heterocyclic compounds

Abstract

The objective is to provide novel heterocyclic compounds and methods for producing the same. [Solution] A heterocyclic compound represented by the following general formula (1) is provided, where R 2 is a monovalent hydrocarbon group or hydrogen atom, and R 3 X is a hydrogen atom, a methyl group, or an ethyl group, X is a triazole or tetrazole structure represented by the following formula (2), and Y is a sulfur atom or an NH group, and in general formula (2), R 1 This is a monovalent hydrocarbon group or a hydrogen atom. JPEG2026086780000025.jpg87170

Description

Technical Field

[0001] The present invention relates to a heterocyclic compound, a method for producing the same, and the like.

Background Art

[0002] A heterocyclic compound is a cyclic compound containing at least two different elements in the ring. Examples of the ring include a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring, an eight-membered ring, a nine-membered ring, a fused ring, etc., and any of them may be saturated or unsaturated. Combinations of, for example, a carbon (C) atom and at least one kind of heteroatom are known as the heteroatoms in the ring, and examples of the heteroatom include a boron (B) atom, a nitrogen (N) atom, an oxygen (O) atom, a phosphorus (P) atom, a sulfur (S) atom, etc.

[0003] Heterocyclic compounds are used in various fields such as, for example, chemical synthesis, heterocyclic chemistry, nucleic acids and drugs derived therefrom, bio-derived resources, biofuels, dyes, optical materials, electronic materials, transmission lines, etc. Among them, in the formation of a metal-clad laminate usable for high-frequency transmission and fifth-generation (5G) communication systems, heterocyclic compounds containing a nitrogen atom have attracted attention as adhesion aids for improving the adhesion between a member and a metal surface.

[0004] For example, Patent Document 1 describes that a triazole ring compound having a 1,2,3-triazole ring or a 1,2,4-triazole ring is contained in a curable resin composition in order to enhance the adhesion between a cured product and a conductor layer.

[0005] For example, Patent Document 2 describes adhesion-imparting agents such as imidazole-based, thiazole-based, and triazole-based agents as additives.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] The triazole compound described in Patent Document 1 does not have a polymerizable group and has poor polycondensability with the target member. Further, since the curable resin composition described in Patent Document 1 enhances the adhesion between the cured product and the conductor layer by a combination of an epoxy compound, a triazole compound, and a tertiary amine, it does not focus on improving the adhesion by the triazole compound alone.

[0008] Also, the adhesion promoter described in Patent Document 2 does not disclose the specific structure or embodiment of an imidazole-based compound having a polymerizable group.

[0009] Furthermore, the heterocyclic compound containing a nitrogen atom described in Patent Document 1 and Patent Document 2 still has room for improvement in achieving both improvement in the adhesion between the member and the metal surface and protection from corrosion of the metal surface in adhesion, bonding, lamination, etc.

[0010] Therefore, an object of the present invention is to provide a novel heterocyclic compound, a method for producing the same, and use thereof to improve the adhesion between a member and a metal surface and protect the metal surface from corrosion.

Means for Solving the Problems

[0011] The above problems can be solved by the following examples of technical means. [1] The following general formula (1):

Chemical formula

[0012] According to the present invention, a novel heterocyclic compound and a method for producing the same are provided. The novel heterocyclic compound can be used as a starting material or intermediate to carry out various chemical reactions, polymerization reactions, synthesis, or compounding. For example, it can be used as an adhesion aid in adhesion, bonding, and lamination between a component and a metal surface, or to achieve both protection from corrosion or rust on the metal surface and improved adhesion. [Brief explanation of the drawing]

[0013] [Figure 1] This is a 1H-NMR chart of a heterocyclic compound according to one embodiment of the present invention. [Figure 2] This is a GPC chart of a heterocyclic compound according to one embodiment of the present invention. [Figure 3] This is a 1H-NMR chart of a heterocyclic compound according to another embodiment of the present invention. [Figure 4] This is a 1H-NMR chart of a heterocyclic compound according to yet another embodiment of the present invention. [Modes for carrying out the invention]

[0014] <Heterocyclic compounds> The heterocyclic compound according to this embodiment is given by the following general formula (1): [ka] {where, R 2 is a monovalent hydrocarbon group or a hydrogen atom, and R 3 is a hydrogen atom, a methyl group, or an ethyl group, and X is represented by the following general formula (2): [ka] (In the formula, R 1 is a monovalent hydrocarbon group or hydrogen atom. The structure is a triazole or tetrazole structure represented by ), and Y is a sulfur atom or an NH group. It is represented as follows.

[0015] The heterocyclic compound represented by the general formula (1) forms a complex with a metal due to a triazole structure or a tetrazole structure represented by the general formula (2), forms a chemical bond of an acryloyl group, a methacryloyl group, or an ethacryloyl group with a resin having an ethylenically unsaturated group, and -OR at the connecting part 2 By controlling the polarity by modification, there is a tendency to achieve both the adhesion between the metal surface and the adherend and the rust prevention property of the metal. This tendency is remarkable when the metal surface is made of copper (Cu) and the Cu surface is a low roughness surface, an ultra-low roughness surface, or a non-roughened surface.

[0016] In the general formula (1), R 2 is a monovalent hydrocarbon group or a hydrogen atom. The monovalent hydrocarbon group as the R 2 group may have 1 to 33 carbon atoms, may be substituted or unsubstituted, may be saturated or unsaturated, may be chain-like or cyclic, and / or may be aliphatic or aromatic. When it is chain-like, it may be linear or branched. When it is substituted, the substituent may be a monovalent aliphatic or aromatic group having 1 to 10 carbon atoms. For example, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups; vinyl, allyl, propenyl, 3-butenyl, 2-butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, octenyl, nonenyl, decenyl, ethynyl, propynyl, butynyl, pentynyl, and hexynyl groups; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups; phenyl, aryl, and benzyl groups, etc.

[0017] R 2 Specific examples of the monovalent hydrocarbon group as the R

[0018] R 2The substituted or unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferably 1 to 10, 1 to 15, or 4 to 12 carbon atoms in the case of a chain, and preferably 3 to 18 or 3 to 20 carbon atoms in the case of an alicyclic structure. Specific examples of substituted or unsubstituted aliphatic hydrocarbon groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups. Examples include linear or branched alkyl groups; unsaturated aliphatic hydrocarbon groups such as vinyl, allyl, propenyl, 3-butenyl, 2-butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, octenyl, nonenyl, decenyl, ethynyl, propynyl, butynyl, pentynyl, and hexynyl groups; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.

[0019] R 2 Specific examples of substituted or unsubstituted aromatic groups with 6 to 24 carbon atoms include phenyl, aryl, benzyl, naphthyl, anthryl, and phenanthryl groups.

[0020] From the viewpoint of preventing the deposit on the metal surface from degrading the dielectric properties of the metal-clad laminate, in general formula (1), R 2 It is preferably a hydrogen (H) atom. In general formula (1), -OR 2 When is -OH, the linkage between the triazole or tetrazole structure and the acryloyl group, methacryloyl group, or ethacryloyl group is -OH modified, thereby suppressing the increase in the Df (dielectric loss tangent) value of the adherend even when the resin composition for forming the adherend contains a heterocyclic compound represented by general formula (1).

[0021] In general formula (1), R 3The group is a hydrogen atom, a methyl group, or an ethyl group. From the viewpoint of availability of raw materials for the synthesis of heterocyclic compounds represented by general formula (1), it is preferably a hydrogen atom or a methyl group. From the viewpoint of protection from corrosion or rust on metal surfaces and improvement of adhesion to the substrate, it is preferably a methyl group. From the viewpoint of the bulkiness of the resulting heterocyclic compound, it is preferably an ethyl group.

[0022] In general formula (1), Y is a sulfur (S) atom or an NH group, and forms -S- or -NH- as a link between the triazole structure or tetrazole structure and an acryloyl group, methacryloyl group, or ethacryloyl group.

[0023] In general formula (1), the presence of the linkage Y is a triazole or tetrazole structure capable of complex formation with copper (Cu), an acryloyl group, a methacryloyl group, or an ethacryloyl group capable of chemical bonding to the constituent resin of the adherend, and -OR 2 By allowing the modified portion to coexist within a single molecule, it becomes possible to improve the adhesion strength between the substrate containing that molecule and the metal surface while suppressing an increase in the Df (dielectric loss tangent) value of the substrate.

[0024] In general formula (1), X is a triazole structure or tetrazole structure represented by general formula (2), and in the case of a triazole structure, the following formula (2A-1): [ka] (In the formula, R 1 (This is a monovalent hydrocarbon group or a hydrogen atom.) A monovalent group having a substituted or unsubstituted 1,2,4-triazole skeleton represented by the following formula (2A-2): [ka] It is a monovalent group derived from 3-amino-1,2,4-triazole, represented by the formula (2Z) below, and in the case of a tetrazole structure, it is represented by the formula (2Z): [ka] It is a monovalent group derived from tetrazole, represented by [formula].

[0025] In the 1,2,4-triazole ring represented by formula (2A-1), the linkage to Y in general formula (1) and R 1 Their relative positions are 3rd and 5th, or vice versa.

[0026] In equation (2A-1), R 1 R is a monovalent hydrocarbon group or a hydrogen (H) atom, 1 In the case of =H, the monovalent group represented by formula (2A-1) is an unsubstituted 1,2,4-triazole group, which can be linked to Y in general formula (1) at the 3-position of the 1,2,4-triazole ring.

[0027] R 1 The monovalent hydrocarbon group as a base may have 1 to 33 carbon atoms, may be substituted or unsubstituted, saturated or unsaturated, linear or cyclic, and / or aliphatic or aromatic. If linear, it may be linear or branched. If substituted, the substituent may be a monovalent aliphatic or aromatic group having 1 to 10 carbon atoms, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups; vinyl, allyl, propenyl, 3-butenyl, 2-butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, octenyl, nonenyl, decenyl, ethinyl, propynyl, butynyl, pentynyl, and hexynyl groups; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups; phenyl, aryl, and benzyl groups, etc.

[0028] R 1 Specific examples of monovalent hydrocarbon groups as a base include substituted or unsubstituted aliphatic hydrocarbon groups having 1 to 20 carbon atoms, or substituted or unsubstituted aromatic groups having 6 to 24 carbon atoms.

[0029] R 1 The substituted or unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferably 1 to 10, 1 to 15, or 4 to 12 carbon atoms in the case of a chain, and preferably 3 to 18 or 3 to 20 carbon atoms in the case of an alicyclic structure. Specific examples of substituted or unsubstituted aliphatic hydrocarbon groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups. Examples include linear or branched alkyl groups; unsaturated aliphatic hydrocarbon groups such as vinyl, allyl, propenyl, 3-butenyl, 2-butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, octenyl, nonenyl, decenyl, ethynyl, propynyl, butynyl, pentynyl, and hexynyl groups; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.

[0030] R 1 Specific examples of substituted or unsubstituted aromatic groups with 6 to 24 carbon atoms include phenyl, aryl, benzyl, naphthyl, anthryl, and phenanthryl groups.

[0031] The monovalent group represented by formula (2A-2) has an amino group substituted at the 3rd position of the 1,2,4-triazole ring, and can be linked to Y in general formula (1) at the 5th position.

[0032] The monovalent group represented by formula (2Z) can be linked to Y in general formula (1) at the 5-position of the tetrazole ring.

[0033] The molecular weights of heterocyclic compounds represented by general formula (1) are X, Y, and R. 1 , R 2 or R 3 The range is determined by the selection, for example, within the ranges of 200-1,030, 200-830, 200-630, 200-530, 200-430, 200-380, or 200-330.

[0034] Regarding heterocyclic compounds represented by general formula (1), from the viewpoint of protection from corrosion or rust on metal surfaces and improvement of adhesion to the substrate, X, Y and R 2 and R 3 The following are preferred combinations: Heterocyclic compound I {X = monovalent group represented by formula (2A-1), Y = S, R} 2 =H, R 3 =methyl group}; Heterocyclic compound II {X = monovalent group represented by formula (2A-2), Y = S, R} 2 =H, R 3 =methyl group}; and Heterocyclic compound III {X = monovalent group represented by formula (2Z), Y = NH, R 2 =H, R 3 =methyl group}.

[0035] Heterocyclic compound I is specifically defined by the following general formula (I): [ka] {where, R 1 This is as defined for equations (2) and (2A-1). It is represented as follows.

[0036] From the viewpoint of corrosion prevention on metal surfaces and adhesion between the metal surface and the substrate, heterocyclic compound I is expressed by the following formula (I-1): [ka] It is preferable that the compound is represented by [formula].

[0037] Heterocyclic compound II is specifically represented by the following formula (II): [ka] It is represented as follows.

[0038] Heterocyclic compound III is specifically represented by the following formula (III): [ka] It is represented as follows.

[0039] Heterocyclic compounds I to III can be included in the resin composition independently or in any combination, thereby suppressing deterioration of the dielectric properties of the cured resin composition, improving the adhesion of the cured resin to metal surfaces, and preventing metal corrosion or rust in metal-clad laminates.

[0040] <Method for producing heterocyclic compounds> The method for producing heterocyclic compounds according to this embodiment may include, for example, epoxide cleavage reactions, epoxide addition reactions, oxiran ring-opening reactions, amine-epoxide reactions, thiol-epoxide reactions, (partial) crosslinking or curing reactions of epoxy compounds, reaction acceleration of epoxides with imidazoles or tetrazoles, reaction acceleration of thiol-epoxides with tertiary amines, and reaction acceleration by other catalytic actions. These can be used individually or in combination.

[0041] Specifically, glycidyl acrylate (GA), glycidyl methacrylate (GMA), glycidyl ethanolacrylate (GEA), or any combination thereof (hereinafter collectively referred to as "glycidyl (alkyl) acrylate compounds") and the following formula: X-SH {wherein X is as defined in equation (1) above}; and / or X-NH2 {wherein X is as defined in equation (1) above} By reacting it with a compound represented by the above general formula (1), a heterocyclic compound represented by the above general formula (1) can be obtained.

[0042] As glycidyl(alkyl) acrylate compounds, GA, GMA, GEA, or any combination thereof, are defined as the R in general formula (1). 3The appropriate choice depends on the following: GA or GMA is preferred from the viewpoint of raw material availability; GMA is preferred from the viewpoint of protection from corrosion or rust on the metal surface and improved adhesion to the substrate; and GEA is preferred from the viewpoint of the bulk of the reaction product.

[0043] For the reaction between a glycidyl (alkyl) acrylate compound and a compound represented by formula X-SH and / or X-NH2, it is preferable to use an organic solvent as the reaction solvent. For example, ketones such as acetone; alcohols such as methanol and ethanol; and glycol-based solvents such as glycol ethers, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate may be used.

[0044] Regarding the reaction conditions, the reaction temperature may be at room temperature or room temperature, for example, within the range of 15°C to 40°C or 20°C to 35°C; the reaction time may be within the range of 3 hours to 120 hours, 4 hours to 118 hours, 4 hours to 50 hours, or 6 hours to 25 hours; and the reaction atmosphere is preferably under fume hood drying or vacuum drying.

[0045] After the reaction is complete, the product can be separated by methods such as filtration, evaporation to dryness, vacuum drying, standing, decantation, precipitation, redissolution, reprecipitation, gel permeation chromatography (GPC), and nuclear magnetic resonance (NMR) measurement, either individually or in appropriate combinations, from the viewpoint of improving the yield of the product or identifying the product.

[0046] In the reaction between a glycidyl (alkyl) acrylate compound and a compound represented by formula X-SH and / or X-NH2, R in general formula (1) 2 Heterocyclic compounds in which the atom is a hydrogen (H) atom tend to be easily obtained.

[0047] In general formula (1), R 2 If a heterocyclic compound in which is a monovalent hydrocarbon is obtained, (i) in the above reaction, 2 OH (however, R 2A nucleophile such as (which is a monovalent hydrocarbon) is used in the ring-opening of the epoxide, resulting in -OR 2 Base (however, R 2 (ii) A method for forming a product or intermediate having (a monovalent hydrocarbon); (ii) In general formula (1), R 2 The -OH group of a heterocyclic compound that is =H is converted to sodium alkoxide (-O) using a base such as sodium hydride or sodium hydroxide. - Na + After being converted to metal alkoxides such as ), they react with halogen compounds such as alkyl halides, or in the presence of tertiary amines such as triethylamine, to form -OR 2 Base (however, R 2 Methods such as those for forming a monovalent hydrocarbon can be employed.

[0048] In the reaction between a glycidyl(alkyl) acrylate compound and a compound represented by formula X-SH or X-NH2, the molar ratio of the two (glycidyl(alkyl) acrylate compound: compound represented by formula X-SH or X-NH2) is preferably 1:1.0 to 1.3 or 1:1.0 to 1.2, and more preferably 1:1.0 to 1.1, from the viewpoint of improving the yield of the product or suppressing the isomerization reaction.

[0049] As the reaction product with the glycidyl(alkyl)acrylate compound, if X has a triazole structure, the compound represented by formula X-SH is preferred, and if X has a tetrazole structure, the compound represented by formula X-NH2 is preferred.

[0050] Compounds represented by formula X-SH, when X has a triazole structure, are given by the following formula: [ka] {where, R 1 This is as defined in equations (2) and (2A-1) above. The compound is preferably represented by , or 3-amino-5-mercapto-1,2,4-triazole, and more preferably 3-mercapto-1,2,4-triazole or 3-amino-5-mercapto-1,2,4-triazole.

[0051] The compound represented by formula X-NH2 is preferably 5-aminotetrazole when X has a tetrazole structure.

[0052] For the reaction between a glycidyl(alkyl) acrylate compound and a compound represented by formula X-SH and / or X-NH2, it is preferable to use a basic catalyst or a strong basic catalyst. When using a basic catalyst or a strong basic catalyst, the molar ratio of the glycidyl(alkyl) acrylate compound to the catalyst (glycidyl(alkyl) acrylate compound: catalyst) is preferably 1:0.09 to 0.13, and more preferably 1:0.10 to 0.13, from the viewpoint of suppressing the formation of isomers. From a similar viewpoint, the molar ratio of the glycidyl(alkyl) acrylate compound, the compound represented by formula X-SH or X-NH2, and the catalyst (glycidyl(alkyl) acrylate compound: compound represented by formula X-SH or X-NH2: catalyst) is preferably 1:1.0 to 1.3:0.09 to 0.13.

[0053] While we do not wish to be bound by theory, it is known that primary, secondary, and tertiary amino groups exhibit significantly different reactivity with epoxy groups. Primary amino groups are the most reactive, secondary amino groups are the least reactive, and tertiary amines, lacking active hydrogen, do not react with epoxy groups. Instead, they function as catalysts for reactions between epoxy groups or between epoxy groups and other functional groups (e.g., primary amino groups, mercapto groups, alcoholic hydroxyl groups). Therefore, using a tertiary amine such as triethylamine (TEA) as a basic catalyst can accelerate the reaction of mercapto groups through the catalytic action of the tertiary amine, or allow for catalytic use of the tertiary amine without inhibiting the reaction between compounds containing primary amino groups and glycidyl (alkyl) acrylate compounds.

[0054] Furthermore, it was found that using a tertiary amine such as TEA as a catalyst in the reaction to obtain the heterocyclic compound according to this embodiment tends to suppress isomerization reactions and improve the yield of the desired heterocyclic compound.

[0055] In the reaction to obtain the heterocyclic compound according to this embodiment, if it is desirable to suppress the progress of the crosslinking or curing reaction of epoxy groups derived from GA, GMA, GEA, or combinations thereof, it is preferable to avoid the inclusion of polyfunctional compounds such as polyamino compounds and polymercapto compounds.

[0056] On the other hand, depending on the application of the heterocyclic compound according to this embodiment, it may be preferable to allow a crosslinking or curing reaction of epoxy groups derived from 2 moles of glycidyl (alkyl) acrylate compound to proceed. In that case, it is preferable to promote a curing or crosslinking reaction between the heterocyclic compound and other crosslinking agents, either in-situ or in a separate reaction system, during or after the reaction to obtain the heterocyclic compound, in order to form a cured product or crosslinked network containing structural units derived from the heterocyclic compound.

[0057] <Resin composition> Another aspect of the present invention involves the following components: (A) Heterocyclic compounds according to the present embodiment as described above; (B) Resins having ethylenically unsaturated groups; and (C) Polymerization initiator The present invention provides a resin composition containing the following:

[0058] A resin composition containing components (A) to (C) has the advantage of maintaining the dielectric properties of the cured product while simultaneously achieving good adhesion to the support and corrosion resistance when the support or substrate has a metal surface, in applications such as lamination of the cured product with a support, manufacture of metal-clad laminates, manufacture of printed circuit boards, and manufacture of high-speed communication modules.Optionally, the resin composition may further contain (D) a solvent, additives, etc., in addition to components (A) to (C).

[0059] Component (A) is a heterocyclic compound represented by general formula (1), as described above, and is preferably a compound represented by any of formulas (I) to (III).

[0060] Component (B) is a resin having an ethylenically unsaturated group, and from the viewpoint of the dielectric properties of the cured product when the resin composition is cured, and the chemical bonding with the acryloyl group, methacryloyl group, or ethacryloyl group of component (A), it is preferable that it is at least one resin selected from the group consisting of polyphenylene ether, polystyrene, resins having an alicyclic structure, polybenzoxazole precursor resin, polyimide precursor resin, and phenol resin.

[0061] The mass ratio (A:B) of component (A) to component (B) in the resin composition is not particularly limited, but may be, for example, 1:7 to 50, 1:8 to 46, or 1:9 to 44.

[0062] Component (C) is a polymerization initiator and is preferably at least one selected from the group consisting of oxime esters and peroxides, from the viewpoint of exposure and / or curing of the resin composition.

[0063] Examples of oxime esters include 1-phenyl-1,2-propanedione-2-O-benzoyl oxime and 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime.

[0064] As peroxides, organic peroxides are preferred, and examples include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3, di-t-butyl peroxide, t-butylcumyl peroxide, di(2-t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di(trimethylsilyl)peroxide, trimethylsilyltriphenylsilyl peroxide, and the like. Furthermore, radical generators such as 2,3-dimethyl-2,3-diphenylbutane can also be used as reaction initiators for resin compositions.

[0065] The content of component (C) is preferably 0.05% by mass or more, more preferably 0.5% by mass or more or 1% by mass or more, and even more preferably 1.5% by mass or more, with the total content of components (A) and (B) as a reference of 100% by mass, from the viewpoint of increasing the reaction rate of the photopolymerization reaction or curing reaction, and preferably 5% by mass or less, more preferably 4.5% by mass or less, and even more preferably 4.0% by mass or less, from the viewpoint of keeping the dielectric constant and dielectric loss tangent of the resulting cured product low.

[0066] The photosensitive resin composition may contain additives such as crosslinking agents (e.g., triallyl isocyanurate, α,α'-di(t-butylperoxy)diisopropylbenzene, etc.), elastomers (e.g., hydrogenated styrene-based thermoplastic resins, etc.), flame retardants, inorganic fillers (e.g., silica fillers, etc.), heat stabilizers, antioxidants, UV absorbers, surfactants, lubricants, etc. The content of the additives is preferably 0.01 to 100% by mass, more preferably 0.1 to 80% by mass, and even more preferably 1 to 50% by mass, based on the total content of components (A) and (B) as 100% by mass.

[0067] If the resin composition contains (D) a solvent, it may be in the form of a varnish in which the solid components in the resin composition are dissolved or dispersed in the solvent.

[0068] From the viewpoint of solubility, preferred solvents include aromatic compounds such as toluene and xylene; alcohols such as methanol and ethanol; and at least one of acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether, and chloroform. These solvents can be used individually or in combination of two or more.

[0069] (D) From the viewpoint of suitably dissolving components (A) and / or (B) in the solvent and easily ensuring suitable fluidity of the resin composition even at room temperature, solvents of aromatic compounds such as toluene and xylene are more preferred as solvent (D), and for example, toluene-methyl ethyl ketone mixed solvent, toluene-cyclohexane mixed solvent, and toluene-cyclopentanone mixed solvent are even more preferred. Furthermore, from the viewpoint of impregnation into the substrate, toluene alone is also preferred as solvent (D).

[0070] (D) The amount of solvent used can be arbitrarily determined, for example, depending on the predetermined viscosity of the resin composition, the means of applying the resin composition to the support, the material of the support, the level of surface roughening of the support, etc.

[0071] <Laminate> In one embodiment, a laminate is provided comprising the resin composition or varnish thereof described above and a support or substrate. When the laminate is used as a material for an electronic circuit board such as a printed wiring board, it is preferable that the laminate is formed using the varnish described above. The laminate can be designed to suit the material of the support or substrate, or the method of application to the support or substrate, and specifically, it is a resin film, an impregnated composite of a substrate and a resin (hereinafter also referred to as "prepreg"), a resin-coated metal foil, or a metal-clad laminate, or a laminate containing at least one of these.

[0072] Methods for applying a resin composition or its varnish to a support or substrate are not particularly limited, but include, for example, coating, applying or spraying the resin composition onto the support or substrate; bonding or laminating a molded article, cured product, or dry film resist of the resin composition to the support or substrate; immersion of the support or substrate in the resin composition; impregnation of the support or substrate with the resin composition; transfer or re-attachment of the resin composition from the support to the substrate; other compounding; and drying of the resin composition or varnish. The application methods listed above can be used individually or in any combination.

[0073] Examples of support materials include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate and polyethylene naphthalate; polycarbonate; polyimide; metal foils such as copper foil and aluminum foil; and release paper.

[0074] If the support is to be removed from the cured resin composition afterward, it may be subjected to chemical or physical treatments such as matte finishing, corona treatment, or mold release treatment. On the other hand, if the support has a metal surface such as copper or aluminum, or if it is used together with the cured resin composition to manufacture printed circuit boards or high-speed communication modules, it is preferable that it has a low-roughness surface (e.g., 1.2 μm ≤ Rz < 1.4 μm) or an ultra-low-roughness surface (e.g., 0.9 μm ≤ Rz < 1.2 μm), or is not roughened (e.g., Rz < 0.9 μm), from the viewpoint of optimizing the effect of component (A) contained in the resin composition, i.e., the heterocyclic compound represented by general formula (1).

[0075] The laminate has the following characteristics (i) and / or (ii) (i) Peel strength of the cured resin composition on the support ≥ 0.4N (ii) Df2 - Df1 ≤ 0.001 {In the formula, Df2 represents the dielectric loss tangent of the cured resin composition containing component (A), and Df1 represents the dielectric loss tangent of the cured resin composition excluding component (A).} It is preferable that the condition (i) and (ii) are met, and it is more preferable that the condition (ii) and (ii) are met.

[0076] Regarding characteristic (i), if the peel strength of the cured resin composition on the support is 0.4 N or higher, it tends to be easier to ensure the adhesive strength or bonding strength of the adherend to the metal surface in the manufacturing process of the laminate using the resin composition. From the viewpoint of further improving the adhesive strength or bonding strength, the peel strength of the cured resin composition on the support is more preferably 0.5 N or higher.

[0077] Regarding characteristic (ii), the value obtained by subtracting Df1 from Df2 is an indicator of the effect of adding heterocyclic compounds to the resin composition. If Df2-Df1 ≤ 0.001, as explained above, the deterioration of dielectric properties tends to be suppressed even if heterocyclic compounds represented by general formula (1) are included in the resin composition. From this viewpoint, Df2-Df1 < 0.0005 is even more preferable.

[0078] The resin film is obtained by applying the varnish described above either alone or on a support such as a support film, and then drying and removing the organic solvent in the resin varnish to form a film. The resin film can be suitably used as an interlayer insulating sheet, adhesive film, etc., for laminates such as multilayer printed circuit boards.

[0079] The prepreg comprises a substrate and the resin composition of this embodiment impregnated or coated onto the substrate. The prepreg can be obtained, for example, by impregnating a substrate such as glass cloth with the varnish and then drying off the solvent using a hot air dryer or the like.

[0080] Examples of prepreg substrates include various glass cloths such as roving cloth, cloth, chopped mat, and surfacing mat; asbestos cloth, metal fiber cloth, and other synthetic or natural inorganic fiber cloths; woven or nonwoven fabrics obtained from liquid crystal fibers such as fully aromatic polyamide fibers, fully aromatic polyester fibers, and polybenzoxazole fibers; natural fiber cloths such as cotton cloth, linen cloth, and felt; natural cellulose-based substrates such as carbon fiber cloth, kraft paper, cotton paper, and cloths obtained from paper-glass blended yarns; and polytetrafluoroethylene porous films. These substrates can be used individually or in combination of two or more.

[0081] The proportion of solid content in the resin composition within the prepreg is preferably 30 to 80% by mass, and more preferably 40 to 70% by mass. When the proportion of solid content in the resin composition is 30% by mass or more, the prepreg tends to exhibit superior insulation reliability when used for electronic circuit boards, etc. When the proportion of solid content in the resin composition is 80% by mass or less, the mechanical properties such as flexural modulus tend to exhibit superior performance in applications such as electronic circuit boards.

[0082] The metal-clad laminate according to this embodiment is obtained by laminating and curing the resin composition or prepreg of this embodiment with a metal foil. The metal-clad laminate preferably has a form in which the cured prepreg (also called a "cured composite") and the metal foil are laminated and in close contact, and is suitably used as a material for electronic circuit boards. Examples of metal foils include aluminum foil and copper foil, and among these, copper foil is preferred because of its low electrical resistance. The cured composite combined with the metal foil may be one or more sheets, and depending on the application, the metal foil is layered on one or both sides of the composite to process it into a laminate.

[0083] One method for manufacturing a metal-clad laminate is to form a composite (e.g., the aforementioned prepreg) with a resin composition and a substrate, then layer this with metal foil, and finally cure the resin composition to obtain a laminate in which a cured laminate and metal foil are laminated. One particularly preferred application of this laminate is a printed circuit board. In the case of a printed circuit board, it is preferable that at least a portion of the metal foil is removed from the metal-clad laminate.

[0084] <Printed wiring board> The printed circuit board according to this embodiment comprises at least one of the laminates described above, thereby providing excellent electrical properties (e.g., low dielectric constant and low dielectric loss tangent) and insulation reliability, as well as corrosion resistance. From the viewpoint of electrical properties, the printed circuit board is preferably configured such that a portion of the metal foil is removed from the metal-clad laminate.

[0085] The printed circuit board of this embodiment can typically be formed by a method of pressurized heating molding using the prepreg of this embodiment described above; or by a method of wiring the metal foil of the laminate described above. The wiring patterning of the metal foil can be carried out by, for example, physical etching, chemical etching, plating, immersion, etc.

[0086] The printed circuit board according to this embodiment is preferable for mounting in a high-speed communication module because it has excellent electrical properties, insulation reliability, and corrosion resistance. The high-speed communication module is a terminal that, when incorporated into a product, can communicate information about that product, such as location information and operating status, at high speed. Specifically, the high-speed communication module can be incorporated into a high-frequency transmission or fifth-generation (5G) communication system and used for information communication, remote control of industrial equipment and machinery, the Internet of Things (IoT), etc. [Examples]

[0087] <Example 1>

[0088] (Synthesis reaction) The synthesis reaction was carried out according to Scheme 1 below. [ka]

[0089] 52 g of acetone (non-volatile component concentration = 38.5%) was added to a three-necked flask as a solvent, 13.0 g of 3-mercapto-1,2,4-triazole (3MTA) and 18.27 g of glycidyl methacrylate (GMA) were added as reactants, and 1.30 g of triethylamine (TEA) was added as a catalyst. The reaction was carried out for 24 hours under fume hood drying. After that, the solvent was removed by distillation using an evaporator to obtain the product in the flask. Identification of the product was performed. 1 The heterocyclic compound I was obtained by 1H-NMR (JEOL "ECS-400", heavy DMSO). 1 The 1H-NMR chart is shown in Figure 1.

[0090] In Figure 1, the ratio of peaks derived from methacrylate, observed around 5.7 ppm and 6.1 ppm, to the peak derived from the triazole ring around 8.4 ppm is approximately 1:1. Therefore, it was determined that heterocyclic compound I was obtained. The reason the above ratio is not exactly 1:1 is presumed to be because a mixture of isomers A and B was obtained, rather than a single compound.

[0091] (Effect of reaction conditions on heterocyclic compound I) Reactions (a) and (b) were carried out in the same manner as in Scheme 1 above, except that the reaction conditions were changed as shown in Table 1.

[0092] [Table 1]

[0093] Reaction (A) continued for 117 hours, but a sample was taken from the reaction system at 42 hours. Reaction (B) also continued for 42 hours, but a sample was taken from the reaction system at 19 hours. The starting material (3MTA) alone, the sampled product and final product of reaction (A), and the sampled product and final product of reaction (B) were analyzed by gel permeation chromatography (GPC, developing solvent THF), and the resulting GPC charts are shown in Figure 2. 1 Identification was performed by 1H-NMR (JEOL "ECS-400", heavy DMSO).

[0094] Reactions (A) and (B) 1 From the comparison of H-NMR charts (not shown), based on the presence or absence of a peak around 14 ppm, which is presumed to originate from -SH, it was found that in the presence of solvent ethanol and without a catalyst, isomers A and B are obtained in approximately a 1:1 (molar ratio), whereas when a catalyst is used, isomer B is obtained almost entirely.

[0095] Figure 2 suggests the following possibilities (i) and (ii): (i) At 19 hours in reaction (a) and at 42 hours in reaction (b), the raw material peaks disappeared, suggesting that the reactions may have finished earlier than the sampling time in both cases. (ii) In reaction (a), the peaks originating from high molecular weight components were significantly fewer, and there was almost no increase over time. On the other hand, in reaction (b), two peaks originating from high molecular weight components were observed, and they increased over time. Therefore, when the catalyst is used in the presence of solvent ethanol, the number of reaction sites may increase.

[0096] <Example 2>

[0097] (Synthesis reaction) The synthesis reaction was carried out according to Scheme 2 below. [ka]

[0098] 60 g of ethanol (non-volatile component concentration = 36.5%) was added as a solvent to a three-necked flask. At room temperature, 15.0 g of 3-amino-5-mercapto-1,2,4-triazole (3A5MTA) and 18.27 g of glycidyl methacrylate (GMA) were added as reaction components, and 1.30 g of triethylamine (TEA) was added as a catalyst. The reaction was carried out for 24 hours under fume hood drying. After that, the solvent was removed by distillation using an evaporator to obtain the product in the flask. Identification of the product was performed. 1 The heterocyclic compound II was obtained by 1H-NMR (JEOL "ECS-400", heavy DMSO). 1 The H-NMR chart is shown in Figure 3.

[0099] In Figure 3, the ratio of peaks derived from methacrylate, observed around 5.7 ppm and 6.1 ppm, to the peak derived from the heterocyclic compound around 12 ppm is approximately 1:1. Therefore, it was determined that heterocyclic compound II was obtained. The reason the above ratio is not exactly 1:1 is presumed to be because a mixture of isomers C and D was obtained, rather than a single compound.

[0100] (Effect of reaction conditions on heterocyclic compound II) Synthesis reactions (c) to (e) were carried out in the same manner as in Scheme 2 above, except that a 20 mL bottle was used as the reaction vessel, and the reaction conditions shown in Table 2 were met at room temperature, and stirring was performed using a stirring bar.

[0101] [Table 2]

[0102] In reaction (c), since the dried product was insoluble in DMSO, as a post-treatment (c), the undried product was sampled after being left in a fume hood overnight. 1 The sample was subjected to 1H-NMR (using JEOL's "ECS-400" and heavy DMSO).

[0103] In reaction (E), since the dried product was insoluble in DMSO, as a post-treatment E, the undried product was sampled after being left in a fume hood overnight. 1 The sample was subjected to 1H-NMR (using JEOL's "ECS-400" and heavy DMSO).

[0104] In reaction (O), after 24 hours of reaction time, stirring was stopped and the 20 mL bottle was allowed to stand. A precipitate was observed, so as a post-treatment (O), the supernatant was collected. 1 The sample was subjected to 1H-NMR (JEOL "ECS-400", heavy DMSO) measurement, and then stirring was resumed to collect the entire mixture. 1 The samples were subjected to 1H-NMR measurements.

[0105] The undried product of reaction (E) left overnight in the fume hood, the supernatant of reaction (O), and the stirred sample of the product of reaction (O) are as follows: 1 The 1H-NMR peaks (not shown) were nearly identical, confirming the reproducibility of the reaction.

[0106] Furthermore, reactions (E) and (O) 1 The H-NMR chart (not shown) shows the reaction (c). 1 When compared with the 1H-NMR chart (not shown), the peaks around 6 ppm for reactions (E) and (O) are broader, and a broad peak is observed around 5.5 ppm, suggesting the presence of multiple products, such as isomer C and isomer D.

[0107] <Example 3>

[0108] (Synthesis reaction) The synthesis reaction was carried out according to Scheme 3 below. [ka]

[0109] 60 g of ethanol (non-volatile component concentration = 33.7%) was added to a three-necked flask as a solvent. At room temperature, 11.0 g of 5-aminotetrazole (5ATz) and 18.27 g of glycidyl methacrylate (GMA) were added as reactants, and 1.3 g of triethylamine (TEA) was added as a catalyst. The reaction was carried out under vacuum drying with stirring for 24 hours. After that, the solvent was removed by distillation using an evaporator to obtain the product. Identification of the product was performed. 1 The heterocyclic compound III was obtained by 1H-NMR (JEOL "ECS-400", heavy DMSO). 1 The H-NMR chart is shown in Figure 4.

[0110] In Figure 4, the ratio of peaks derived from methacrylate, observed around 5.7 ppm and 6.1 ppm, to the peak derived from the heterocyclic compound around 6.6 ppm is approximately 1:1, leading to the conclusion that heterocyclic compound III was obtained. The reason the above ratio is not exactly 1:1 is presumed to be because a mixture of isomers E and F was obtained, rather than a single compound.

[0111] (Effect of reaction conditions on heterocyclic compound III) The synthesis reactions (k) and (ki) were carried out in the same manner as in Scheme 3 above, except that a screw-cap tube was used as the reaction vessel, and the mixture was stirred with a stirring bar for 24 hours at room temperature under the reaction conditions shown in Table 3.

[0112] [Table 3]

[0113] The DMSO solutions obtained are shown in Table 3. 1 In addition to being subjected to H-NMR analysis, the EtOH solution is also collected during product processing as needed. 1 The sample will be subjected to 1H-NMR analysis. Furthermore, for the identification of isomer E, it will be dissolved in a mixed solution of DMSO and PGME and analyzed as needed.

[0114] <Varnish preparation> As shown in Table 4, glass cloth, copper foil, and compounding components were prepared. According to the composition shown in Table 5, heterocyclic compounds having ethylenically unsaturated groups, PPE components, elastomers, and other additives were mixed with toluene as a solvent and stirred until dissolved. Then, a crosslinking agent and an initiator were added to the solution, and the mixture was stirred thoroughly to obtain a varnish.

[0115] <Preparation of resin-coated copper foil> The resulting varnish was applied to the copper foil so that the film thickness after drying would be 25 μm, and the resin-coated copper foil was prepared by drying it in a forced-air oven at 90°C for 10 minutes. Furthermore, the two resulting resin-coated copper foils were bonded together so that the resin sides were in contact, and then heated from room temperature at a heating rate of 2°C / min, at 200°C for 60 minutes under a pressure of 10 kg / cm². 2 Double-sided copper-clad plates were fabricated by vacuum pressing and lamination.

[0116] <Prepreg fabrication> Furthermore, after impregnating the glass cloth substrate with the obtained varnish, the excess varnish was scraped off by passing it through a predetermined slit, and the material was dried in a 120°C drying oven for a predetermined time to remove toluene, thereby obtaining a prepreg. This prepreg was then cut to a predetermined size.

[0117] <Fabrication of copper-clad laminates> A copper-clad laminate was obtained by stacking a predetermined number of prepregs and then applying metal foil to both sides of the stacked prepregs, followed by vacuum pressing. In this vacuum pressing process, the temperature conditions were as follows: heating from room temperature at a rate of 2°C / min, holding at 200°C for 60 minutes, and applying a pressure of 40 kg / cm². 2 It was pressurized.

[0118] <Metal layer adhesive strength> The stress was measured when peeling copper foil from double-sided copper-clad sheets and copper-clad laminates formed by the vacuum press described above at a constant speed. Specifically, the double-sided copper-clad sheets or copper-clad laminates were cut to a size of 10 mm wide x 100 mm long. Using an Autograph (AG-5000D, manufactured by Shimadzu Corporation), the average load was measured when the copper foil was peeled from the copper-clad laminate at a 90° angle at a speed of 50 mm / min, and the average of three measurements was calculated. The calculated average value was considered as the peel strength or metal layer adhesion strength between the prepreg and the copper foil. The metal layer adhesion strength was ranked according to the following criteria. ◎ (Excellent) 0.45 ≤ Metal layer adhesion strength (N) 〇(Good) 0.4≦Metal layer adhesive strength (N)<0.45 ×(Poor) Metal layer adhesive strength (N)<0.4

[0119] <Rust prevention / Migration resistance> An inner layer circuit substrate was fabricated on the copper-clad laminate obtained above, having an alternating positive and negative electrode wiring pattern with a wiring width of 100 μm and a spacing of 100 μm between wirings. On this inner layer circuit substrate, the resin-coated copper foil or prepreg and copper foil were layered, and the temperature was increased from room temperature at 2°C / min, then heated to 200°C for 60 minutes under a pressure of 40 kg / cm². 2 Samples for migration evaluation were prepared by laminating under vacuum pressing conditions, then forming electrode sections by routing from the inner layer circuit. For migration resistance measurement, a DC voltage of 50V was applied under conditions of 85°C and 85% relative humidity, and the change in insulation resistance and the presence or absence of copper dendrite growth were observed, and the samples were ranked according to the following criteria. ○ (Good): The insulation resistance value after 500 hours exceeds 1 × 10⁸ Ω, and no dendrite growth is observed. △ (Acceptable): Insulation resistance value exceeds 1 × 10⁸ Ω after 500 hours, or no dendrite growth is observed. × (Defective): The insulation resistance value after 500 hours falls below 1 × 10⁸ Ω, and dendrite growth is observed.

[0120] <Dielectric constant and dielectric loss tangent> The dielectric constant and dielectric loss tangent of laminates and glass samples at 10 GHz were measured using the cavity resonance method. A network analyzer (N5230A, Agilent Technologies) and a cavity resonator (Cavity Resornator CP series, Kanto Electronics Applied Development Co., Ltd.) were used as the measurement equipment. Laminates or glass samples with a thickness of approximately 0.5 mm were cut to a size of approximately 2 mm in width and 50 mm in length, with the warp threads of the glass cloth being the longer side for the laminates. Next, the samples were placed in an oven at 105°C ± 2°C and dried for 2 hours, and then left to stand for 96 ± 5 hours in an environment of 23°C and 50 ± 5% relative humidity. After that, the dielectric constant and dielectric loss tangent of the samples were measured using the above measurement equipment in an environment of 23°C and 50 ± 5% relative humidity.

[0121] Furthermore, for each of the copper foil grades a to c, the difference between the dielectric loss tangent Df1 of the comparative example using a varnish that does not contain heterocyclic compounds having ethylenically unsaturated groups and the dielectric loss tangent Df2 of the example using a varnish that contains heterocyclic compounds having ethylenically unsaturated groups was calculated, and the grades were ranked according to the following criteria. 〇(Good) Df2 - Df1 ≦ 0.0005 △ (Acceptable) 0.0005 < Df2 - Df1 ≤ 0.001 × (Poor) Df2 - Df1 > 0.001

[0122] <Evaluation Results> Table 5 shows the results of the evaluation of the copper-clad laminates obtained in the examples and comparative examples, as described above.

[0123] [Table 4]

[0124] [ka]

[0125] [Table 5]

[0126] The abbreviations used in this specification are as follows: <Explanation of Abbreviations> 3MTA:3-mercapto-1,2,4-triazole 3A5MTA:3-amino-5-mercapto-1,2,4-triazole 5ATz: 5-aminotetrazole GA: Glycidyl acrylate GMA: Glycidyl methacrylate GEA: Glycidylate ethanol TEA: Triethylamine DMSO: Dimethyl sulfoxide Heavy DMSO:dimethyl sulfoxide-D6 EtOH: Ethanol PGME: Propylene glycol monomethyl ether TAIC: Triallyl isocyanurate

Claims

1. The following general formula (1): 【Chemistry 1】 {In the formula, R 2 is a monovalent hydrocarbon group or a hydrogen atom, and R 3 is a hydrogen atom, a methyl group, or an ethyl group, and X is the following general formula (2): 【Chemistry 2】 (In the formula, R 1 The structure is a triazole or tetrazole structure represented by a monovalent hydrocarbon group or a hydrogen atom, and Y is a sulfur atom or an NH group. A heterocyclic compound represented by [formula].

2. (A) The heterocyclic compound according to claim 1; (B) Resins having ethylenically unsaturated groups; (C) polymerization initiator; and (D) Solvent; A resin composition characterized by containing the following:

3. The resin composition according to claim 2, wherein the (B) resin having an ethylenically unsaturated group is at least one resin selected from the group consisting of polyphenylene ether, polystyrene, resin having an alicyclic structure, polybenzoxazole precursor resin, polyimide precursor resin, and phenol resin.

4. The resin composition according to claim 2 or 3, wherein the (C) polymerization initiator is at least one selected from the group consisting of oxime esters and peroxides.

5. A laminate comprising the resin composition according to any one of claims 2 to 4 and a support or substrate.

6. The following characteristics: (i) Peel strength ≥ 0.4 N; (ii) Df2 - Df1 ≦ 0.001; The laminate according to claim 5, satisfying the following formula: {wherein Df2 represents the dielectric loss tangent of the cured resin composition containing component (A), and Df1 represents the dielectric loss tangent of the cured resin composition obtained by removing component (A) from the resin composition.

7. A printed circuit board comprising the laminate according to claim 5 or 6.

8. A high-speed communication module comprising a printed circuit board as described in claim 7.

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