preferably a compound represented by formula (GU)) is also preferably 1,500 or less, more preferably 1,000 or less, more preferably 800 or less, and may also be 700 or less or 600 or less. By setting the molecular weight of the allyl compound having a glycoluril structure to the above upper limit or less, the low thermal expansion property of the obtained cured product tends to be further improved.

When the resin composition of this embodiment contains an allyl compound having a glycoluril structure (preferably a compound represented by formula (GU)), its content is preferably 1 part by mass relative to 100 parts by mass of the resin solid content in the resin composition. parts by mass or more, more preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and 10 parts by mass or more. By setting the content of the allyl compound having a glycoluril structure to the above lower limit value or more, the low dielectric properties and heat resistance of the obtained cured product tend to be further improved. Furthermore, the upper limit of the content of the allyl compound having a glycoluril structure (preferably a compound represented by formula (GU)) is preferably 40 parts by mass or less based on 100 parts by mass of the resin solid content in the resin composition. It is more preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and it may be 20 parts by mass or less. By setting the content of the allyl compound having a glycoluril structure to the above upper limit or less, the low thermal expansion property of the obtained cured product tends to be further improved. The resin composition of this embodiment may contain only one type of allyl compound having a glycoluril structure, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

＜＜Polyphenylene ether compounds containing more than 2 carbon-carbon unsaturated double bonds＞＞ The resin composition of this embodiment may contain a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds. The polyphenylene ether compound containing more than 2 carbon-carbon unsaturated double bonds is preferably a polyphenylene ether compound having more than 2 carbon-carbon unsaturated double bonds at the end, and the polyphenylene ether compound having more than 2 optional freedoms at the end ( A polyphenylene ether compound containing a group consisting of a meth)acrylic acid group, a maleimide group, or a vinyl benzyl group is more preferred. By using these polyphenylene ether compounds, the dielectric properties and low water absorption of printed wiring boards and the like tend to be more effectively improved. Their details are explained below.

The polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is exemplified by a compound having a phenylene ether skeleton represented by the following formula (X1).

[Chemical 45] In formula (X1), R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁷ may be the same or different, and represent an alkyl group having 6 or less carbon atoms, an aryl group, a halogen atom, or a hydrogen atom.

Polyphenylene ether compounds containing more than two carbon-carbon unsaturated double bonds may further contain repeating units represented by formula (X2) and/or repeating units represented by formula (X3). [Chemical 46] In formula (X2), R ²⁸ , R ²⁹ , R ³⁰ , R ³⁴ , and R ³⁵ may be the same or different, and represent an alkyl group or phenyl group having 6 or less carbon atoms. R ³¹ , R ³² , and R ³³ may be the same or different, and may be a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. [Chemical 47] In the formula (X3), R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , and R ⁴³ may be the same or different, and may be a hydrogen atom, an alkyl group having 6 or less carbon atoms, or phenyl. -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

The polyphenylene ether compound containing more than two carbon-carbon unsaturated double bonds is preferably a modified polyphenylene ether compound in which part or all of the terminals are functionalized with ethylenically unsaturated groups (hereinafter sometimes referred to as "modified polyphenylene ether compound"). Polyphenylene ether compound (g)") is a modified polyphenylene ether having at least two terminal groups selected from the group consisting of (meth)acrylic acid groups, maleimide groups, and vinyl benzyl groups. Compounds are better. By using such a modified polyphenylene ether compound (g), the dielectric loss tangent (Df) of the cured resin composition can be further reduced, and low water absorption and metal foil peeling strength can be improved. One type of these may be used, or two or more types may be used in combination.

Examples of the modified polyphenylene ether compound (g) include compounds represented by formula (OP-1). [Chemical 48] In Formula ⁽ _OP - ¹ ) ^, Base, n ₁ represents an integer from 1 to 6, n ₂ represents an integer from 1 to 100, and n ₃ represents an integer from 1 to 4. When n ₂ and/or n ₃ are an integer of 2 or more, the n ₂ structural units (YO) and/or the n ₃ structural units may be the same or different, respectively. n ₃ is preferably 2 or more, more preferably 2.

The modified polyphenylene ether compound (g) in this embodiment is preferably a compound represented by formula (OP-2). [Chemical 49] Here, -(OXO)- is preferably represented by formula (OP-3) and/or formula (OP-4). [Chemical 50] In formula (OP-3), R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , and R ¹¹ may be the same or different, and may be an alkyl group or phenyl group having 6 or less carbon atoms. R ⁷ , R ⁸ , and R ⁹ may be the same or different, and may be a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. [Chemistry 51] In the formula (OP-4), R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , and R ¹⁹ may be the same or different, and they may be a hydrogen atom and a carbon number of 6 or less. Alkyl or phenyl. -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

In addition, -(YO)- is preferably represented by formula (OP-5). [Chemistry 52] In formula (OP-5), R ²⁰ and R ²¹ may be the same or different, and may be an alkyl group or phenyl group having 6 or less carbon atoms. R ²² and R ²³ may be the same or different, and may be a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. In the formula (OP-2), a and b represent at least one of them that is not 0 and an integer from 0 to 100, preferably an integer from 0 to 50, and more preferably an integer from 1 to 30. When a and/or b are an integer of 2 or more, two or more -(YO)- may be independently arranged in one structure, or two or more structures may be arranged in blocks or randomly.

Examples of -A- in the formula (OP-4) include: methylene, ethylene, 1-methylethylene, 1,1-propylene, 1,4-phenylenebis(1- Methylethylene), 1,3-phenylbis(1-methylethylene), cyclohexylene, phenylmethylene, naphthylmethylene, 1-phenylethylene, etc. 2 Valence organic base, but not limited to this.

Among the above-mentioned modified polyphenylene ether compounds (g), it is preferable that R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ , R ²⁰ and R ²¹ are alkyl groups having 3 or less carbon atoms, and R ⁷ and R ^8. Polyphenylene ether in which R ⁹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²² , and R ²³ are hydrogen atoms or alkyl groups with less than 3 carbon atoms. The compound is -(OXO) represented by formula (OP-3) or formula (OP-4) - is formula (OP-9), formula (OP-10) and/or formula (OP-11), and formula ( The -(YO)- represented by OP-5) is particularly preferably the formula (OP-12) or the formula (OP-13). When a and/or b is an integer of 2 or more, the two or more -(YO)- can be independently arranged by two or more formulas (OP-12) and/or formula (OP-13) structure, or a structure formed by block or random arrangement of Formula (OP-12) and Formula (OP-13).

[Chemistry 53] [Chemistry 54] In formula (OP-10), R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , and R ⁴⁷ may be the same or different, and may be a hydrogen atom or a methyl group. -B- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms. Specific examples of -B- are the same as those of -A- in formula (OP-4). [Chemical 55] In the formula (OP-11), -B- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms. Specific examples of -B- are the same as those of -A- in formula (OP-4). [Chemical 56] [Chemistry 57]

For details on other polyphenylene ether compounds containing more than two carbon-carbon unsaturated double bonds, please refer to the records in Japanese Patent Application Laid-Open No. 2018-016709, and these contents are incorporated into this specification.

Average number of polystyrene-converted polyphenylene ether compounds (preferably modified polyphenylene ether compounds (g)) containing two or more carbon-carbon unsaturated double bonds using GPC (gel permeation chromatography) method The molecular weight is preferably 500 or more and 3,000 or less (in detail, following the method described in the Examples described later). When the number average molecular weight is 500 or more, when the resin composition of this embodiment is formed into a coating film, adhesion tends to be further suppressed. When the number average molecular weight is 3,000 or less, the solubility in solvents tends to be further improved. In addition, the polystyrene-converted weight average molecular weight of a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds (preferably a modified polyphenylene ether compound (g)) using GPC (details are as follows) The method described in the Examples) is preferably 800 or more and 10,000 or less, more preferably 800 or more and 5,000 or less. By setting it above the above-mentioned lower limit value, the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition tend to become lower. By setting it below the above-mentioned upper limit value, , there will be a tendency to further improve the solubility, low viscosity and formability of the resin composition in solvents when making varnishes and the like described later. In addition, when the modified polyphenylene ether compound (g) is used, the terminal carbon-carbon unsaturated double bond equivalent per carbon-carbon unsaturated double bond is preferably 400 to 5000 g, more preferably 400 to 2500 g. good. By setting it to the above lower limit or more, the relative dielectric constant (Dk) and the dielectric loss tangent (Df) of the cured product of the resin composition tend to become lower. By setting it below the above upper limit, the solubility, low viscosity and moldability of the resin composition in a solvent tend to be further improved.

When the resin composition of this embodiment contains a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, the lower limit of the content of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is , relative to 100 parts by mass of the resin solid content in the resin composition, it is preferably at least 1 part by mass, more preferably at least 3 parts by mass, more preferably at least 5 parts by mass, more preferably at least 7 parts by mass, and 10 Quality parts and above are better. By setting it to above the lower limit, the low water absorbency and low dielectric properties (Dk and/or Df) of the obtained cured material tend to be further improved. Furthermore, the upper limit of the content of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is preferably 50 parts by mass or less and 45 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. More preferably, it is not more than 40 parts by mass, still more preferably not more than 35 parts by mass, still more preferably not more than 30 parts by mass, still more preferably not more than 25 parts by mass, and may be not more than 20 parts by mass. By setting it below the upper limit, the heat resistance and chemical resistance of the obtained cured product tend to be further improved. The resin composition in this embodiment may contain only one type of polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

Moreover, the resin composition in this embodiment may have a structure which does not substantially contain the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds. Substantially free means that the content of a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is less than 0.1 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition, preferably less than 0.01 parts by mass, and may be less than 0.001 parts by mass.

When the resin composition of this embodiment contains other thermosetting compounds (C), its content (total amount) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and 10 parts by mass based on 100 parts by mass of the resin solid content. More preferably, it is more than 20 parts by mass, more preferably not less than 20 parts by mass, and it may be more than 30 parts by mass. By setting it to above the lower limit, the heat resistance, plating adhesion, low thermal expansion, etc. of the obtained hardened material tend to be further improved. Furthermore, the upper limit of the content of the other thermosetting compound (C) is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and still more preferably 40 parts by mass or less based on 100 parts by mass of the resin solid content. By setting it below the upper limit, the low dielectric properties (Dk and/or Df) and low water absorption of the obtained cured product tend to be further improved. The resin composition of this embodiment may contain only one type of other thermosetting compound (C), or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

＜Filling material (D)＞ The resin composition of this embodiment preferably contains filler (D). By containing the filler (D), physical properties such as dielectric characteristics (low dielectric constant, low dielectric loss tangent, etc.), flame resistance, and low thermal expansion of the resin composition or its hardened product can be further improved. Moreover, it is more preferable that the filler (D) used in this embodiment has excellent low dielectric properties (Dk and/or Df). For example, the relative dielectric constant (Dk) of the filling material (D) used in this embodiment measured by the resonant cavity perturbation method at a frequency of 10 GHz is preferably 8.0 or less, and more preferably 6.0 or less. It is better if it is below 4.0. In addition, it is more practical that the lower limit value of the relative dielectric constant is, for example, 2.0 or more. In addition, the dielectric loss tangent (Df) of the filler (D) used in this embodiment measured by the resonant cavity perturbation method at a frequency of 10 GHz is preferably 0.05 or less, more preferably 0.01 or less. In addition, it is more practical that the lower limit value of the dielectric loss tangent is, for example, 0.0001 or more.

The type of filler (D) used in this embodiment is not particularly limited, and those commonly used by those with ordinary knowledge in the technical field to which the invention pertains can be preferably used. Specific examples include: natural silica, fused silica, synthetic silica, amorphous silica, fumed silica (AEROSIL), hollow silica and other silicas; alumina, white carbon , titanium dioxide, titanium oxide, zinc oxide, magnesium oxide, zirconium oxide and other metal oxides; zinc borate, zinc stannate, forsterite (forsterite), barium titanate, strontium titanate, calcium titanate and other composite oxides; Nitrides such as boron nitride, condensed boron nitride, silicon nitride, aluminum nitride, etc.; aluminum hydroxide, aluminum hydroxide heat-treated products (aluminum hydroxide is heated to remove part of the crystal water), soft aluminum Metal hydroxides (including hydrates) such as boehmite and magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdate; barium sulfate, clay, kaolin, talc, calcined clay, calcined kaolin ( kaolin), calcined talc (talc), mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, short glass fibers (including E Glass, T glass, D glass, S glass, Q glass and other glass fine powders), insulating glass, spherical glass and other inorganic filling materials; in addition, styrene type, butadiene type, acrylic type Organic fillers such as type rubber powder, core-shell rubber powder, polysilicone resin powder, polysilicone rubber powder, polysilicone composite powder, etc. In this embodiment, the inorganic filler preferably contains a material selected from the group consisting of silicon dioxide, aluminum hydroxide, aluminum nitride, boron nitride, forsterite, titanium oxide, barium titanate, strontium titanate, and calcium titanate. More preferably, one or more types from the group are selected. From the viewpoint of low dielectric properties (Dk and/or Df), one or more types selected from the group consisting of silicon dioxide and aluminum hydroxide is more preferred, including both. Silicon oxide is even better. By using these inorganic fillers, the heat resistance, dielectric properties, thermal expansion properties, dimensional stability, flame retardancy and other properties of the cured resin composition will be further improved.

The content of the filler (D) in the resin composition of this embodiment can be appropriately set according to the desired characteristics and is not particularly limited. It is preferably 10 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. parts by mass or more, more preferably at least 20 parts by mass, more preferably at least 40 parts by mass, more preferably at least 60 parts by mass, and more preferably at least 80 parts by mass. By setting it to the lower limit value or more, the low thermal expansion and low dielectric loss tangent of the obtained hardened material tend to be further improved. Moreover, the upper limit of the content of the filler (D) is preferably 1,600 parts by mass or less, more preferably 1,000 parts by mass or less, and still more preferably 300 parts by mass or less, based on 100 parts by mass of the resin solid content. It is more preferably not more than 250 parts by mass, and still more preferably not more than 200 parts by mass, or not more than 120 parts by mass. By setting it below the upper limit, the moldability of the resin composition tends to be further improved. In the resin composition of this embodiment, as an example of an ideal embodiment, it is preferable that the content of the filler (D) is 1 to 95 mass % of the components excluding the solvent, and is 30 to 80 mass %. % is more ideal. The resin composition of this embodiment may contain only one type of filler (D), or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

In the resin composition of this embodiment, when a filler (D) is used, especially when an inorganic filler is used, a silane coupling agent may be further included. By containing a silane coupling agent, the dispersibility of the filler (D), the resin component, and the bonding strength between the filler (D) and the base material described below tend to be further improved. The silane coupling agent is not particularly limited, and examples thereof include silane coupling agents commonly used for surface treatment of inorganic substances, such as aminosilane compounds (such as γ-aminopropyltriethoxysilane, N-β- (Aminoethyl)-γ-aminopropyltrimethoxysilane, etc.), epoxysilane compounds (such as γ-glycidoxypropyltrimethoxysilane, etc.), vinylsilane compounds (such as Vinyltrimethoxysilane, etc.), styrene silane compounds (such as p-styrenetrimethoxysilane, etc.), acrylic silane compounds (such as γ-acryloxypropyltrimethoxysilane, etc.), cationic silane compounds Compounds (for example, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, etc.), phenylsilane compounds, etc. A silane coupling agent can be used individually by 1 type, or in combination of 2 or more types. The content of the silane coupling agent is not particularly limited, and may be 0.1 to 5.0 parts by mass relative to 100 parts by mass of the resin solid content.

<Low molecular vinyl compound with a molecular weight of less than 1000 and containing one organic group containing a carbon-carbon unsaturated bond in the molecule> The resin composition of this embodiment may also contain a molecular weight of less than 1000 and containing one carbon-containing unsaturated bond in the molecule. -Low-molecular vinyl compounds with organic groups of unsaturated carbon bonds (hereinafter sometimes referred to as "low-molecular vinyl compounds"). By blending a low molecular weight vinyl compound, the low dielectric properties (Dk and/or Df) and moisture absorption and heat resistance of the obtained cured product tend to be further improved. Here, the concept that the carbon-carbon unsaturated bond constituting the organic group containing the carbon-carbon unsaturated bond does not include it as part of an aromatic ring. On the other hand, it is a concept including a carbon-carbon unsaturated bond contained as part of a non-aromatic ring. Examples of the carbon-carbon unsaturated bond contained as part of a non-aromatic ring include cyclohexenyl and the like. In addition, it also includes the concept of parts other than the ends of linear or branched organic groups, that is, carbon-carbon unsaturated bonds (such as vinylene groups) contained in the linear or branched chain. In this embodiment, the organic group containing a carbon-carbon unsaturated bond preferably has a CH ₂ =C(X)-(X is a hydrogen atom or a methyl group) structure. In this way, by using a compound containing a carbon-carbon unsaturated bond at the end of the molecule, it can react more efficiently with the vinyl group of the polymer (V) having the structural unit represented by the formula (V). The aforementioned organic group containing a carbon-carbon unsaturated bond is more preferably one selected from the group consisting of vinyl, allyl, acrylic, and methacrylic groups, and even more preferably vinyl.

The low-molecular vinyl compound used in this embodiment is preferably composed only of atoms selected from the group consisting of carbon atoms, hydrogen atoms, oxygen atoms, nitrogen atoms, and silicon atoms. More preferably, it is composed of atoms from the group consisting of carbon atoms, oxygen atoms, and silicon atoms. Even more preferably, it is composed only of atoms selected from the group consisting of carbon atoms, hydrogen atoms, and oxygen atoms. The low molecular weight vinyl compound used in this embodiment may or may not have a polar group. The low molecular weight vinyl compound used in this embodiment is preferably one that does not have a polar group. Examples of polar groups include amino group, carboxyl group, hydroxyl group, and nitro group.

In this embodiment, the molecular weight of the low-molecular vinyl compound is preferably 70 or more, more preferably 80 or more, and still more preferably 90 or more. By setting it as above the said lower limit value, the tendency of the low molecular weight vinyl compound to volatilize from the resin composition of this embodiment, its hardened|cured material, etc. can be suppressed. The upper limit of the molecular weight of the low molecular vinyl compound is preferably 500 or less, more preferably 400 or less, more preferably 300 or less, more preferably 200 or less, and may also be 150 or less. By setting it below the upper limit, the effect of improving the reactivity with the polymer (V) having the structural unit represented by the formula (V) tends to be further improved. When the resin composition of this embodiment contains two or more types of low molecular vinyl compounds, the average molecular weight value of the low molecular vinyl compound is preferably within the above range, and the molecular weight of each compound is more preferably within the above ideal range. .

In this embodiment, the boiling point of the low molecular weight vinyl compound is preferably 110°C or higher, more preferably 115°C or higher, still more preferably 120°C or higher. By being equal to or more than the aforementioned lower limit, volatilization of the low-molecular vinyl compound when the resin composition is thermally cured can be suppressed, and the polymer (V) having the structural unit represented by the formula (V) can be more effectively cured. The vinyl groups contained react with low molecular weight vinyl compounds. The boiling point of the low molecular weight vinyl compound is preferably 300°C or lower, more preferably 250°C or lower, still more preferably 200°C or lower. By setting it below the upper limit, it becomes less likely to remain in the cured product as a residual solvent. When the resin composition of this embodiment contains two or more low molecular weight vinyl compounds, the average boiling point only needs to fall within the above range, but the boiling point of each compound is preferably within the above ideal range.

Examples of low molecular weight vinyl compounds: (meth)acrylate compounds, aromatic vinyl compounds (preferably styrene compounds), saturated fatty acid vinyl ester compounds, cyanide vinyl compounds, ethylenically unsaturated carboxylic acids, ethylene Unsaturated carboxylic anhydride, ethylenically unsaturated dicarboxylic acid monoalkyl ester, ethylenically unsaturated carboxamide, vinyl silane compound (such as vinyl trialkoxy silane, etc.), acrylic silane compound (such as acrylic silane compound) trialkoxysilane, etc.), methacrylic silane compounds (such as methacrylic trialkoxysilane, etc.), styrene silane compounds (such as styrene trialkoxysilane, etc.), etc. The first form of the low molecular vinyl compound is selected from the group consisting of (meth)acrylate compounds, aromatic vinyl compounds, saturated fatty acid vinyl ester compounds, cyanide vinyl compounds, ethylenically unsaturated carboxylic acids, and ethylenically unsaturated carboxylic acids. At least one kind from the group consisting of acid anhydride, ethylenically unsaturated dicarboxylic acid monoalkyl ester, and ethylenically unsaturated carboxamide. The second form of the low molecular vinyl compound is selected from (meth)acrylate compounds, aromatic vinyl compounds, saturated fatty acid vinyl ester compounds, vinyl silane compounds, acrylic silane compounds, methacrylic silane compounds, benzene At least one type of the group consisting of vinylsilane compounds is preferably an aromatic vinyl compound and/or a vinylsilane compound. Specific examples of low molecular weight vinyl compounds include methylstyrene, ethylvinylbenzene, vinyltrimethoxysilane, and vinyltriethoxysilane.

In the resin composition of this embodiment, the content of the low molecular vinyl compound is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and more preferably 2.5 parts by mass or more based on 100 parts by mass of the resin solid content. By making it the said lower limit value or more, the unreacted functional group in the hardened|cured material obtained tends to reduce, and there exists a tendency to improve the moisture absorption and heat resistance of the hardened|cured material obtained. In addition, the upper limit of the content of the low molecular vinyl compound is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 8 parts by mass or less, based on 100 parts by mass of the resin solid content. More preferably not more than 5 parts by mass. By setting it below the upper limit, the low dielectric properties (Dk and/or Df) of the obtained hardened material tend to be further improved. The resin composition of this embodiment may contain only one low molecular weight vinyl compound, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

In the resin composition of this embodiment, the mass ratio of the polymer (V) having the structural unit represented by the formula (V) and the low molecular vinyl compound is relative to the mass ratio of the polymer (V) having the structural unit represented by the formula (V). )1 is preferably 0.025 or more, more preferably 0.05 or more. By making it the said lower limit value or more, the unreacted functional group in the hardened|cured material obtained tends to reduce, and there exists a tendency to improve the moisture absorption and heat resistance of the hardened|cured material obtained. The upper limit of the mass ratio of the polymer (V) having the structural unit represented by the formula (V) and the low molecular weight vinyl compound is preferably 0.7 or less relative to the polymer (V) 1 having the structural unit represented by the formula (V). , it is more preferably 0.5 or less, more preferably 0.4 or less, still more preferably 0.3 or less, and may also be 0.25 or less. By setting it below the upper limit, the low dielectric properties (Dk and/or Df) of the obtained hardened material tend to be further improved.

＜Oligomers with ethylenically unsaturated groups＞ In the resin composition of this embodiment, in order to improve thermosetting properties and curing properties by active energy rays (for example, photocuring properties by ultraviolet rays), an oligomer having an ethylenically unsaturated group may be used in combination. The oligomer having an ethylenically unsaturated group used in this embodiment is not particularly limited as long as it is an oligomer having one or more ethylenically unsaturated groups per molecule. Examples include vinyl, allyl, etc. The oligomer containing a vinyl group, a (meth)acrylyl group, etc. is preferably an oligomer having a vinyl group. In addition, in this specification, if a compound is classified as an oligomer having an ethylenically unsaturated group and a compound is also classified as a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, it is classified as containing Polyphenylene ether compounds with more than 2 carbon-carbon unsaturated double bonds. The oligomer having an ethylenically unsaturated group is preferably a styrene oligomer. The styrene oligomer according to this embodiment is preferably obtained by polymerizing at least one selected from the group consisting of styrene, the above-mentioned styrene derivatives, and vinyl toluene. The number average molecular weight of the styrene oligomer is preferably 178 or more and 1,600 or less. In addition, the styrene oligomer is preferably a compound having an average aromatic ring number of 2 to 14, a total aromatic ring number of 2 to 14 of 50 mass % or more, and a boiling point of 300° C. or more without a branched structure.

Examples of the styrene oligomer used in this embodiment include styrene polymer, vinyltoluene polymer, α-methylstyrene polymer, vinyltoluene-α-methylstyrene polymer, styrene -α-styrene polymer, etc. Commercially available styrene polymers can also be used, and examples include Picolastic A5 (manufactured by Eastman Chemical Co., Ltd.), Picolastic A-75 (manufactured by Eastman Chemical Co., Ltd.), Piccotex 75 (manufactured by Eastman Chemical Co., Ltd.), and FTR-8100 (Mitsui Chemical Co., Ltd. (Co., Ltd.), FTR-8120 (Co., Ltd. Mitsui Chemicals Co., Ltd.). Examples of the vinyltoluene-α-methylstyrene polymer include Piccotex LC (manufactured by Eastman Chemical Co., Ltd.). Examples of α-methylstyrene polymers include Crystalex 3070 (manufactured by Eastman Chemical Co., Ltd.), Crystalex 3085 (manufactured by Eastman Chemical Co., Ltd.), Crystalex (3100), Crystalex 5140 (manufactured by Eastman Chemical Co., Ltd.), and FMR-0100 (Mitsui Chemical Co., Ltd.), FMR-0150 (Mitsui Chemical Co., Ltd.). Moreover, examples of the styrene-α-styrene polymer include FTR-2120 (manufactured by Mitsui Chemicals Co., Ltd.). These styrene oligomers may be used individually or in combination of 2 or more types. In the resin composition of this embodiment, the α-methylstyrene oligomer is excellent in thermal hardening, good embedding properties of fine wiring, solder heat resistance, low relative dielectric constant, and low dielectric loss tangent. Therefore it is more ideal.

When the resin composition of this embodiment contains an oligomer having an ethylenically unsaturated group, its content is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the resin solid content in the resin composition. , more preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and may be 5 parts by mass or more. By setting it to the lower limit value or more, the low dielectric property of the obtained hardened material tends to be further improved. Moreover, the upper limit of the content of the oligomer having an ethylenically unsaturated group is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition. More preferably, it is not more than 15 parts by mass, and still more preferably not more than 10 parts by mass. By setting it below the upper limit, the heat resistance of the obtained hardened material tends to be further improved. In addition, the low dielectric constant, low dielectric loss tangent, and chemical resistance of the obtained hardened material tend to be further improved. The resin composition of this embodiment may contain only one type of oligomer having an ethylenically unsaturated group, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

＜Thermoplastic elastomer＞ The resin composition of this embodiment may contain a thermoplastic elastomer. The thermoplastic elastomer in this embodiment is not particularly limited, and examples thereof include polyisoprene, polybutadiene, styrene butadiene, butyl rubber, ethylene propylene rubber, styrene butadiene, Styrene butadiene styrene, styrene isoprene styrene, styrene ethylene butylene styrene, styrene propylene styrene, styrene ethylene propylene styrene, fluorine rubber, silicone rubber, and their hydrogenated compounds , their alkyl compounds, and their copolymers.

The number average molecular weight of the thermoplastic elastomer used in this embodiment is preferably 50,000 or more. By setting the number average molecular weight to 50,000 or more, the low dielectric properties (Dk and/or Df) of the obtained hardened material tend to be more excellent. The number average molecular weight is preferably 60,000 or more, more preferably 70,000 or more, and still more preferably 80,000 or more. The upper limit of the number average molecular weight of the thermoplastic elastomer is preferably 400,000 or less, more preferably 350,000 or less, and still more preferably 300,000 or less. By setting it below the upper limit, the solubility of the thermoplastic elastomer component in the resin composition tends to be further improved. When the resin composition of this embodiment contains two or more types of thermoplastic elastomers, the number average molecular weight of their mixture is preferably within the above range.

In this embodiment, the thermoplastic elastomer is preferably a thermoplastic elastomer containing styrene monomer units and conjugated diene monomer units (hereinafter referred to as "thermoplastic elastomer (E)"). By using such a thermoplastic elastomer (E), the obtained hardened material has further excellent low dielectric properties (Dk and/or Df).

The above-mentioned thermoplastic elastomer (E) contains styrene monomer units. By containing styrene monomer units, the solubility of the thermoplastic elastomer (E) into the resin composition will be improved. Examples of styrene monosystem include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene (vinylstyrene), N,N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene, etc., among them, styrene, α-methylstyrene, and p-methylstyrene are preferred from the viewpoint of availability and productivity. Among them, styrene is particularly good. The content of the styrene monomer units in the thermoplastic elastomer (E) is preferably in the range of 10 to 50 mass% of all monomer units, more preferably in the range of 13 to 45 mass%, and in the range of 15 to 40 mass% Even better. If the content of the styrene monomer unit is 50% by mass or less, the adhesion and adhesion to the base material will be improved. In addition, if it is 10% by mass or more, the increase in adhesive strength is suppressed, adhesive residue and stop marks are less likely to occur, and the adhesion surfaces tend to be easily peelable from each other, so this is preferable. The thermoplastic elastomer (E) may contain only one type of styrene monomer unit, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range. The method for measuring the content of styrene monomer units in the thermoplastic elastomer (E) of this embodiment can be referred to the records in International Publication No. 2017/126469, and the content is incorporated into this specification. The same applies to the conjugated diene monomer units described below.

The above-mentioned thermoplastic elastomer (E) contains conjugated diene monomer units. By containing conjugated diene monomer units, the solubility of the thermoplastic elastomer (E) into the resin composition will be improved. The conjugated diene monomer is not particularly limited as long as it is a diene having one pair of conjugated double bonds. Examples of conjugated diene monomers include: 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene Diene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and bacteriogreen (farnesene), preferably 1,3-butadiene, and isoprene, preferably 1,3-butadiene. The thermoplastic elastomer (E) may contain only one type of conjugated diene monomer unit, or may contain two or more types.

In the above-mentioned thermoplastic elastomer (E), the mass ratio of styrene monomer units and conjugated diene monomer units is preferably styrene monomer unit/conjugated diene monomer unit = 5/95 to 80/20. The range is preferably from 7/93 to 77/23, and the range from 10/90 to 70/30 is even better. If the mass ratio of styrene polymer units and conjugated diene monomer units is in the range of 5/95 to 80/20, an increase in adhesive strength can be suppressed and high adhesive force can be maintained, and the adhesive surfaces can be easily peeled off from each other.

In the above-mentioned thermoplastic elastomer (E), all of the conjugated diene bonds of the thermoplastic elastomer may be hydrogenated, part of them may be hydrogenated, or they may not be hydrogenated.

The above-mentioned thermoplastic elastomer (E) may or may not contain other monomer units in addition to styrene monomer units and conjugated diene monomer units. Examples of other monomer units include aromatic vinyl compound units other than styrene monomer units. In the above-mentioned thermoplastic elastomer (E), the total of styrene monomer units and conjugated diene monomer units is preferably 90 mass% or more of all monomer units, more preferably 95 mass% or more, and still more 97 mass% or more. Even better, it is 99 mass % or more, and it is still better. As described above, the thermoplastic elastomer (E) may contain only one type of styrene monomer unit and conjugated diene monomer unit, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

The thermoplastic elastomer (E) used in this embodiment may be a block polymer or a random polymer. In addition, the conjugated diene monomer unit may be a hydrogenated elastomer that is hydrogenated, an unhydrogenated elastomer that is not hydrogenated, or a partially hydrogenated elastomer that is partially hydrogenated. In one embodiment of this embodiment, the thermoplastic elastomer (E) is a non-hydrogenated elastomer. An unhydrogenated elastomer refers to one in which the proportion of double bonds that are hydrogenated based on the conjugated diene monomer units in the elastomer, that is, the hydrogenation rate (hydrogenation rate), is 20% or less. The aforementioned hydrogenation rate is preferably 15% or less, more preferably 10% or less, and still more preferably 5% or less.

Examples of commercially available types of thermoplastic elastomer (E) used in this embodiment include SEPTON (registered trademark) 2104 manufactured by Kuraray Co., Ltd., S.O.R. (registered trademark) S1606, S1613, S1609, S1605, and JSR manufactured by Asahi Kasei Co., Ltd. DYNARON (registered trademark) 9901P, TR2250, etc., which are joint-stock companies.

When the resin composition of this embodiment contains a thermoplastic elastomer (preferably thermoplastic elastomer (E)), its content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, based on 100 parts by mass of the resin solid content. More preferably, it is 10 parts by mass or more, and it may be 15 parts by mass or more. By setting it to the lower limit value or more, the low dielectric properties (Dk and/or Df) of the obtained hardened material tend to be further improved. In addition, the upper limit of the content of the thermoplastic elastomer is preferably 45 parts by mass or less, more preferably 40 parts by mass or less, more preferably 35 parts by mass or less, based on 100 parts by mass of the resin solid content. More preferably, it may be 25 parts by mass or less. By setting it below the upper limit, the heat resistance of the obtained hardened material tends to be further improved. The resin composition of this embodiment may contain only one type of thermoplastic elastomer, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

＜Flame retardant＞ The resin composition of this embodiment may also contain a flame retardant. Examples of flame retardants include phosphorus-based flame retardants, halogen-based flame retardants, inorganic-based flame retardants and polysiloxane-based flame retardants. Phosphorus-based flame retardants are preferred. Known flame retardants can be used, and examples include: brominated epoxy resin, brominated polycarbonate, brominated polystyrene, brominated styrene, brominated phthalamide, tetrabromobisphenol A, (methane base) Pentabromobenzyl acrylate, pentabromotoluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1,2-pentabromophenylethane, chlorinated polystyrene, chlorinated paraffin, etc. Halogen flame retardants; red phosphorus, tricresyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tris(xylyl)phosphate, trialkyl phosphate, dialkyl phosphate, ethyl chloride ester), phosphine nitrogen, 1,3-phenylenebis(2,6-di(dylyl)phosphate), 10-(2,5-dihydroxyphenyl)-10H-9-oxa- Phosphorus flame retardants such as 10-phosphaphenanthrene-10-oxide; inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, part of boehmite, boehmite, zinc borate, antimony trioxide; polysiloxane Polysilicone flame retardants such as rubber and polysilicone resin. In this embodiment, among them, 1,3-phenylenebis(2,6-di(xylyl)phosphate) does not impair the low dielectric properties (Dk and/or Df). More ideal.

When the resin composition of this embodiment contains a flame retardant, its content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and 10 parts by mass or more based on 100 parts by mass of the resin solid content in the resin composition. More preferably, it may be 15 parts by mass or more. In addition, the lower limit of the content of the flame retardant is preferably 30 parts by mass or less, more preferably 25 parts by mass or less. A flame retardant can be used individually by 1 type or in combination of 2 or more types. When two or more types are used, the total amount shall be within the above range.

＜Active ester compound＞ The resin composition of this embodiment may contain an active ester compound within a range that does not impair the effects of the present invention. The active ester compound is not particularly limited. For example, the descriptions in paragraphs 0064 to 0066 of International Publication No. 2021/172317 can be referred to, and the content thereof is incorporated into this specification.

When the resin composition of this embodiment contains an active ester compound, it is preferably 1 part by mass or more and 50 parts by mass or less based on 100 parts by mass of the resin solid content in the resin composition. The resin composition in this embodiment may contain only one type of active ester compound, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range. Furthermore, the resin composition in this embodiment may be substantially free of active ester compounds. Substantially free means that the content of the active ester compound is less than 1 part by mass relative to 100 parts by mass of the resin solid content in the resin composition, preferably less than 0.1 part by mass, and more preferably less than 0.01 part by mass.

＜Dispersant＞ The resin composition of this embodiment may also contain a dispersant. As the dispersant, those used for general coating purposes can be ideally used, and the type thereof is not particularly limited. The dispersant should be a copolymer-based wetting dispersant. Specific examples include: DISPERBYK (registered trademark)-110, 111, 161, 180, 2009, 2152, 2155, BYK (registered trademark) manufactured by BYK Co., Ltd. W996, W9010, W903, W940, etc.

When the resin composition of this embodiment contains a dispersant, the lower limit of its content is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, based on 100 parts by mass of the resin solid content in the resin composition. It may also be 0.3 parts by mass or more. In addition, the upper limit of the content of the dispersant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and may be 3 parts by mass or less based on 100 parts by mass of the resin solid content in the resin composition. A dispersant can be used individually by 1 type or in combination of 2 or more types. When two or more types are used, the total amount shall be within the above range.

＜Harding accelerator＞ The resin composition of this embodiment may further contain a hardening accelerator. The hardening accelerator is not particularly limited, and examples thereof include imidazoles such as 2-ethyl-4-methylimidazole and triphenylimidazole; benzoyl peroxide, lauryl peroxide, acetyl peroxide, and p-chloroperoxide. Benzyl oxide, di(tertiary butyl)-di-perphthalate, α,α'-di(tertiary butyl peroxide) dicumyl, 2,5-dimethyl-2 , 5-di(tertiary butyl peroxide) hexane, 2,5-dimethyl-2,5-bis(tertiary butyl peroxide) hexane-3-yne and other organic peroxides; azobis Azo compounds such as nitriles; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine , quinoline, N-methyl𠰌line, triethanolamine, triethylenediamine, tetramethylbutylenediamine, N-methylpiperidine and other tertiary amines; phenol, xylenol, cresol, m-phenylene Phenols such as diphenols and catechol; high temperature decomposition free radical generators such as 2,3-dimethyl-2,3-diphenylbutane; lead naphthenate, lead stearate, naphthenic acid Zinc, zinc octoate, manganese octoate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, iron acetyl acetonate and other organic metal salts; dissolve these organic metal salts in phenol, bisphenol, etc. Compounds containing hydroxyl groups; inorganic metal salts such as tin chloride, zinc chloride, aluminum chloride; organic tin compounds such as dioctyltin oxide, other alkyltin, alkyltin oxides, etc. Ideal hardening accelerators are imidazoles and organometallic salts, and a combination of imidazoles and organometallic salts is more preferred.

When the resin composition of this embodiment contains a hardening accelerator, the lower limit of its content is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, based on 100 parts by mass of the resin solid content in the resin composition. Quality parts and above are better. Furthermore, the upper limit of the content of the hardening accelerator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 2 parts by mass or less based on 100 parts by mass of the resin solid content in the resin composition. The hardening accelerator can be used individually by 1 type or in combination of 2 or more types. When two or more types are used, the total amount shall be within the above range.

＜Solvent＞ The resin composition of this embodiment may also contain a solvent, and preferably contains an organic solvent. When a solvent is contained, the resin composition of this embodiment is preferably in a form (solution or varnish) in which at least part and all of the above-mentioned various resin solid contents are dissolved or compatible with the solvent. The solvent is not particularly limited as long as it is a polar organic solvent or a non-polar organic solvent that can dissolve or be compatible with at least part and preferably all of the solid components of the various resins mentioned above. Examples of the polar organic solvent include ketones (such as Acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), cellulosides (such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), esters (such as ethyl lactate, methyl acetate, ethyl acetate, Butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.), amides (such as dimethoxyacetamide, dimethylformamide) etc.), non-polar organic solvents include aromatic hydrocarbons (such as toluene, xylene, etc.). A solvent can be used individually by 1 type or in combination of 2 or more types. When two or more types are used, the total amount shall be within the above range.

＜Other ingredients＞ In addition to the above-mentioned components, the resin composition of this embodiment may also contain various polymer compounds such as thermoplastic resins and oligomers thereof, and various additives. Additives can be listed: ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, dyes, pigments, tackifiers, flow regulators, lubricants, defoaming agents, leveling agents, brighteners agents, polymerization inhibitors, etc. These additives can be used individually by 1 type or in combination of 2 or more types.

＜Use＞ The resin composition of this embodiment can be used as a cured product. Specifically, the resin composition of this embodiment can be suitably used as a low relative dielectric constant material and/or a low dielectric loss tangent material, and can be suitably used as an insulating layer of a printed wiring board or a material for a semiconductor package. etc., and can be ideally used as a resin composition for electronic materials. The resin composition of this embodiment can be suitably used as a material for prepregs, metal foil-clad laminates using prepregs, resin composite sheets, and printed wiring boards.

The resin composition of this embodiment should preferably have a low relative dielectric constant (Dk) when molded into a hardened plate with a thickness of 0.8 mm. Specifically, the relative dielectric constant (Dk) measured by the resonant cavity perturbation method at a frequency of 10 GHz is preferably 2.60 or less, and more preferably 2.50 or less. The lower limit of the relative dielectric constant (Dk) is not particularly limited, but it is practical to set it to 0.01 or more, for example. Furthermore, the resin composition of this embodiment should preferably have a low dielectric loss tangent (Df) when molded into a hardened plate with a thickness of 0.8 mm. Specifically, the dielectric loss tangent (Df) measured by the resonant cavity perturbation method at a frequency of 10 GHz should be less than 0.0020, preferably less than 0.0018, and even more preferably less than 0.0014. There is no particular restriction on the lower limit value of the dielectric loss tangent (Df). For example, it is more practical to set the lower limit value to 0.0001 or more. Such low dielectric properties (Dk and/or Df) are achieved by mainly using the polymer (V) having the structural unit represented by the formula (V) and the compound (M1) represented by the formula (M1). The relative dielectric constant (Dk) and dielectric loss tangent (Df) of the above-mentioned hardened plate were measured more systematically by the method described in the following examples.

The glass transition temperature of the hardened product of the resin composition of this embodiment according to DMA (Dynamic Mechanical Measurement) is preferably 230°C or higher, more preferably 250°C or higher. Such a high glass transition temperature is mainly achieved by using the compound (M) represented by the formula (M). The upper limit of the glass transition temperature is, for example, 350°C or less. More specifically, the glass transition temperature is measured by the method described in the examples below.

In addition, the insulating layer obtained by using the resin composition of this embodiment is often subjected to drilling processing, and it is preferable to have excellent slag removal resistance. That is, when removing slag after drilling, it is ideal to suppress the deterioration of the insulating layer and to have excellent slag removal properties. Specifically, the mass reduction rate in the desmear test when the resin composition of this embodiment is formed into a hardened plate with a thickness of 0.8 mm is preferably in the range of -4.0 mass% to -2.0 mass%. The desmear resistance was measured according to the description of the Examples mentioned later.

The resin composition of this embodiment can be made into a layered material (including concepts such as film form, sheet form, etc.) such as a prepreg or a resin composite sheet that serves as an insulating layer of a printed wiring board. , its thickness should be more than 5 μm, preferably more than 10 μm. The upper limit of the thickness is preferably 200 μm or less, more preferably 180 μm or less. In addition, the thickness of the above-mentioned layered material means including the thickness of the glass cloth when, for example, the resin composition of the present embodiment is impregnated with glass cloth. The material made of the resin composition of this embodiment can be used for pattern formation by exposure and development, or can be used without exposure and development. Especially suitable for applications where exposure and development are not required.

＜＜Prepreg＞＞ The prepreg system of this embodiment is formed from a base material (prepreg base material) and the resin composition of this embodiment. The prepreg of this embodiment can be made by applying (for example, impregnating and/or coating) the resin composition of this embodiment to a base material, and then drying it by heating (for example, at 120 to 220° C. for 2 to 15 minutes). method, etc.) to semi-harden it. At this time, the adhesion amount of the resin composition to the base material, that is, the amount of the resin composition (including the filler (D)) relative to the total amount of the semi-hardened prepreg, is preferably in the range of 20 to 99 mass %, which is 20 The range of ~80 mass% is more preferable.

The base material is not particularly limited as long as it is a base material used for various printed wiring board materials. Examples of the material of the substrate include: glass fiber (such as E-glass, D-glass, L-glass, S-glass, T-glass, Q-glass, UN-glass, NE-glass, spherical glass, etc.), Inorganic fibers other than glass (such as quartz, etc.), organic fibers (such as polyimide, polyamide, polyester, liquid crystal polyester, polytetrafluoroethylene, etc.). The form of the base material is not particularly limited, and examples include woven fabrics: nonwoven fabrics, rovings, cut-strand felts, surface-processed felts, etc. These base materials may be used alone, or two or more types may be used in combination. Among these base materials, from the viewpoint of dimensional stability, it is preferable to use a fabric that has been subjected to ultra-fiber opening treatment and hole filling treatment. From the viewpoint of strength and low water absorption, the thickness of the base material is preferably 200 μm or less and the mass is 250 g. / ^m2 or less, from the viewpoint of moisture absorption and heat resistance, glass fabrics that have been surface-treated with silane coupling agents such as epoxy silane and aminosilane are preferred. From the viewpoint of electrical properties, low-dielectric glass cloth composed of glass fibers that exhibit low relative permittivity and low dielectric loss tangent, such as L-glass, NE-glass, and Q-glass, is better. Examples of the base material with low relative dielectric constant include a base material with a relative dielectric constant of 5.0 or less (preferably 3.0 to 4.9). Examples of the base material with low dielectric loss tangent include a base material with a dielectric loss tangent of 0.006 or less (preferably 0.001 to 0.005). The relative dielectric constant and dielectric loss tangent are measured using a perturbation method cavity resonator at a frequency of 10 GHz.

＜＜Metal foil clad laminate＞＞ The metal foil-clad laminate of this embodiment includes at least one layer made of the prepreg of this embodiment, and one-sided or double-sided metal foil arranged on the layer made of the prepreg. Examples of methods for producing the metal foil-clad laminate of this embodiment include arranging at least one piece (preferably two or more pieces) of the prepreg of this embodiment, and arranging metal foil on one or both sides of the prepreg. Layer forming method. More specifically, it can be produced by arranging metal foils such as copper and aluminum on one or both sides of the prepreg and performing lamination molding. The number of prepreg sheets is preferably 1 to 10 sheets, more preferably 2 to 10 sheets, and even more preferably 2 to 9 sheets. If metal foil is used as a material for printed wiring boards. There are no particular restrictions, and examples thereof include copper foils such as rolled copper foil and electrolytic copper foil. The thickness of the metal foil (preferably copper foil) is not particularly limited, and may be about 1.5 to 70 μm. In addition, when copper foil is used as the metal foil, the copper foil should be adjusted so that the surface roughness Rz of the copper foil measured in accordance with JIS B0601:2013 is 0.2 to 4.0 μm. By adjusting the roughness Rz of the copper foil surface to 0.2 μm or more, the roughness of the copper foil surface becomes an appropriate size, and the copper foil peeling strength tends to be further improved. On the other hand, by adjusting the roughness Rz of the copper foil surface to 4.0 μm or less, the roughness of the copper foil surface becomes an appropriate size, and the dielectric loss tangent characteristics of the obtained hardened material tend to be further improved. The roughness Rz of the copper foil surface, from the viewpoint of reducing the dielectric loss tangent, is preferably 0.5 μm or more, more preferably 0.6 μm or more, particularly preferably 0.7 μm or more, and 3.5 μm or less, more preferably 3.0 A thickness of µm or less is more preferably 2.0 µm or less.

The method of laminate molding includes methods commonly used when molding laminated boards and multilayer boards for printed wiring boards. More specific examples include the use of a multilayer press, a multilayer vacuum press, a continuous forming machine, a high-temperature and high-pressure (autoclave) forming machine, etc. , a method of laminate forming at a temperature of about 180 to 350°C, a heating time of about 100 to 300 minutes, and a surface pressure of about 20 to 100kg/ ^cm2 . In addition, a multilayer board can also be produced by combining the prepreg of this embodiment with a separately produced wiring board for the inner layer and performing lamination molding. The multilayer board can be manufactured, for example, by arranging approximately 35 μm copper foil on both sides of one prepreg of this embodiment, laminating it using the above-mentioned molding method, forming an inner layer circuit, and applying black coating to the circuit. chemical treatment to form an inner circuit board, and then alternately arrange the inner circuit board and the prepreg of this embodiment one by one, and then arrange the copper foil on the outermost layer, and use the above conditions to laminate it preferably under vacuum. Shaping to make multilayer boards. The metal foil-clad laminated board of this embodiment can be ideally used as a printed wiring board.

The peel strength of the metal foil-clad laminate of this embodiment measured according to the provisions of JIS C6481 5.7 "Peel Strength" is preferably 0.28kN/m or more, more preferably 0.38kN/m or more, and 0.50kN/m or more. Even better. The upper limit of the peel strength is not particularly limited, but is, for example, 2.00 kN/m or more. The peel strength was measured according to the description of the Examples mentioned later.

As described above, the resin composition for electronic materials obtained by using the resin composition of this embodiment (a resin composition composed of a combination of specific components) can be made into a cured product having low dielectric properties (low dielectric constant). , low dielectric loss tangent), moisture absorption and heat resistance, and has excellent characteristics of heat resistance, slag removal resistance, metal foil peeling strength, crack resistance, hardened appearance, and low thermal expansion.

＜＜Printed wiring board＞＞ The printed wiring board of this embodiment is a printed wiring board including an insulating layer and a conductor layer arranged on the surface of the insulating layer, and the insulating layer includes a layer formed of the resin composition of this embodiment and a prepreg of this embodiment. At least one of the layers of body formation. Such a printed wiring board can be manufactured according to common methods, and the manufacturing method is not particularly limited. An example of a manufacturing method of a printed wiring board is illustrated below. First, a metal foil-clad laminate such as the above-mentioned copper foil laminate is prepared. Then, etching is performed on the surface of the metal foil-clad laminate to form an inner circuit, and an inner substrate is produced. The inner circuit surface of the inner substrate is subjected to surface treatment to improve the bonding strength when necessary, and then a required number of the above-mentioned prepregs are stacked on the inner circuit surface, and then the outer circuit is laminated on the outside. The metal foil is then heated and pressed to form a single piece. In this manner, a multilayer laminate is produced in which an insulating layer composed of a base material and a cured product of a resin composition is formed between the inner circuit and the metal foil for the outer circuit. Then, the multi-layer laminate board is subjected to drilling processing for through holes and guide holes, and a plated metal film is formed on the wall surface of the hole to conduct the metal foil for the inner circuit and the outer circuit, and then the outer layer is Printed wiring boards are manufactured by etching metal foil used for circuits to form outer circuits.

The printed wiring board obtained in the above production example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer is composed of the resin composition of the present embodiment and/or its hardened product. That is, the above-mentioned prepreg of the present embodiment (for example, a prepreg formed of a base material and the resin composition of the present embodiment impregnated or coated thereon), the above-mentioned metal foil-clad laminate of the present embodiment. The layer formed of the resin composition serves as the insulating layer in this embodiment. Furthermore, this embodiment also relates to a semiconductor device including the printed wiring board. For details of the semiconductor device, reference can be made to the descriptions in paragraphs 0200 to 0202 of Japanese Patent Application Laid-Open No. 2021-021027, and these contents are incorporated into this specification.

Furthermore, it is preferable that the surface roughness of the insulating layer formed of the cured product of the resin composition of this embodiment be reduced after the roughening treatment. Specifically, the arithmetic mean roughness Ra of the surface of the insulating layer after roughening is preferably 200 nm or less, more preferably 150 nm or less, particularly preferably 100 nm or less. The lower limit of the arithmetic mean roughness Ra is not particularly limited, but may be 10 nm or more, for example. The arithmetic mean roughness Ra of the surface of the insulating layer is measured using a non-contact surface roughness meter in VSI mode using a 50x lens. As a non-contact surface roughness meter, WYKONT3300 manufactured by Veeco Instruments was used.

＜＜Resin composite sheet＞＞ The resin composite sheet of this embodiment includes a support and a layer formed of the resin composition of this embodiment arranged on the surface of the support. Resin composite sheets can be used as build-up films or dry film solder resists. The manufacturing method of the resin composite sheet is not particularly limited. For example, a solution obtained by dissolving the resin composition of the present embodiment in a solvent is applied to a support and dried to obtain a resin composite sheet. method.

Examples of the support used here include polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylene tetrafluoroethylene copolymer film, and coating strips on the surface of these films. Release films made of molding agents, organic film substrates such as polyimide films, conductor foils such as copper foil and aluminum foil, glass plates, SUS (Steel Use Stainless) plates, FRP (Fiber-Reinforced Plastics) and other plates There are no special restrictions for those who have the status.

Examples of the coating method (coating method) include a solution in which the resin composition of the present embodiment is dissolved in a solvent, and coating with a coating bar, die coater, doctor blade, Baker applicator, etc. method on the support. Alternatively, a single-layer sheet may be produced by peeling off the support or etching the resin composite sheet in which the support and the resin composition are laminated after drying. In addition, it is also possible to form a sheet without using a support by supplying a solution in which the resin composition of the present embodiment is dissolved in a solvent into a mold having a sheet-shaped mold cavity and drying it. Obtain single layer slices.

In addition, when the single-layer sheet or resin composite sheet of this embodiment is produced, the drying conditions for removing the solvent are not particularly limited. If the temperature is low, the solvent will easily remain in the resin composition. If the temperature is high, the curing of the resin composition will proceed. , so it is advisable to dry at a temperature of 20°C to 200°C for 1 to 90 minutes. In addition, the single-layer sheet or the resin composite sheet can be used in an uncured state in which the solvent is simply dried, or in a semi-cured (B-staged) state if necessary. In addition, the thickness of the resin layer in the single-layer sheet or resin composite sheet of this embodiment can be adjusted by using the concentration and coating thickness of the solution of the resin composition of this embodiment used during coating. There is no particular limitation. Generally speaking, if the coating thickness is thick, the solvent will easily remain during drying, so it is preferably 0.1 to 500 μm. [Example]

The present invention will be described in more detail below with reference to examples. The materials, usage amounts, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the concept of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. If the measurement equipment used in the examples is difficult to obtain due to discontinuation of production, etc., other equipment with equivalent performance can be used for measurement.

＜Measurement of weight average molecular weight and number average molecular weight＞ The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the following polymer (va) having a structural unit represented by the formula (V) and the like are measured by gel permeation chromatography (GPC). A liquid delivery pump (LC-20AD, manufactured by Shimadzu Corporation), a differential refractive index detector (RID-10A, manufactured by Shimadzu Corporation), and a GPC column (GPC KF-801, 802, 803, manufactured by Showa Denko Corporation) were used. 804), the solvent was tetrahydrofuran, the flow rate was 1.0 mL/min, the column temperature was 40°C, and a calibration line made of monodisperse polystyrene was used for implementation.

<Synthesis Example 1 Synthesis of polymer (va) having a structural unit represented by formula (V)> Put 2.25 moles of divinylbenzene (292.9g), 1.32 moles of ethylvinylbenzene (172.0g), 11.43 moles of styrene (1190.3g), and 15.0 moles of n-propyl acetate (1532.0g) into the reactor. , add 600 mmol of boron trifluoride diethyl ether complex at 70°C, and react for 4 hours. After stopping the polymerization reaction with an aqueous sodium bicarbonate solution, the oil layer was washed three times with pure water, devolatilized under reduced pressure at 60° C., and the polymer (va) having the structural unit represented by formula (V) was recovered. The obtained polymer (va) having the structural unit represented by the formula (V) was weighed, and it was confirmed that 860.8 g of the polymer (va) having the structural unit represented by the formula (V) was obtained.

The obtained polymer (va) having the structural unit represented by the formula (V) had a number average molecular weight Mn of 2,060, a weight average molecular weight Mw of 30,700, and a monodispersity Mw/Mn of 14.9. By carrying out ¹³ C-NMR and ¹ H-NMR analysis, it was observed that the polymer (va) having the structural unit represented by the formula (V) has a resonance line derived from each monomer unit used as a raw material. Based on the NMR measurement results and GC analysis results, the ratio of each monomer unit (structural unit derived from each raw material) in the polymer (va) having the structural unit represented by formula (V) was determined as follows. Structural units derived from divinylbenzene: 20.9 mol% (24.3 mass%) Structural units derived from ethylvinylbenzene: 9.1 mol% (10.7 mass%) Structural units derived from styrene: 70.0 mol% (65.0 mass% %) Furthermore, the structural unit having residual vinyl groups derived from divinylbenzene was 16.7 mol % (18.5 mass %).

Example 1 21.0 parts by mass of a compound represented by formula (M-2) and having m=0 (manufactured by Nippon Kayaku Co., Ltd., "MIR-5000"), and having a structural unit represented by formula (V) obtained in Synthesis Example 1 Polymer (va) 21.0 parts by mass, maleimide compound (m1a) having the following structure (manufactured by DIC, "NE-X-9470S", compound represented by formula (M1)) 21.0 parts by mass, thermoplastic 16.0 parts by mass of elastomer (SBS, manufactured by JSR Corporation, TR2250) and 21.0 parts by mass of phosphorus-based flame retardant (PX-200, manufactured by Daihachi Chemical Co., Ltd.) were dissolved in methyl ethyl ketone (solvent) and mixed to obtain a varnish. In addition, each addition amount mentioned above represents the solid content amount.

Maleimide compound (m1a) [Chemical 58] n is an integer from 1 to 20.

<Production of a test piece of a hardened plate with a thickness of 0.8 mm> The solvent was evaporated and distilled from the obtained varnish to obtain a resin composition powder. The resin composition powder was filled into a mold with a side of 100 mm and a thickness of 0.8 mm, and copper foil with a thickness of 12 μm (3EC-M2S-VLP, manufactured by Mitsui Metals Mining Co., Ltd.) was placed on both sides, and the pressure was 30 kg/cm ² . Perform vacuum pressing at a temperature of 220°C for 120 minutes to obtain a hardened plate with a side of 100mm and a thickness of 0.8mm. The obtained hardened plate was used to evaluate the relative dielectric constant (Dk), dielectric loss tangent (Df), glass transition temperature (Tg), peel strength, desmear resistance and moisture absorption heat resistance. The evaluation results are shown in Table 1.

＜Measurement method and evaluation method＞ (1) Relative dielectric constant (Dk) and dielectric loss tangent (Df) The copper foil on both sides of the obtained hardened plate was removed by etching, and then the size was reduced to 10 mm x 1 mm to obtain an evaluation sample. The obtained evaluation sample was dried at 120° C. for 60 minutes, and then the dried relative permittivity (Dk) and dielectric loss tangent (Df) at a frequency of 10 GHz were measured using a perturbation method cavity resonator. The measurement temperature was set to 23°C. The perturbation method cavity resonator was manufactured by Agilent Technologies, Agilent8722ES. Relative dielectric constant (Dk) A: Below 2.50 B: More than 2.50 and below 2.60 C: More than 2.60 Dielectric loss tangent (Df) S: 0.0014 or less A: More than 0.0014 and less than 0.0018 B: More than 0.0018 and less than 0.0020 C: More than 0.0020

(2) Glass transition temperature (Tg) The glass transition temperature is based on JIS-K7244-4: 1999 (Plastics - Dynamic) using a dynamic viscoelasticity measuring device after removing the copper foil on both sides of the hardened plate obtained by etching and reducing the size to 12.7mm × 30mm. Test methods for mechanical properties - Part 4: Tensile vibration - non-resonant method), measure dynamic viscoelasticity at a starting temperature of 30°C, an ending temperature of 400°C, a heating rate of 5°C/min, a measurement frequency of 1Hz, and a nitrogen environment. The temperature at which the loss tangent (tanδ) obtained at this time reaches the maximum value is defined as the glass transition temperature. The dynamic viscoelasticity measuring device used was EXSTAR6000 DMS6100 manufactured by Seiko Instruments Co., Ltd. Evaluation was performed as follows. A: Above 230℃ B: Above 200℃ and less than 230℃ C: Less than 200℃

(3) Peel strength Using the hardened plate (10 mm × 100 mm × 0.8 mm) obtained as above, the copper foil peel strength (adhesion strength) was measured twice according to the provisions of JIS C6481 5.7 "Peel strength" and the average value was obtained. The measurement temperature was set to 23°C. Evaluation was performed as follows. S: 0.50kN/m or more A: 0.38kN/m or more and less than 0.50kN/m B: 0.28kN/m or more but less than 0.38kN/m C: Less than 0.28kN/m

(4) Slag removal resistance The copper foil on both sides of the obtained hardened plate was removed by etching and the sample was reduced in size (50 mm × 50 mm), and the following immersion treatment was performed. First, the obtained sample was immersed in a swelling liquid (Swelling Dip Securiganth P, manufactured by Atotech Japan) at 80° C. for 10 minutes. Then, the immersed sample was immersed in a roughening liquid (Concentrate Compact CP, manufactured by Atotech Japan) at 80° C. for 5 minutes. Then, the immersed sample was immersed in a neutralizing solution (Reduction Conditioner Securiganth P500, manufactured by Atotech Japan) at 45° C. for 10 minutes. The mass reduction rate (mass %) of the sample after the immersion treatment was performed twice was measured. Evaluation was performed as follows. A negative sign indicates a decrease in mass. A: The mass reduction rate ranges from -4.0 mass% to -2.0 mass%. B: The mass reduction rate is outside the above range.

(5) Moisture absorption and heat resistance The obtained hardened board is cut (reduced in size) to 50 mm × 50 mm, and all the copper foil on one side is removed by etching. On the other side, half of the copper foil on the other side is removed by etching to obtain moisture absorption and heat resistance. Samples for sex determination. After drying the obtained sample at 120°C for 60 minutes, use a pressure cooker testing machine to let it stand for 5 hours in the presence of saturated water vapor at 121°C and 2 atmospheres, and then dip it into a solder bath at 260°C for 30 seconds. Visually observe whether there are any abnormal changes in appearance. The pressure cooker testing machine used was model PC-3 manufactured by Hirayama Seisakusho Co., Ltd. Each measurement was performed three times, and among the three tablets, when swelling was observed in 0 tablets, it was rated as "A", when swelling was observed in 1 to 2 tablets, it was rated as "B", and when swelling was observed in 3 tablets, it was rated as "C". The appearance observation is carried out by majority vote of 5 experts.

Example 2 In Example 1, the content of the compound represented by formula (M-2) and having m=0 (manufactured by Nippon Kayaku Co., Ltd., "MIR-5000") was changed to 18.9 parts by mass, and Synthesis Example 1 obtained a compound having the formula The content of the polymer (va) of the structural unit represented by (V) was changed to 21.8 parts by mass, and the content of the maleimide compound (m1a) (manufactured by DIC Corporation, "NE-X-9470S") was changed to 22.3 parts by mass. , others are implemented in the same way. The results are shown in Table 1.

Example 3 In Example 1, the content of the compound represented by formula (M-2) and having m=0 (manufactured by Nippon Kayaku Co., Ltd., "MIR-5000") was changed to 20.9 parts by mass, and Synthesis Example 1 obtained a compound having the formula The content of the polymer (va) of the structural unit represented by (V) was changed to 16.8 parts by mass, and the content of the maleimide compound (m1a) (manufactured by DIC Corporation, "NE-X-9470S") was changed to 25.3 parts by mass. , others are implemented in the same way. The results are shown in Table 1.

Example 4 In Example 1, the content of the compound represented by formula (M-2) and having m=0 ("MIR-5000" manufactured by Nippon Kayaku Co., Ltd.) was changed to 13.0 parts by mass, and Synthesis Example 1 obtained a compound having the formula The content of the polymer (va) of the structural unit represented by (V) was changed to 5.0 parts by mass, and the content of the maleimide compound (m1a) (manufactured by DIC Corporation, "NE-X-9470S") was changed to 45.0 parts by mass. , others are implemented in the same way. The results are shown in Table 1.

Example 5 In Example 1, the content of the compound represented by formula (M-2) and having m=0 (manufactured by Nippon Kayaku Co., Ltd., "MIR-5000") was changed to 24.0 parts by mass, and Synthesis Example 1 obtained a compound having the formula The content of the polymer (va) of the structural unit represented by (V) was changed to 34.0 parts by mass, and the content of the maleimide compound (m1a) (manufactured by DIC Corporation, "NE-X-9470S") was changed to 5.0 parts by mass. , others are implemented in the same way. The results are shown in Table 1.

Example 6 In Example 1, the content of the compound represented by formula (M-2) and having m=0 (manufactured by Nippon Kayaku Co., Ltd., "MIR-5000") was changed to 5.0 parts by mass, and Synthesis Example 1 obtained a compound having the formula The content of the polymer (va) of the structural unit represented by (V) was changed to 29.0 parts by mass, and the content of the maleimide compound (m1a) (manufactured by DIC Corporation, "NE-X-9470S") was changed to 29.0 parts by mass. , others are implemented in the same way. The results are shown in Table 1.

Example 7 In Example 1, the content of the compound represented by formula (M-2) and having m=0 (manufactured by Nippon Kayaku Co., Ltd., "MIR-5000") was changed to 18.0 parts by mass, and a compound having the formula was obtained in Synthesis Example 1. The content of the polymer (va) of the structural unit represented by (V) was changed to 40.0 parts by mass, and the content of the maleimide compound (m1a) (manufactured by DIC Corporation, "NE-X-9470S") was changed to 5.0 parts by mass. , others are implemented in the same way. The results are shown in Table 1.

Comparative example 1 The compound represented by the formula (M-2) in Example 1 and having m=0 (manufactured by Nippon Kayaku Co., Ltd., "MIR-5000") and the polymer having the structural unit represented by the formula (V) ( va), and the content of the maleimide compound (m1a) (manufactured by DIC, "NE-X-9470S") was changed to 63.0 parts by mass, and the other operations were carried out in the same manner. The results are shown in Table 2.

Comparative example 2 The polymer (va) and the maleimide compound (m1a) (manufactured by DIC Corporation, "NE-X-9470S") having the structural unit represented by formula (V) in Example 1 were not used, and the formula ( The content of the compound represented by M-2) and having m=0 (manufactured by Nippon Kayaku Co., Ltd., "MIR-5000") was changed to 63.0 parts by mass, and the other operations were carried out in the same manner. The results are shown in Table 2.

Comparative example 3 The compound represented by the formula (M-2) in Example 1 and having m=0 (manufactured by Nippon Kayaku Co., Ltd., "MIR-5000") and the maleimide compound (m1a) (manufactured by DIC Corporation) were not used. , "NE-X-9470S"), and the content of the polymer (va) having the structural unit represented by formula (V) was changed to 63.0 parts by mass, and the other operations were carried out in the same manner. The results are shown in Table 2.

Comparative example 4 In Example 1, the content of the compound represented by formula (M-2) and m=0 (manufactured by Nippon Kayaku Co., Ltd., "MIR-5000") was changed to 31.5 parts by mass, and the content of the maleimide compound ( The content of m1a) (manufactured by DIC, "NE-X-9470S") was changed to 31.5 parts by mass, and the polymer (va) having the structural unit represented by the formula (V) was not used, and the other operations were carried out in the same manner. The results are shown in Table 2.

Comparative example 5 In Example 1, the compound represented by the formula (M-2) and having m=0 (manufactured by Nippon Kayaku Co., Ltd., "MIR-5000") was not used, and the polymerization of the structural unit having the structural unit represented by the formula (V) was carried out The content of the substance (va) was changed to 31.5 parts by mass, the content of the maleimide compound (m1a) (manufactured by DIC, "NE-X-9470S") was changed to 31.5 parts by mass, and the other operations were carried out in the same manner. The results are shown in Table 2.

Comparative Example 6 In Example 1, 21.0 parts by mass of the polymer (va) having a structural unit represented by formula (V) was replaced with an equivalent amount of a maleimide compound (MIR-3000, manufactured by Nippon Kayaku Co., Ltd. (as shown in the above structure), others are implemented in the same way. The results are shown in Table 2. [Chemistry 59]

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Relative dielectric constant (Dk) A A A A A A A Dielectric loss tangent (Df) S A A A B B A Glass transition temperature (Tg) A A A A A A A Peel strength(kN/m) S A A A A A A Slag removal resistance A A A A A A B Moisture absorption and heat resistance A A A A A A A [Table 2] Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Relative dielectric constant (Dk) A C A A A B Dielectric loss tangent (Df) A C A B A A Glass transition temperature (Tg) A C C B B A Peel strength(kN/m) B S C B C B Slag removal resistance B A A B B B Moisture absorption and heat resistance B C C C C B

Claims (21)

A resin composition containing: a compound (M) represented by formula (M), a polymer (V) having a structural unit represented by formula (V), and a compound (M1) represented by formula (M1); In the formula (M), R each independently represents a hydrocarbon group with 1 to 10 carbon atoms that may be substituted by a halogen atom, R ^mx each independently represents a methylene group, an ethylene group, or a 2,2-propylene group, and R ^my is a base selected from the following group (A); m represents an integer from 0 to 3, n is the average of repeated numbers, and represents 1.00≦n≦20.00; (Group (A)) In group (A), R ^y is each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may have a substituent, and ny is each independently an alkyl group having 0 to 3 carbon atoms. Integer, * is the bonding position with R ^mx ; In formula (V), Ar represents an aromatic hydrocarbon linking group; * represents a bonding position; In the formula (M1), R ^M1 , R ^M2 , R ^M3 and R ^M4 each independently represent a hydrogen atom or an organic group; R ^M5 and R ^M6 each independently represent a hydrogen atom or an alkyl group; Ar ^M represents a divalent aromatic group. ; A is an alicyclic group with 4 to 6 members; R ^M7 and R ^M8 are each independently an alkyl group; mx is 1 or 2, lx is 0 or 1; R ^M9 and R ^M10 independently represent a hydrogen atom or an alkyl group; group; ^RM11 , ^RM12 , ^RM13 and ^RM14 each independently represent a hydrogen atom or an organic group; ^RM15 each independently represents an alkyl group with 1 to 10 carbon atoms, an alkyloxy group with 1 to 10 carbon atoms, a carbon Alkylthio group with 1 to 10 carbon atoms, aryl group with 6 to 10 carbon atoms, aryloxy group with 6 to 10 carbon atoms, arylthio group with 6 to 10 carbon atoms, halogen atom, hydroxyl group or mercapto group; px represents an integer from 0 to 3; nx represents an integer from 1 to 20. The resin composition of claim 1, wherein the content of the compound (M) represented by the formula (M) is 5 to 50 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. The resin composition of claim 1 or 2, wherein the content of the polymer (V) having the structural unit represented by formula (V) is 5 to 50 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. share. The resin composition of claim 1 or 2, wherein the content of the compound (M1) represented by the formula (M1) is 5 to 50 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. The resin composition of claim 1 or 2, wherein in the compound (M) represented by the formula (M), n is 1.05≦n≦20.00. The resin composition of claim 1 or 2, wherein the compound (M) represented by the formula (M) includes a compound represented by the formula (M-1); In formula (M-1), R each independently represents a hydrocarbon group with 1 to 10 carbon atoms that may be substituted by a halogen atom; m represents an integer from 0 to 3, n is the average of the repeat numbers, and represents 1.00≦n≦ 20.00. The resin composition of claim 1 or 2, wherein the compound (M) represented by the formula (M) includes a compound represented by the formula (M-2); In the formula (M-2), R ^z independently represents a hydrocarbon group having 1 to 10 carbon atoms; m represents an integer from 0 to 3, n is the average of the repeat numbers, and represents 1.00≦n≦20.00. The resin composition of claim 1 or 2, wherein the weight average molecular weight of the polymer (V) having the structural unit represented by formula (V) is 3,000 to 130,000. The resin composition of claim 1 or 2, wherein the weight average molecular weight of the polymer (V) having the structural unit represented by formula (V) is 10,000 to 130,000. The resin composition of claim 1 or 2 further contains a maleimide compound or an epoxy compound selected from the compound (M) represented by the formula (M) and the compound (M1) represented by the formula (M1). , a group consisting of phenolic compounds, oxetane resins, benzodiazepine compounds, (meth)allyl-containing compounds, and polyphenylene ether compounds containing more than two carbon-carbon unsaturated double bonds. One or more other thermosetting compounds (C). The resin composition of claim 10, wherein the content of the other thermosetting compound (C) is 1 to 50 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. For example, the resin composition of claim 1 or 2 further contains a filler (D). The resin composition of claim 12, wherein the content of the filler (D) in the resin composition is 10 to 1600 parts by mass relative to 100 parts by mass of the resin solid content. For example, the resin composition of claim 1 or 2 further contains a thermoplastic elastomer. The resin composition of claim 1 or 2, wherein the content of the compound (M) represented by the formula (M) is 5 to 50 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition, and the compound (M) having the formula The content of the polymer (V) of the structural unit represented by (V) is 5 to 50 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition, and the compound (M1) represented by the formula (M1) is The content of the resin solid content in the resin composition is 5 to 50 parts by mass per 100 parts by mass, the compound (M) represented by the formula (M) includes the compound represented by the formula (M-1), and n is 1.05≦n≦20.00 , the weight average molecular weight of the polymer (V) having the structural unit represented by formula (V) is 3,000 to 130,000; In formula (M-1), R each independently represents a hydrocarbon group with 1 to 10 carbon atoms that may be substituted by a halogen atom; m represents an integer from 0 to 3, n is the average of the repeat numbers, and represents 1.00≦n≦ 20.00. A cured product is a cured product of the resin composition according to any one of claims 1 to 15. A prepreg formed from a base material and a resin composition according to any one of claims 1 to 15. A metal foil laminated board containing: at least 1 layer formed from a prepreg as claimed in claim 17, and A single-sided or double-sided metal foil placed on the layer formed of the prepreg. A resin composite sheet containing: support, and A layer formed of the resin composition according to any one of claims 1 to 15 is arranged on the surface of the support. A printed wiring board includes an insulating layer and a conductor layer arranged on the surface of the insulating layer, the insulating layer including at least one layer formed of the resin composition according to any one of claims 1 to 15. A semiconductor device including the printed wiring board according to claim 20.