Resin compositions, cured products, and articles

Abstract

To provide: a resin composition which can form a cured product that expresses excellent adhesion and low dielectric properties; and a cured product and an article that are obtained by using the resin composition.SOLUTION: The resin composition contains: an indane ring-containing compound (A) having a structural unit represented by the general formula (1a) in the figure such that at least one of terminal moieties bonded to the structural unit is an alkenyl group; a compound (B) having a polymerizable unsaturated group; and a photoinitiator.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to resin compositions, cured products obtained from said resin compositions, and articles. [Background technology]

[0002] In recent years, curable compositions, such as active energy ray curable compositions that can be cured by active energy rays like ultraviolet light, and thermosetting compositions that can be cured by heat, have been widely used in fields such as inks, paints, coatings, adhesives, and optical components.

[0003] In particular, since the above-mentioned coating agents require various properties depending on the application, including curability, heat resistance, and low dielectric properties, it is essential to manufacture them using appropriate materials that match these properties. In this regard, Patent Document 1 describes a material that tends to exhibit excellent low dielectric properties in the cured product. Patent Document 1 discloses a hydrocarbon resin made of a polyindane derivative having a predetermined indane skeleton, which has a low dielectric constant even without the introduction of pores and is suitable as an interlayer insulating film material. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2007-311732 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, in low-dielectric materials made from polyindane derivatives obtained by the technology of Patent Document 1, the amount of vinyl groups remaining in the molecule is limited. Therefore, when used in the above-mentioned coating agent, the adhesion of the cured product to the substrate is not at a practical level. Consequently, the various physical properties of the cured product do not meet current market demands, and there remains room for further consideration regarding the application of the technology of Patent Document 1 to the above-mentioned coating agent. Therefore, the object of this disclosure is to provide a resin composition capable of obtaining a cured coating film having excellent adhesion and low dielectric properties. Furthermore, the object of this disclosure is to provide a cured product obtained using the resin composition, and an article using such cured product. [Means for solving the problem]

[0006] In order to solve the above problems, the inventors conducted extensive research and found that a resin composition containing a specific indan ring-containing compound (A), a compound having a polymerizable unsaturated group (B), and a photopolymerization initiator exhibits excellent adhesion and low dielectric properties, thus completing the present invention as described below. The resin composition of this disclosure contains an indan ring-containing compound (A) having a structural unit represented by the following general formula (1a), wherein at least one of the terminal sites bonded to the structural unit is an alkenyl group; a compound (B) having a polymerizable unsaturated group; and a photopolymerization initiator. [ka] (In the above general formula (1a), R 11 , R 12 and R 13 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n 12 (This represents the number of repeating units.) [Effects of the Invention]

[0007] This disclosure provides a resin composition capable of obtaining a cured coating film having excellent adhesion and low dielectric properties. Furthermore, this disclosure provides a cured product obtained using the resin composition, and an article using such a cured product. [Brief explanation of the drawing]

[0008] [Figure 1] Figure 1 shows the GPC chart of the indane ring-containing compound (A-1) obtained in Synthesis Example 1. [Figure 2] Figure 2 shows the GPC chart of the indane ring-containing compound (A-2) obtained in synthesis example 2. [Figure 3] Figure 3 shows the GPC chart of the indane ring-containing compound (A-3) obtained in synthesis example 3. [Figure 4] Figure 4 shows the GPC chart of the indane ring-containing compound (A-4) obtained in synthesis example 4. [Figure 5] Figure 5 shows the GPC chart of the indane ring-containing compound (A-5) obtained in synthesis example 5. [Figure 6] Figure 6 shows the FD-MS chart of the indane ring-containing compound (A-1) obtained in Synthesis Example 1. [Figure 7] Figure 7 shows the 13C-NMR chart of the indan ring-containing compound (A-1) obtained in Synthesis Example 1. [Modes for carrying out the invention]

[0009] The embodiments of this disclosure (hereinafter referred to as "these embodiments") will be described in detail below, but this disclosure is not limited to the following description and can be implemented in various modifications within the scope of its gist.

[0010] Unless otherwise specified in this specification, the following terms may be applied: [term] In this specification, "reaction raw material" refers to a compound used to obtain a target compound by a chemical reaction such as combination or decomposition, and which partially constitutes the chemical structure of the target compound. Substances that act as aids to chemical reactions, such as solvents and catalysts, are excluded. In particular, in this specification, "reaction raw material" refers to a precursor for obtaining an indan ring-containing compound (A) (including a mixture containing one or more indan ring-containing compounds (A)) by a chemical reaction.

[0011] In this specification, the "aromatic group" preferably has an aromatic ring having 3 to 30 carbon atoms, and more preferably has an aromatic ring having 4 to 26 carbon atoms. Furthermore, in this specification, the hydrogen atoms of the aromatic ring in the "aromatic group" may be substituted with substituents, such as alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogen atoms. In addition, the "aromatic group" may include heteroaromatic compounds, and the -CH2- or -CH= atoms in the "aromatic group" may be substituted with -O-, -S-, or -N= such that they are not adjacent to each other. Examples of the aromatic rings include monocyclic aromatic rings, fused aromatic rings, and ring-aggregated aromatic rings. Examples of monocyclic aromatic rings include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine. Examples of fused aromatic rings include naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine. Examples of ring-aggregated aromatic rings include biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl. Furthermore, the hydrogen atoms of the aromatic rings in the aromatic group may be substituted with, for example, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom. A monovalent aromatic group is an aromatic group from which one hydrogen atom has been removed, a divalent aromatic group is an aromatic group from which two hydrogen atoms have been removed, and a trivalent to hexavalent aromatic group is an aromatic group from which three to six hydrogen atoms have been removed. In this specification, "aryl group" refers to, for example, a phenyl group, naphthyl group, phenalenyl group, phenantrenyl group, anthryl group, azlenyl group, indenyl group, indanyl group, tetralinyl group, etc. Furthermore, the hydrogen atoms of the aromatic ring in the "aryl group" may be substituted with, for example, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or a halogen atom. The "arylene group" refers to a divalent group obtained by removing one arbitrary hydrogen atom from the "aryl group" mentioned above. Examples of "aralkyl groups" as used herein include benzyl groups, diphenylmethyl groups, biphenyl groups, naphthylmethyl groups, and the like. The hydrogen atoms of the aromatic ring in the aralkyl group may be substituted with, for example, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom. An "aralkylene group" is a divalent group obtained by removing one arbitrary hydrogen atom from the "aralkyl group" as described above. In this specification, "alkyl group" may be linear, branched, or cyclic, and examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, (n-)heptyl group, (n-)octyl group, (n-)nonyl group, (n-)decyl group, (n-)undecyl group, (n-)dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, or cyclononyl group. In this specification, "cycloalkyl group" refers to a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, or adamantyl group, etc.

[0012] In this specification, "alkenyl group" refers to groups such as 1-propynyl group, 2-propynyl group, 2-butynyl group, pentynyl group, hexynyl group, vinyl group, allyl group, isopropenyl group, acrylic group, or methacrylic group. Furthermore, "alkenylene group" refers to a divalent group obtained by removing one arbitrary hydrogen atom from the aforementioned "alkenyl group". In this specification, "alkoxy group" refers to, for example, a methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyloxy group, or nonyloxy group. In this specification, "aryl group" refers to a phenyl group, a 1-naphthyl group, or a 2-naphthyl group, among others. In this specification, "aryloxy group" refers to a phenoxy group, naphthyloxy group, anthuryloxy group, phenanthryloxy group, or pyrenyloxy group, among others. In this specification, "halogen atom" refers to, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. In this specification, the "alkylene group" may be linear, branched, or cyclic, and may be a group obtained by removing one hydrogen atom at any position from the example groups of "alkyl groups" described above. Examples include the methylene group, ethylene group, propylene group, 1-methylmethylene group, 1,1-dimethylmethylene group, 1-methylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, isopropylene group, isopropylidene group, propylenene group, butylene group, 1-methylpropylene group, 2-methylpropylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, and the like.

[0013] In this specification, "fluoroalkyl group" refers to an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. A "fluoroalkyl group" can be a linear or branched fluoroalkyl group. The number of fluorine atoms in a "fluoroalkyl group" can be one or more, preferably 1 to 11. Furthermore, "fluoroalkyl group" includes perfluoroalkyl groups in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms. In this specification, "perfluoroalkyl group" refers to, for example, a trifluoromethyl group (-CF3), a pentafluoroethyl group (-C2F5), a heptafluoropropyl group (-CF2CF2CF3), and a heptafluoroisopropyl group (-CF(CF3)2). In this specification, "fluoroalkyl group" refers to, for example, monofluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, perfluoroethyl group, tetrafluoropropyl group, hexafluoropropyl group, perfluorobutyl group, octafluoropentyl group, perfluoropentyl group, and perfluorohexyl group. In this specification, "monovalent organic group" refers to an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. In the case of an aryl group having 6 to 20 carbon atoms, one or more hydrogen atoms in the aryl group may be substituted with halogen atoms, amino groups, alkyl groups, alkenyl groups, or alkoxy groups. Furthermore, in this specification, "amino group" includes not only -NH2 but also substituted amino groups, for example, -NR a R b (R a and R b Each of these independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In this specification, "structural unit" refers to a (repeating) unit of chemical structure formed during a reaction or polymerization. In other words, in a compound formed by a reaction or polymerization, it refers to a substructure other than the chemical bond structure involved in the reaction or polymerization, and is commonly known as a residue.

[0014] [Resin composition] This disclosure relates to a resin composition containing an indan ring-containing compound (A) (hereinafter also referred to as component (A)), a compound (B) having a polymerizable unsaturated group (hereinafter also referred to as component (B)), and a photopolymerization initiator. The indan ring-containing compound (A) comprises a structural unit represented by the above general formula (1a), and at least one of the terminal sites bonded to the structural unit is an alkenyl group. Due to the very high proportion of carbon and hydrogen atoms in the constituent atoms of the indan ring-containing compound (A) of this embodiment, the entire indan ring-containing compound (A) exhibits low polarity, resulting in an extremely low dielectric loss tangent, and excellent chemical thermal stability due to the fused ring structure of the indan ring. Furthermore, because the indan ring-containing compound (A) has alkenyl groups at the ends of its molecular chains, when combined with compound (B) having polymerizable unsaturated groups, the resulting cured product exhibits excellent adhesion and low dielectric properties.

[0015] In the resin composition of this disclosure, the content of the indan ring-containing compound (A) is preferably in the range of 1 to 50% by mass relative to the total amount (100% by mass) of the resin composition, from the viewpoint of improving excellent adhesion and low dielectric properties in a balanced manner. The upper or lower limit of the content of the indan ring-containing compound (A) is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and also preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. Furthermore, in the resin composition of this disclosure, the content of compound (B) having a polymerizable unsaturated group is preferably in the range of 10 to 95% by mass with respect to the total amount (100% by mass) of the resin composition. The upper or lower limit of the content of compound (B) having a polymerizable unsaturated group is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less. Furthermore, in the resin composition of this disclosure, the content of the photopolymerization initiator is preferably in the range of 0.1 to 14% by mass with respect to the total amount (100% by mass) of the resin composition. The upper or lower limit of the photopolymerization initiator content is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, even more preferably 0.8% by mass or more, and preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 6% by mass or less.

[0016] In this embodiment, the mass ratio of solids [(A) / (B)] between the indan ring-containing compound (A) and the compound having a polymerizable unsaturated group (B) is preferably in the range of 5 / 95 to 50 / 50 from the viewpoint of improving excellent adhesion and low dielectric properties in a balanced manner. From the same viewpoint, the upper or lower limit of the above mass ratio [(A) / (B)] is more preferably 10 / 90 or more, even more preferably 20 / 80 or more, and even more preferably 40 / 60 or less.

[0017] The resin composition in this embodiment may further contain optional additives in addition to the essential components: an indan ring-containing compound (A), a compound having an acid group and a polymerizable unsaturated group (B), and a photopolymerization initiator. Furthermore, the resin composition in this embodiment may substantially consist only of component (A), component (B), a photopolymerization initiator, and optionally added additives. Moreover, it may consist only of component (A), component (B), and a photopolymerization initiator. The total content of component (A), component (B), and photopolymerization initiator in the total amount (100% by mass) of the resin composition of this embodiment is preferably 40% by mass or more, more preferably 50% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less, from the viewpoint of improving excellent adhesion and low dielectric properties in a balanced manner. The phrase "only consisting of the above component (A), component (B), photoinitiator, and additive component" means that, relative to the total amount (100% by mass) of the resin composition, preferably 40 to 98% by mass, or at least 50 to 95% by mass, is the component (A), component (B), and photoinitiator, or the component (A), component (B), photoinitiator, and additive component. Further, in the preferred resin composition of the present embodiment, the total amount of the above component (A), component (B), photoinitiator, inorganic filler, and additive component can preferably be 80 to 100% by mass, more preferably 90 to 99% by mass, relative to the total amount (100% by mass) of the resin composition. Note that the resin composition of the present embodiment may contain inevitable impurities in addition to the component (A), component (B), photoinitiator, and additive component as long as the effects of the present disclosure are not impaired. Hereinafter, the indane ring-containing compound (A), compound (B) having a polymerizable unsaturated group, photoinitiator, and additive component, which are each component contained in the resin composition in the present embodiment, will be described.

[0018] (Indane Ring-Containing Compound (A)) The indane ring-containing compound (A) according to the present disclosure has a structural unit represented by the following general formula (1a) and has an alkenyl group at at least one of the terminal sites of the molecular chain of the indane ring-containing compound (A). [Chemical formula] (In the above general formula (la), R 11 , R 12 and R 13 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n 12 represents the average number of repeating units.) Due to the fact that the proportion of carbon atoms and hydrogen atoms among the constituent atoms of the indane ring-containing compound (A) of the present embodiment is very high, the entire indane ring-containing compound (A) exhibits low polarity, so the dielectric loss tangent is extremely low, and due to the condensed ring structure of the indane ring, it has excellent chemical thermal stability. Accordingly, it is considered that excellent heat resistance and low dielectric loss tangent can be achieved simultaneously at a high level.

[0019] In this embodiment, the indan ring-containing compound (A) has a structural unit represented by general formula (1a) and at least one of the terminal sites of the molecular chain of the indan ring-containing compound (A) has an alkenyl group, and may be a single compound or a mixture.

[0020] In the above general formula (1a), R 11 , R 12 and R 13 Each of these is preferably an alkyl group having 1 to 4 carbon atoms, specifically a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group. Among these, R 11 , R 12 and R 13 Preferably, they are the same alkyl group. In the above general formula (1a), n 12 represents the average number of repeating units, and specifically, it is preferably in the range of 0.5 to 20, more preferably in the range of 0.8 to 15, and even more preferably in the range of 1 to 10. Average number of repeating units n 12 However, a range of 0.5 to 20 is preferable because it allows for the formation of a relatively high molecular weight indan ring-containing compound (A). Also, the average number of repeating units n 12 When the range is as described above, the distance between crosslinking points becomes relatively short, which is preferable from the viewpoint of improving heat resistance due to increased crosslinking density. In addition, since the proportion of carbon and hydrogen atoms in the constituent atoms of the indan ring-containing compound (A) of this embodiment is high, the entire indan ring-containing compound (A) tends to exhibit low polarity, and the dielectric loss tangent can be further reduced.

[0021] The indan ring-containing compound (A) in this embodiment has an alkenyl group at at least one terminal site of its molecular chain. As a result, the indan ring-containing compound (A) exhibits thermosetting and photocuring properties (hereinafter also referred to as UV curing), and can be applied to various reactions or uses. In particular, from the viewpoint of good developability, it is preferable that the indan ring-containing compound (A) as a whole resin composition exhibits excellent photocuring properties (UV curing properties). In this embodiment, the alkenyl group bonded to the terminal portion of the molecular chain of the indan ring-containing compound (A) is preferably a linear or branched alkenyl group having 2 to 10 carbon atoms, more preferably a linear or branched alkenyl group having 2 to 6 carbon atoms, and even more preferably a linear or branched alkenyl group having 2 to 4 carbon atoms. In this embodiment, the alkenyl group can be any of the various alkenyl groups described in the "Definition" section above, but it is preferably an alkenyl group having at least one quaternary carbon, more preferably an alkenyl group having at least one quaternary carbon and in which one of the bonds of the quaternary atom is chemically bonded directly or indirectly to a structural unit represented by general formula (1a), and even more preferably an alkenyl group represented by the following general formula (x). [ka] (In the above general formula (x), R x1 R represents an alkyl group with 1 to 6 carbon atoms. x2 * represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and * represents a bond that is chemically bonded to another atom.

[0022] In this embodiment, the indan ring-containing compound (A) has an alkenyl group at at least one terminal site of its molecular chain, and there are no particular restrictions on the other terminal sites of the molecular chain, including hydrogen atoms, halogen atoms, amino groups, or monovalent organic groups. From the viewpoint of exhibiting excellent UV curability, it is preferable that many alkenyl groups are introduced into the terminal sites of the molecular chain of the indan ring-containing compound (A) in this embodiment, and ideally, it is preferable that all terminal sites of the molecular chain of the indan ring-containing compound (A) are alkenyl groups. For example, if the structural unit represented by general formula (1a) has (n 12 =10), preferably having one or more alkenyl groups.

[0023] In the embodiment, the indan ring-containing compound (A) has a linear molecular chain or a branched molecular chain, and it is preferable that the molecular chain is composed of a structural unit represented by the above general formula (1a) as the main chain. More specifically, when the indan ring-containing compound (A) in this embodiment is a linear molecular chain, a preferred embodiment of the indan ring-containing compound (A) has a chemical structure in which structural units represented by the general formula (1a) are linearly linked, and an alkenyl group is bonded to at least one end of the linearly linked structural units represented by the general formula (1a). Furthermore, the group at the other end of the linearly linked structural units represented by the general formula (1a) is not particularly limited and may be a hydrogen atom, a halogen atom, an amino group, or a monovalent organic group, and it is preferable that the group at the other end of the linearly linked structural units represented by the general formula (1a) is an alkenyl group. On the other hand, if the indan ring-containing compound (A) in this embodiment has a branched molecular chain, a preferred embodiment of the indan ring-containing compound (A) is a structure in which three or more fused ring-containing molecular chains are linearly linked structural units represented by the general formula (1a), and one end of each of the three or more fused ring-containing molecular chains is chemically bonded to a trivalent or higher organic group or to a carbon atom of the benzene ring in the general formula (1a), and the other end of each of the three or more fused ring-containing molecular chains is chemically bonded to a hydrogen atom, a halogen atom, an amino group, an alkenyl group or a monovalent organic group, and furthermore, at least one of the other ends of the three or more is chemically bonded to an alkenyl group. In this specification, "trivalent organic group" refers to a group obtained by removing two hydrogen atoms at arbitrary positions from the "monovalent organic group" described above. In this embodiment, the indane ring-containing compound (A) is more preferably composed of linear molecular chains. Having a linear indane skeleton is preferable because it provides better flexibility and is expected to improve brittleness.

[0024] The number-average molecular weight (Mn) of the indan ring-containing compound (A) of this disclosure is preferably in the range of 320 to 3,000, and more preferably in the range of 350 to 2,000. Furthermore, the weight-average molecular weight (Mw) of the indan ring-containing compound (A) is preferably in the range of 350 to 7,000, and more preferably in the range of 400 to 4,000. The indan ring-containing compound (A) of this disclosure preferably has a molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) in the range of 1.1 to 15, more preferably 1.1 to 10, and even more preferably 1.1 to 8, as calculated from gel permeation chromatography (GPC) measurements, in order to have excellent heat resistance and dielectric properties. When the molecular weight distribution is wide and there are many high molecular weight components as shown in the GPC chart obtained from the GPC measurement, the proportion of high molecular weight components that contribute to flexibility increases. Therefore, compared to cured products using conventional indan ring-containing compounds (A), brittleness is suppressed, and a cured product with excellent flexibility and pliability can be obtained, which is a preferred embodiment. The number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of the indan ring-containing compound (A) in this embodiment were measured using gel permeation chromatography (hereinafter abbreviated as "GPC") under the measurement conditions described in the examples below.

[0025] In this embodiment, if the indan ring-containing compound (A) is a linear molecular chain, that is, if the structural units represented by the general formula (1a) are linked linearly, and an alkenyl group is bonded to at least one end of the linearly linked structural units represented by the general formula (1a), then a preferred form of the indan ring-containing compound (A) will be described below, using this as an example.

[0026] <Preferred form of indan ring-containing compound (A)> The indan ring-containing compound (A) in this embodiment is the following general formula (1b): [ka] (In the above general formula (1b), R 11 , R 12 and R 13 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Q 11 Q 12 , L 11 and L 12 Each of these independently represents a single bond or an alkylene group having 1 to 8 carbon atoms, wherein the -CH2-CH2- in the alkylene group may be substituted with -CH=CH-. P 11 and P 12 Each of these independently represents a hydrogen atom, a polar group, an alkyl group having 1 to 6 carbon atoms which may be substituted with the polar group, an alkenyl group having 2 to 10 carbon atoms, or a group represented by the following general formula (2): M 11 and M 12 Each of these independently represents a single bond or a group represented by the following general formula (3): n 12n represents the average number of repeating units. 11 and n 13 Each of these independently represents a number from 0 to 20. However, P 11 and P 12 At least one of them is an alkenyl group having 2 to 10 carbon atoms. [ka] [In the above general formula (2), R 15 Each of these independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms, n 2 This represents an integer between 0 and 4 (inclusive). [In the above general formula (3), R 16 Each of these independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms, n 3 This represents an integer between 0 and 4 (inclusive). In general formulas (2) and (3) above, * represents a bond with another atom. It is preferable that it be represented as ). Furthermore, the indane ring-containing compound (A) in this embodiment may be a compound represented by general formula (1b), or a mixture of multiple compounds represented by general formula (1b). In this specification, the embodiment in which the indane ring-containing compound (A) is a mixture will be referred to as an indane-based mixture and described later.

[0027] In the above general formula (1b) of this embodiment, n 12 If the number is 2 or more, there are multiple R 11 , R 12 and R 13 Each of them is independent and may be the same as or different from one another. Also, n 11 If there are 2 or more, there are multiple M 11 Each of them is independent and may be the same as or different from one another. Similarly, there may be multiple L 11 Each of them is independent and may be the same as or different from one another. Furthermore, n 13 If there are 2 or more, there are multiple M 12Each of them is independent and may be the same as or different from one another. Similarly, there may be multiple L 12 Each of them is independent and may be the same as or different from one another.

[0028] In the above general formula (2), n 2 If the number is 2 or more, there are multiple R 15 Each of them is independent and may be the same as or different from one another. In the above general formula (3), n 3 If the number is 2 or more, there are multiple R 16 Each of them is independent and may be the same as or different from one another.

[0029] In the general formula (1b) above, R 11 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Also, n 12 If the number is 2 or more, there are multiple R 11 These may be the same or different from each other. Particularly preferred R in general formula (1b) 11 These are a methyl group, an ethyl group, or an n-propyl group. Note that R in general formula (1b) 11 The benzene ring in the bonded indan ring corresponds to the benzene ring of aromatic compound (i) described later.

[0030] In the general formula (1b) above, R 12 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Also, n 12 If the number is 2 or more, there are multiple R 12 These may be the same or different from each other. Particularly preferred R in general formula (1b) 12 These are a methyl group, an ethyl group, or an n-propyl group. Note that R in general formula (1b) 12 The benzene ring in the bonded indan ring corresponds to the benzene ring of aromatic compound (i) described later.

[0031] In the general formula (1b) above, R 13 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. Also, n 12 If the number is 2 or more, there are multiple R 13 These may be the same or different from each other. Particularly preferred R in general formula (1b) 13 These are a methyl group, an ethyl group, or an n-propyl group. Note that R in general formula (1b) 13 The benzene ring in the bonded indan ring corresponds to the benzene ring of aromatic compound (i) described later.

[0032] In the above general formula (1b), Q 11 It is preferable that Q represents a single bond or an alkylene group having 1 to 8 carbon atoms. However, Q 11 If is an alkylene group having 2 or more carbon atoms, the -CH2-CH2- in the alkylene group may be replaced with -CH=CH-. In the above general formula (1b), Q 11 A single bond, an alkylene group having 1 to 6 carbon atoms, or an alkenylene group having 2 to 6 carbon atoms is more preferable, and a single bond or an alkylene group having 1 to 4 carbon atoms is even more preferable. Particularly preferred Q in general formula (1b) 11 These include a single bond, a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an isopropylidene group, a propylidene group, an n-butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, an n-pentylene group, an isopentylene group, a tert-pentylene group, a neopentylene group, or a 1,2-dimethylpropylene group. In the above general formula (1b), Q 12 It is preferable that Q represents a single bond or an alkylene group having 1 to 8 carbon atoms. However, Q 12 If is an alkylene group having 2 or more carbon atoms, the -CH2-CH2- in the alkylene group may be replaced with -CH=CH-. In the above general formula (1b), Q 12is more preferably a single bond, an alkylene group having 1 to 6 carbon atoms or an alkenylene group having 2 to 6 carbon atoms, and even more preferably a single bond or an alkylene group having 1 to 4 carbon atoms. Particularly preferred Q in general formula (1b) 12 is the above particularly preferred Q 11 is the same as that. Further, Q 11 and Q 12 may be the same as or different from each other.

[0033] In the above general formula (1b), L 11 preferably represents a single bond or an alkylene group having 1 to 8 carbon atoms. However, when L 11 [ is an alkylene group having 2 or more carbon atoms, -CH2-CH2- in the alkylene group may be substituted with -CH=CH-. In the above general formula (1b), L 11 is more preferably a single bond, an alkylene group having 1 to 6 carbon atoms or an alkenylene group having 2 to 6 carbon atoms, and even more preferably a single bond or an alkylene group having 1 to 4 carbon atoms. Particularly preferred L in general formula (1b) 11 is a single bond, a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an isopropylidene group, a propylidene group, an n-butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, an n-pentylene group, an isopentylene group, a tert-pentylene group, a neopentylene group or a 1,2-dimethylpropylene group.

[0034] In the above general formula (1b), L 12 preferably represents a single bond or an alkylene group having 1 to 8 carbon atoms. However, when L 12 is an alkylene group having 2 or more carbon atoms, -CH2-CH2- in the alkylene group may be substituted with -CH=CH-. In the above general formula (1b), L 12 is more preferably a single bond, an alkylene group having 1 to 6 carbon atoms or an alkenylene group having 2 to 6 carbon atoms, and even more preferably a single bond or an alkylene group having 1 to 4 carbon atoms. Particularly preferred L in general formula (1b) 12Examples include a single bond, a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an isopropylidene group, a propylidene group, an n-butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, an n-pentylene group, an isopentylene group, a tert-pentylene group, a neopentylene group, or a 1,2-dimethylpropylene group. Also, L 11 and L 12 may be the same as or different from each other.

[0035] In the general formula (1b) above, P 11 and P 12 are each independently a hydrogen atom, a polar group, an alkyl group having 1 to 6 carbon atoms which may be substituted with the polar group, an alkenyl group having 2 to 10 carbon atoms, or a group represented by the following general formula (2).

Chemical formula

Chemical formula

[0036] In the general formula (1b) above, M 11 and M 12 Each of these is independently a single bond or a group represented by the following general formula (3). [ka] (In the above general formula (3), R 16 Each of these independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms, n 3 represents an integer between 0 and 4 (inclusive). Preferably, R 16Each of these is independently an amino group, a fluoroalkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 3 carbon atoms, n 3 (This is 0, 1, or 2.) In the above general formula (1b), M 11 The phenylene group is preferably a single bond, or may be substituted with an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms, as shown in the general formula (3) above. Examples of such phenylene groups include 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene groups. Similarly, M in the above general formula (1b) 12 The phenylene group is preferably a single bond, or may be substituted with an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms, as shown in the general formula (3) above. Examples of such phenylene groups include 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene groups. Note that the benzene ring in general formula (3) may correspond to the benzene ring in the aniline compounds described later.

[0037] In the above general formula (1b), n 12 n represents the average number of repeating units, and is preferably in the range of 0.5 to 20, more preferably in the range of 0.8 to 15, and even more preferably in the range of 1 to 10. 12 When the range is as described above, the proportion of carbon and hydrogen atoms in the constituent atoms of the indan ring-containing compound (A) of this embodiment increases, making the entire indan ring-containing compound (A) more likely to exhibit low polarity, and thus further reducing the dielectric loss tangent. In the above general formula (1b), n 11 n represents the average number of repeating units, and is preferably in the range of 0 to 20, more preferably in the range of 0 to 15, and even more preferably in the range of 0 to 10. 11 When the range is as described above, the proportion of carbon and hydrogen atoms in the constituent atoms of the indan ring-containing compound (A) of this embodiment increases, making the entire indan ring-containing compound (A) more likely to exhibit low polarity, and thus further reducing the dielectric loss tangent. In the above general formula (1b), n 13 n represents the average number of repeating units, and is preferably in the range of 0 to 20, more preferably in the range of 0 to 15, and even more preferably in the range of 0 to 10. 13 When the range is as described above, the proportion of carbon and hydrogen atoms in the constituent atoms of the indan ring-containing compound (A) of this embodiment increases, making the entire indan ring-containing compound (A) more likely to exhibit low polarity, and thus further reducing the dielectric loss tangent.

[0038] In this embodiment, the number of alkenyl groups (unsaturated bonds) per molecule of the indan ring-containing compound (A) is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. The lower limit of the number of alkenyl groups (unsaturated bonds) is preferably 1 or more, more preferably 2 or more. The upper limit of the number of alkenyl groups (unsaturated bonds) is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. By leaving an average of two or more alkenyl groups (e.g., vinyl groups or isopropenyl groups) in one molecule of the indan ring-containing compound (A) of this embodiment, the resulting indan ring-containing compound (A) becomes more UV-curable, and as a result, indan-based mixtures containing the indan ring-containing compound (A) or resin compositions containing the indan ring-containing compound (A) become more sensitive and easier to cure. Furthermore, by retaining an average of two or more alkenyl groups (e.g., vinyl groups or isopropenyl groups) in one molecule of the indan ring-containing compound (A), and by including a photopolymerization initiator, the time from UV irradiation to curing of the resin composition can be shortened. In addition, since the resin composition of this embodiment is cured by light, the retention of unexposed areas after development due to heating during drying is less likely to occur, and as a result, it is considered that the developability is superior to that of systems using thermal polymerization initiators. The quantitative determination of the alkenyl group (unsaturated bond) is performed using the "Method for Quantifying Double Bonds" described in Japanese Patent Publication No. 2012-214728, as shown in the Examples section below.

[0039] In this embodiment, the indane ring-containing compound (A) preferably contains 50% to 100% by mass of the structural unit represented by general formula (1b) based on the total amount (100% by mass) of the indane ring-containing compound (A), preferably 55% to less than 100% by mass, and more preferably 55% to 85% by mass. If the proportion of structural units represented by general formula (1b) in the indane ring-containing compound (A) is 55% by mass or more, the fused ring structure of the indane skeleton can exhibit superior chemical and thermal stability.

[0040] <Another preferred form of the indan ring-containing compound (A)> The indan ring-containing compound (A) in this embodiment may be a mixture. When the indan ring-containing compound (A) is a mixture, it is referred to as an indan-based mixture. The indan-based mixture of this embodiment contains multiple indan ring-containing compounds (A) that exhibit excellent low dielectric loss tangent, and therefore the resin composition as a whole exhibits even better low dielectric loss tangent.

[0041] The indane mixture in this embodiment is given by the following general formula (1a): [ka] (In the above general formula (1a), R 11 , R 12 and R 13 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n 12 (This represents the average number of repeating units.) A structural unit represented by, It is composed of an indane ring component having an alkenyl group bonded to at least one terminal portion of the structural unit, The following general formula (1b): [ka] (In the above general formula (1b), R 11 , R 12 and R 13Each of these independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Q 11 Q 12 , L 11 and L 12 Each of these independently represents a single bond or an alkylene group with 1 to 8 carbon atoms. P 11 and P 12 Each of these independently represents a hydrogen atom, a polar group, an alkyl group having 1 to 6 carbon atoms which may be substituted with the polar group, an alkenyl group having 2 to 10 carbon atoms, or the following general formula (2), M 11 and M 12 Each of these independently represents a single bond or the following general formula (3): n 12 n represents the average number of repeating units. 11 and n 13 Each of these independently represents a number from 0 to 20. However, P 11 and P 12 At least one of them is an alkenyl group having 2 to 10 carbon atoms. [ka] [In the above general formula (2), R 15 Each of these independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms, n 2 This represents an integer between 0 and 4 (inclusive). [In the above general formula (3), R 16 Each of these independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms, n 3 This represents an integer between 0 and 4 (inclusive). In general formulas (2) and (3), * represents a bond with another atom. It is preferable to contain two or more compounds represented by ). Furthermore, examples of the polar group include a hydroxyl group, an alkoxy group, or a halogen atom. The alkyl group having 1 to 6 carbon atoms that may be substituted for the polar group refers to a group in which one or more arbitrary hydrogen atoms of the alkyl group having 1 to 6 carbon atoms are substituted for a hydroxyl group, an alkoxy group, or a halogen atom.

[0042] Each compound constituting the indan-based mixture of this embodiment requires an indan ring component with an indan ring skeleton having a very high proportion of carbon and hydrogen atoms. Therefore, the indan-based mixture as a whole exhibits extremely low dielectric loss tangent. Furthermore, each compound constituting the indan-based mixture of this embodiment has excellent chemical thermal stability due to the fused ring structure of the indan ring. This makes it possible to achieve a higher-order balance between superior heat resistance and low dielectric loss tangent. In particular, since the indan-based mixture is a blend of two or more indan ring-containing compounds (A), it is thought that a higher-order balance between superior heat resistance and low dielectric loss tangent can be achieved depending on the composition ratio of each blended indan ring-containing compound (A).

[0043] In the indane-based mixture of this embodiment, the proportion of the compound represented by general formula (1b) relative to 100% by mass of the total amount of the indane-based mixture (= indane ring-containing compound (A)), which has an indane ring component having a structural unit represented by general formula (1a) and an alkenyl group bonded to the end of the structural unit, is preferably in the range of 0.1 to 50% by mass, more preferably in the range of 5 to 95% by mass, even more preferably in the range of 10 to 90% by mass, even more preferably in the range of 15 to 90% by mass, and particularly preferably in the range of 20 to 90% by mass. When the proportion of the indane ring-containing compound (A) represented by general formula (1b) is in the range of 1 to 30% by mass relative to the entire indane ring component having the structural unit represented by general formula (1a), it is easier to exhibit better heat resistance and a lower dielectric loss tangent.

[0044] As one embodiment of the indane-based mixture of this embodiment, the indane-based mixture may contain an indane ring-containing compound (A1) having an aniline skeleton. As a result, the indane-based mixture contains an indane ring-containing compound (A1) having an aromatic ring with an aniline skeleton, which is preferable from the viewpoint of enabling its use in combination with various curable resins such as epoxy resins and bismaleimide resins in order to further improve the heat resistance of the resin composition as a whole. The indan ring-containing compound (A1) having the aniline skeleton preferably has a structural unit represented by the following general formula (1a) and a structural unit represented by the following general formula (2) or general formula (4), and at least one of its terminal sites is an alkenyl group. [ka] (In the above general formula (1a), R 11 , R 12 and R 13 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n 12 (This represents the average number of repeating units.) [ka] (In the above general formula (2), R 15 Each of these independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms, n 2 (This represents an integer between 0 and 4, inclusive.) (In the above general formula (4), R 14 Each of these independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms, n 4 (This represents an integer between 0 and 3, inclusive.) In the above general formula (4), R 14 Each of these is preferably independently an amino group, a fluoroalkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. Also, n 4 It is preferable that this value is 0 or 1. Furthermore, the indane ring-containing compound (A1) having an aniline skeleton in this embodiment is more preferably represented by the following general formula (1c). [ka] (In the above general formula (1c), R 11 , R 12 and R 13 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Q 21 Q 22 , L21 and L 22 Each of these independently represents a single bond or an alkylene group having 1 to 8 carbon atoms, wherein the -CH2-CH2- in the alkylene group may be substituted with -CH=CH-. P 21 and P 22 Each of these independently represents an alkenyl group having 2 to 10 carbon atoms or a group represented by the following general formula (2): M 21 and M 22 Each of these independently represents a single bond or a group represented by the following general formula (5): n 12 n represents the average number of repeating units. 21 and n 23 Each of these independently represents a number from 0 to 20. However, P 21 and P 22 At least one of them is an alkenyl group having 2 to 10 carbon atoms, and n 21 Individual M 21 and n 23 Individual M 22 and P 21 and P 22 Of these, at least one group is substituted with an amino group. [ka] [In the above general formula (2), R 15 Each of these independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms, n 2 This represents an integer between 0 and 4 (inclusive). [In the above general formula (5), R 17 Each of these independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms, n 5 This represents an integer between 0 and 4 (inclusive). In addition, in the above general formulas (2) and (5), * represents a bond with another atom. It is preferable that it be represented as ). Furthermore, if the indane mixture contains an indane ring-containing compound (A1) having an aniline skeleton, one or more of the compounds represented by the above general formula (1b) contained in the indane mixture may be the compound represented by the above general formula (1c).

[0045] The "n" in the above general formula (1c) 21 Individual M 21 and n 23 Individual M 22 and P 21 and P 22 "At least one of the groups is substituted with an amino group." This means that one molecule of an indan ring-containing compound represented by general formula (1c) has at least one aromatic ring having one or more amino groups. More specifically, an indan ring-containing compound represented by general formula (1c) has n 21 Individual M 21 and n 23 Individual M 22 and one P 21 and one P 22 And these "n 21 Individual M 21 , n 23 Individual M 22 , 1 P 21 and one P 22 The total n 21 +n 23 This means that of the two groups, at least one group is an aromatic ring containing an amino group (e.g., an aniline skeleton). Therefore, M in general formula (1c) 21 Or M 22 When the group indicated by is substituted with an amino group (M 21 Or M 22 If the group shown is general formula (5), M 21 Or M 22 Each of these can independently become a base represented by the general formula (4) above. In other words, M in general formula (1c) 21 Or M 22 If the group indicated by is substituted with an amino group, M 21 Or M 22 is a group represented by general formula (5), n 5is an integer greater than or equal to 1, and n 5 There are R 17 at least one of R 17 This is an amino group. Also, P in general formula (1c) 21 or P 22 If the group indicated by is substituted with an amino group, then P 21 or P 22 One of the components may be a group represented by general formula (2), and the other may be an alkenyl group having 2 to 10 carbon atoms.

[0046] In the above general formula (1c), n 21 If there are 2 or more, there are multiple M 21 Each of them is independent and may be the same as or different from one another. Similarly, there may be multiple L 21 Each of them is independent and may be the same as or different from one another. Furthermore, n 23 If there are 2 or more, there are multiple M 22 Each of them is independent and may be the same as or different from one another. Similarly, there may be multiple L 22 Each of them is independent and may be the same as or different from one another.

[0047] In the above general formula (5), n 5 If the number is 2 or more, there are multiple R 17 Each of them is independent and may be the same as or different from one another.

[0048] In the above general formula (1c), Q 21 and Q 22 Each of these preferably independently represents a single bond or an alkylene group having 1 to 8 carbon atoms. However, Q 21 Or Q 22 If is an alkylene group having 2 or more carbon atoms, the -CH2-CH2- in the alkylene group may be replaced with -CH=CH-. In the above general formula (1c), Q 21 Or Q 22Each of these is independently more preferably a single bond, an alkylene group having 1 to 6 carbon atoms, or an alkenylene group having 2 to 6 carbon atoms, and even more preferably a single bond or an alkylene group having 1 to 4 carbon atoms. Particularly preferred Q in general formula (1c) 21 Or Q 22 These include single bonds, methylene groups, ethylene groups, n-propylene groups, isopropylene groups, isopropylidene groups, propylidene groups, n-butylene groups, isobutylene groups, sec-butylene groups, tert-butylene groups, n-pentylene groups, isopentylene groups, tert-pentylene groups, neopentylene groups, or 1,2-dimethylpropylene groups. Also, Q 21 and Q 22 They may be the same or different from one another.

[0049] In the above general formula (1c), L 21 and L 22 Each of these preferably independently represents a single bond or an alkylene group having 1 to 8 carbon atoms. However, L 21 or L 22 If is an alkylene group having 2 or more carbon atoms, the -CH2-CH2- in the alkylene group may be replaced with -CH=CH-. In the above general formula (1c), L 21 and L 22 Each of these is independently more preferably a single bond, an alkylene group having 1 to 6 carbon atoms, or an alkenylene group having 2 to 6 carbon atoms, and even more preferably a single bond or an alkylene group having 1 to 4 carbon atoms. Particularly preferred L in general formula (1c) 21 and L 22 Each of these is independently a single bond, a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an isopropylidene group, a propylidene group, an n-butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, an n-pentylene group, an isopentylene group, a tert-pentylene group, a neopentylene group, or a 1,2-dimethylpropylene group. Also, L 21 and L 22 They may be the same or different from one another.

[0050] In the above general formula (1c), P21 and P 22 Each of these is independently an alkenyl group having 2 to 10 carbon atoms or a group represented by the following general formula (2). [ka] (In the above general formula (2), R 15 Each of these independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms, n 2 (This represents an integer between 0 and 4, inclusive.) Furthermore, the alkenyl group having 2 to 10 carbon atoms is preferably an alkenyl group having at least one quaternary atom, and having at least one quaternary atom, and one of the bonds of the quaternary atom is L 21 or L 22 It is more preferable that the alkenyl group is bonded to the following, and even more preferable that the alkenyl group is represented by the following general formula (x-2). [ka] (In the above general formula (x-2), R x3 R represents an alkyl group with 1 to 6 carbon atoms. x4 * represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and in the general formula (x-2) above, * represents a bond that is chemically bonded to the carbon atom of the aromatic ring. In the above general formula (1c), P 21 or P 22 Preferably, at least one of them is an alkenyl group represented by the general formula (x-2), and P 21 and P 22 It is more preferable that both are alkenyl groups represented by the general formula (x-2). This results in the indan ring-containing compound (A) exhibiting higher UV curability, and thus tending to have improved heat resistance. In this embodiment, P 11 or P 12 When one of the groups is represented by the general formula (2) above, a preferred form of the indan ring-containing compound (A) is, in the general formula (2) above, R 15Each of these independently represents an amino group, a fluoroalkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms, n 2 P can represent an integer between 0 and 4 (inclusive). 21 and P 22 If at least one of the groups is represented by general formula (2), the homopolymerization of the other alkenyl group can be suppressed to some extent. Note that the benzene ring in general formula (2) may correspond to the benzene ring in the aniline compounds described later.

[0051] In the general formula (1c) above, M 21 and M 22 Each of these is independently a single bond or a group represented by the general formula (5) above. M in the general formula (1c) above 21 and M 22 Each of these is independently a phenylene group, preferably a single bond, or may be substituted with an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms, as shown in the general formula (5) above. Examples of such phenylene groups include 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene groups. Note that the benzene ring in general formula (5) may correspond to the benzene ring of the aniline compounds described later.

[0052] In the above general formula (1c), n 21 n represents the average number of repeating units, and is preferably in the range of 0 to 20, more preferably in the range of 0 to 15, and even more preferably in the range of 0 to 10. 21 When the range is as described above, the proportion of carbon and hydrogen atoms in the constituent atoms of the indan ring-containing compound (A) of this embodiment increases, making the entire indan ring-containing compound (A) more likely to exhibit low polarity, and thus further reducing the dielectric loss tangent.

[0053] In the above general formula (1c), n 23 n represents the average number of repeating units, and is preferably in the range of 0 to 20, more preferably in the range of 0 to 15, and even more preferably in the range of 0 to 10. 23When the range is as described above, the proportion of carbon and hydrogen atoms in the constituent atoms of the indan ring-containing compound (A) of this embodiment increases, making the entire indan ring-containing compound (A) more likely to exhibit low polarity, and thus further reducing the dielectric loss tangent. Note that the symbol "R" in the above general formula (1c) 11 , R 12 , R 13 , and n 12 " is "R in the general formula (1b) above 11 , R 12 , R 13 , and n 12 This is synonymous with "."

[0054] In this embodiment, the content of the indane ring-containing compound (A1) having an aniline skeleton represented by general formula (1c) is preferably in the range of 0.1 to 50% by mass, more preferably in the range of 1 to 40% by mass, and even more preferably in the range of 1 to 30% by mass, based on 100% by mass of the total amount of the indane mixture (or the entire indane ring-containing compound (A)). When the content of the indane ring-containing compound (A1) having an aniline skeleton represented by general formula (1c) is within the above range, it becomes possible to use it in combination with various curable resins such as epoxy resins and bismaleimide resins in order to further improve the heat resistance of the resin composition as a whole without degrading the dielectric properties.

[0055] Furthermore, in this embodiment, if the indan ring-containing compound (A1) having an aniline skeleton represented by general formula (1c) has an aminophenyl group derived from an aniline-based compound at its terminal end, it is preferable from the viewpoint of enabling combined use with various curable resins such as epoxy resins and bismaleimide resins in order to further improve heat resistance. In addition, when the indan ring-containing compound (A1) having an aniline skeleton represented by general formula (1c) is included, when combined with other curable resins, for example, a normal addition reaction proceeds with epoxy group-containing curable resins, or a Michael addition-type curing reaction proceeds with maleimide group-containing curable resins, thus an improvement in physical heat resistance (Tg) can be expected. The above is a description of the indan ring-containing compound (A) of this disclosure. The method for producing the indan ring-containing compound (A) of this disclosure will now be described.

[0056] <Method for producing indane ring-containing compound (A)> One example of a method for producing the indan ring-containing compound (A) of this embodiment is a step of reacting an aromatic compound (i) having substituents that form a carbocation (hereinafter also simply referred to as aromatic compound (i)), more preferably an aromatic compound (i) having two or more substituents that form a carbocation bonded to a benzene ring, with an aniline compound in the presence of an acid. Therefore, in another aspect of this embodiment, the indan ring-containing compound (A) of this embodiment can also be said to be a compound that uses an aromatic compound (i) having substituents that form a carbocation as a reaction raw material. An example of a method for producing the indan ring-containing compound (A) of this disclosure is a method comprising the following step (1). Step (1): A step of obtaining the indane ring-containing compound (A) of the present disclosure by reacting an aromatic compound (i) as a reaction raw material in the presence of an aniline compound and an acid (preferably in the presence of a solid acid catalyst). Specifically, the method for producing the indan ring-containing compound (A) of this embodiment preferably includes a step of reacting aromatic compounds (i) in which two or more substituents that form a carbocation are bonded to a benzene ring in the presence of an aniline compound and an acid (preferably in the presence of a solid acid catalyst). By using aniline compounds, the runaway cationic polymerization that leads to high molecular weight formation is suppressed, and an indan ring-containing compound (A) having a terminal double bond (e.g., an isopropenyl group) in the relatively low to medium molecular weight range is obtained. Furthermore, gelation can be suppressed or prevented by using aniline compounds. In particular, when using an aromatic compound (i) as a reaction raw material, for example, a group represented by the general formula (x-1) below and having a structure in which a hydroxyl group is bonded to the α-carbon, water is generated as the reaction proceeds during the heating process, and a violent exothermic reaction occurs accompanied by bumping. Therefore, dehydration is generally required to reach a reaction temperature of, for example, 180-200°C. However, by using aniline compounds, this dehydration can be omitted or the number of dehydration treatments can be reduced.

[0057] In the method for producing the indan ring-containing compound (A) of this embodiment, after step (1) above, known purification steps (for example, washing with a reaction solvent, adsorption, fractional distillation, ion exchange resin treatment, reprecipitation, crystallization, filtration, or removal of the reaction solvent by heating or under reduced pressure) may be performed as necessary. This removes low molecular weight components such as the reaction solvent and unreacted products, ionic impurities, etc., which can further improve the dielectric properties.

[0058] Furthermore, in this embodiment, the reaction product obtained in step (1) may be a mixture containing indane ring-containing compound (A), i.e., the indane-based mixture described above. Therefore, after step (1) or the purification step, indane ring-containing compound (A) having a specific molecular weight, indane ring-containing compound (A) having a specific functional group, or indane ring-containing compound (A) having alkenyl groups at both ends can be recovered using known separation means as necessary. The separation means include fractional distillation, chromatography, adsorption with an adsorbent, crystallization, extraction, or reprecipitation. For example, the crystallization step involves adding a poor solvent to the reaction product obtained in step (1) above and then cooling it to precipitate the target product as crystals; the step involves separating the target product from the liquid mobile phase containing the reaction product using chromatography (high-performance liquid chromatography, column chromatography, or gel permeation chromatography, etc.); or the step involves adsorbing and separating the target product or unwanted substances using an adsorbent such as activated carbon, silica gel, alumina, or Celite. More specifically, when recovering an indan ring-containing compound (A) having a specific molecular weight, separation is preferably performed using gel filtration chromatography, and when recovering an indan ring-containing compound (A) having a specific functional group (e.g., an amine group), separation is preferably performed using ion exchange chromatography.

[0059] The reaction raw materials, aniline compounds, acid catalysts, and reaction conditions used in the method for producing the indan ring-containing compound (A) of this disclosure will be described in order below. <<Aromatic compounds (i)>> In the method for producing the indan ring-containing compound (A) of this disclosure, it is preferable to use an aromatic compound (i) having substituents that form a carbocation as a reaction raw material. More specifically, the aromatic compound (i) mainly comprises a compound in which two or more substituents that form a carbocation are bonded to an aromatic ring. Furthermore, "main component" refers to a compound that accounts for 50% to 100% by mass of the total aromatic compound (i).

[0060] In this embodiment, the substituent that forms the carbocation is preferably a group represented by the following general formula (x-1) or an alkenyl group having 2 to 10 carbon atoms. [ka] (In the above general formula (x-1), X x1 represents a polar group, R x1 or R x2Each of these independently represents an alkyl group with 1 to 6 carbon atoms. In the general formula (x-1) above, * represents a bond that is chemically bonded to the aromatic ring. In the above general formula (x-1), examples of polar groups include hydroxyl groups, alkoxy groups, or halogen atoms. Thus, polar group X x1 The polar group X is relatively easily detached. x1 The α-carbon bonded to it can form a carbocation. Also, X in the general formula (x-1) above x1 Of these, hydroxyl groups are particularly preferred.

[0061] In the substituents forming the carbocation of this embodiment, the 2-10 carbon atom alkenyl group is preferably a 2-10 carbon atom alkenyl group having at least one quaternary carbon, more preferably a 2-10 carbon atom alkenyl group having at least one quaternary carbon and one of the bonds of the quaternary atom being chemically bonded directly or indirectly to a structural unit represented by general formula (1a), and even more preferably a group represented by the following general formula (x-2). [ka] (In the above general formula (x-2), R x3 R represents an alkyl group with 1 to 6 carbon atoms. x4 * represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In the above general formula (x-2), * represents a bond that is chemically bonded to the aromatic ring. If the alkenyl group has 2 to 10 carbon atoms and is represented by the general formula (x-2), the quaternary carbon can relatively stably form a carbocation. In the above general formula (x-2), R x3 R is preferably a linear alkyl group having 1 to 3 carbon atoms. x4 Preferably, it is a hydrogen atom or a linear alkyl group having 1 to 3 carbon atoms.

[0062] In this embodiment, the aromatic compound (i) having a substituent that forms a carbocation may be a monomer that forms a structural unit of general formula (1a) that constitutes the indan ring-containing compound (A). In this embodiment, it is preferable that the aromatic compound (i) having a substituent that forms a carbocation includes a compound represented by the following general formula (i-1). [ka] (In the above general formula (i-1), R i3 Each of these independently represents an alkyl or alkoxy group having 1 to 6 carbon atoms, and R i1 and R i2 Each of these is a substituent that independently forms a carbocation, and n i1 represents an integer between 1 and 5, and n i2 n represents an integer between 0 and 4, where n is greater than or equal to 0. i1 +n i2 (It is 5 or less.) In the above general formula (i-1), R i1 and R i2 Each of them may be the same as or different from each other. Also, n i1 If the value is between 2 and 5, there are multiple R values. i2 These may be identical to each other or different from each other. Furthermore, n i2 If there are 2 or more, there are multiple R i3 These may be identical to each other, or they may be different from each other. In the above general formula (i-1), n i1 It is preferably 1, 2, or 3, and more preferably 1 or 2. i2 n is preferably 0, 1, or 2, and is preferably 0 or 1. i1 +n i2 It is preferable that the value is between 2 and 5. In this embodiment, the compound represented by general formula (i-1) is defined as having R in the above general formula (i-1). i1 and R i2 It is preferable that the two groups are the same.

[0063] In this embodiment, a preferred form of the compound represented by general formula (i-1) is n i1 If is 1, then R is present at positions 1 and 3 of the benzene ring in the above general formula (i-1), or at positions 1 and 4 of the benzene ring in the above general formula (i-1). i1 and R i2 It is preferable that each of them is substituted. Also, n i1 If is 2, then R is added to positions 1, 3 and 5 of the benzene ring in the above general formula (i-1). i1 and two R 42 It is preferable that each of these is substituted. This reduces steric hindrance and allows for a further improvement in the molecular weight or yield of the indan ring-containing compound (A).

[0064] In this embodiment, the aromatic compound (i) having a substituent that forms a carbocation may further include, in addition to the compound represented by the general formula (i-1) above, an aromatic compound (ii) having one substituent that forms a carbocation (for example, a group represented by the general formula (x-1) above). The aromatic compound (ii) is preferably represented by the following general formula (ii-1). [ka] (In the above general formula (ii-1), R ii1 R is a substituent that forms a carbocation (for example, preferably an alkenyl group having 2 to 10 carbon atoms, a group represented by the general formula (x-1) or a group represented by the general formula (x-2) above), ii2 Each of these independently represents an alkyl group with 1 to 6 carbon atoms, and n ii1 (This represents an integer between 0 and 5, inclusive.)

[0065] <Aniline compounds> In this embodiment, the aniline compound mitigates the high molecular weight increase of aromatic compounds having substituents that form carbocations through cationic polymerization in the presence of an acid catalyst. Depending on the amount added, it significantly increases the likelihood of obtaining an indan ring-containing compound (A), which is a terminal alkenyl structure with a number-average molecular weight (Mn) of approximately 3,000 or less and a weight-average molecular weight (Mw) of 7,000 or less, as the main product. As a result, due to the presence of terminal double bonds in the terminal alkenyl structure, the indan ring-containing compound (A) can be used as a photocurable resin. On the other hand, if the aniline compound is not used, high molecular weight increase becomes unavoidable, and the resulting product tends to be mainly composed of thermoplastic resins. In the method for producing the indan ring-containing compound (A) of this embodiment, gelation can be suppressed or prevented by using an aniline compound as a co-catalyst. For example, when using an aromatic compound (i) having a structure in which a hydroxyl group is bonded to the α-carbon and represented by the above general formula (x-1) as a substituent to form a carbocation as a reaction raw material, water is produced as the reaction proceeds, so dehydration treatment is generally required. However, by using an aniline compound, this dehydration treatment can be omitted or the number of dehydration treatments can be reduced. Furthermore, although the aniline compound is used as a co-catalyst, it may be incorporated into a part of the structural unit of the indan ring-containing compound (A) of this disclosure. The aniline compound is preferably represented by the following general formula (iii-1). [ka] (In the above general formula (iii-1), R iii1 Each of these independently represents an amino group, a fluoroalkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms, n iii1 (This represents an integer between 0 and 5, inclusive.) In the above general formula (iii-1), n iii1 If the value is between 2 and 5, there are multiple R values. iii1 These are independent of each other, and there are multiple R's. iii1 They may be identical to each other, or they may be different to each other. In the above general formula (iii-1), the fluoroalkyl group having 1 to 6 carbon atoms is preferably a perfluoroalkyl group having 1 to 6 carbon atoms.

[0066] A preferred form of the aniline compound in this embodiment is n in the general formula (iii-1) above. iii1 R is an integer between 1 and 4, and is between 1 and 4. iii1 Preferably, each of these independently represents an amino group, a fluoroalkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. The aniline compounds of this embodiment can include, for example, aniline, dimethylaniline, diethylaniline, diisopropylaniline, ethylmethylaniline, cyclobutylaniline, cyclopentylaniline, cyclohexylaniline, toluidine, ethylaniline, propylaniline, butylaniline, 2-methyl-3-ethylaniline, 2-methyl-4-isopropylaniline, 2,6-diethylaniline, or 2-ethyl-5-tert-butylaniline, 2,4-diisopropylaniline, trimethylaniline (e.g., 2,4,6-trimethylaniline), diethyltoluenediamine, etc. Furthermore, the propyl includes n-propyl and isopropyl, and the butyl includes n-butyl, tert-butyl and sec-butyl. The aniline compounds of this embodiment may be used individually or in combination of two or more.

[0067] In this embodiment, considering the balance of moldability and curability properties during the production of the resulting cured product, the blending ratio of aromatic compound (i) to aniline compound is preferably 0.01 to 30 parts by mass, and more preferably 0.1 to 15 parts by mass, of aromatic compound (i) per 100 parts by mass of aniline compound. Furthermore, as a specific method for carrying out the above step (1), it is common to either charge all the raw materials together and react them at a predetermined temperature, or to charge either the aromatic compound (i) or the aniline compound, along with an acid catalyst and a reaction solvent, and while maintaining the predetermined temperature, to react by dropping the other aromatic compound (i) or aniline compound, etc. After the reaction, if a solvent is used, the solvent and unreacted products can be removed by distillation as needed to obtain the target product, the indane ring-containing compound (A). If no solvent is used, the target product, the indane ring-containing compound (A), can be obtained by distilling off the unreacted products.

[0068] <Acid catalyst> Examples of acid catalysts used in step (1) of this embodiment include acetates of nickel, cobalt, sodium, calcium, iron, lithium, manganese, etc., inorganic salts such as chlorides, bromides, sulfates, and nitrates, inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid, organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid, solid acids such as activated clay, acid clay, silica alumina, zeolite, and strong acid ion exchange resins, and heteropolyhydrochloric acid. However, solid acids that can be easily removed by filtration after the reaction are preferred from the viewpoint of ease of handling. When using other acids, it is preferable to neutralize with a base and wash with water after the reaction. The amount of the acid catalyst is preferably in the range of 0.1 to 50 parts by mass per 100 parts by mass of the total amount of the raw material to be charged (aromatic compound (i) having substituents that form a carbocation), and more preferably in the range of 1 to 30 parts by mass from the viewpoint of handling and economic efficiency.

[0069] <Reaction conditions> In the method for producing the indan ring-containing compound (A) in this embodiment, a reaction solvent is not necessarily required, but an organic solvent can be used as the reaction solvent. Examples of organic solvents used in the manufacturing method of this embodiment include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, and acetophenone; aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, and sulfolane; cyclic ethers such as dioxane and tetrahydrofuran; esters such as ethyl acetate and butyl acetate; and aromatic solvents such as benzene, toluene, and xylene. These may be used individually or in combination. In step (1) of this embodiment, the amount of organic solvent used is preferably in the range of 10 to 3,000 parts by mass, and more preferably 50 to 1,000 parts by mass, per 100 parts by mass of aromatic compound (i) having substituents that form a carbocation. Furthermore, since the reaction is carried out using aromatic compound (i) as a starting material, a method may be employed in which, if necessary, water contained in the catalyst is azeotropically dehydrated using an azeotropic solvent such as toluene, xylene, or chlorobenzene, and then the water is removed by distillation before carrying out the reaction within the reaction temperature range described later.

[0070] In step (1) of this embodiment, the reaction temperature for the cyclization reaction between aromatic compounds (i) having substituents that form a carbocation is preferably in the temperature range of 80 to 250°C, and more preferably in the temperature range of 100 to 220°C. In step (1) of this embodiment, the reaction time for the aromatic compound (i) having substituents that form a carbocation, that is, the reaction time for the cyclization reaction between the aromatic compounds (i), is usually in the range of 0.5 to 20 hours in total, but preferably in the range of 1 to 10 hours in total, because if the reaction is too short the reaction will not proceed completely, and if it is too long side reactions such as thermal decomposition of the product will occur under the aforementioned reaction temperature conditions. As preferable reaction conditions for step (1) of the present embodiment, the aromatic compound (i), aniline-based compound, acid catalyst, and organic solvent are charged, and the reaction is preferably carried out in a temperature range of 80 to 250°C, more preferably 100 to 220°C, for 0.5 to 20 hours, preferably 1.0 to 10 hours. Then, after raising the reaction temperature to a temperature range of 100 to 220°C, preferably 120 to 210°C, the reaction is carried out for 0.5 to 20 hours, preferably 1.0 to 10 hours. In step (1) of the present embodiment, if necessary, dehydrating agents such as lower aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride, oxides such as phosphorus pentoxide, calcium oxide, and barium oxide, inorganic acids such as sulfuric acid, and porous ceramics such as molecular sieves may be used. Further, instead of the above dehydrating agent, the distilled water may be removed during the reaction.

[0071] (Compound (B) having a polymerizable unsaturated group) The compound (B) having a polymerizable unsaturated group in the present embodiment is one of the essential components in the resin composition of the present embodiment. As the component (B), it only needs to have a polymerizable unsaturated group, and other specific structures, molecular weights, etc. are not particularly limited, and various resins or compounds can be used. The compound (B) having a polymerizable unsaturated group may be used alone or in combination of two or more. In addition, the compound (B) having a polymerizable unsaturated group preferably has a polymerizable unsaturated group but no acid group. Here, the acid group includes, for example, a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc.

[0072] In the present embodiment, examples of the polymerizable unsaturated group possessed by the component (B) include a (meth)acryloyl group, an allyl group, an isopropenyl group, a 1-propenyl group, a styryl group, a styrylmethyl group, a maleimide group, a vinyl ether group, etc.

[0073] Specific examples of the compound (B) having a polymerizable unsaturated group include a (meth)acrylate compound (B0), a resin having a polymerizable unsaturated group, etc.

[0074] The above (meth)acrylate compound (B0) is not particularly limited as long as it has a (meth)acryloyl group, for example, aliphatic mono(meth)acrylate compounds such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, octyl(meth)acrylate, etc.; cyclohexyl(meth)acrylate, Alicyclic mono(meth)acrylate compounds such as isobornyl (meth)acrylate and adamantyl mono(meth)acrylate; heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, Mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds including 2-hydroxy-3-phenoxypropyl(meth)acrylate, phenoxybenzyl(meth)acrylate, benzylbenzyl(meth)acrylate, and phenylphenoxyethyl(meth)acrylate; (poly)oxyalkylene-modified mono(meth)acrylate compounds obtained by introducing polyoxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains into the molecular structure of the various mono(meth)acrylate monomers; lactone-modified mono(meth)acrylate compounds obtained by introducing a (poly)lactone structure into the molecular structure of the various mono(meth)acrylate compounds; aliphatic di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate;Alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate; aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; (poly)oxyen Polyoxyalkylene-modified di(meth)acrylate compounds into which (poly)oxyalkylene chains such as ethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains have been introduced; lactone-modified di(meth)acrylate compounds into which a (poly)lactone structure has been introduced into the molecular structure of the above various di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; molecules of the above aliphatic tri(meth)acrylate compounds (Poly)oxyalkylene-modified tri(meth)acrylate compounds having (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains introduced into their structure; lactone-modified tri(meth)acrylate compounds having a (poly)lactone structure introduced into the molecular structure of the aliphatic tri(meth)acrylate compound; pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth) Aliphatic poly(meth)acrylate compounds with four or more functions, such as acrylates; aliphatic poly(meth)acrylate compounds with four or more functions, obtained by introducing (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains into the molecular structure of the aliphatic poly(meth)acrylate compounds; aliphatic poly(meth)acrylate compounds with four or more functions, obtained by introducing (poly)lactone structures into the molecular structure of the aliphatic poly(meth)acrylate compounds;Hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate (meth)acrylate compounds having hydroxyl groups, such as dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane(meth)acrylate, ditrimethylolpropanedi(meth)acrylate, and ditrimethylolpropanetri(meth)acrylate; (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetraacrylates in the molecular structure of the said hydroxyl group-containing (meth)acrylate compounds; Examples include (poly)oxyalkylene modified compounds with (poly)oxyalkylene chains such as ethylene chains; lactone modified compounds with a (poly)lactone structure introduced into the molecular structure of the hydroxyl group-containing (meth)acrylate compound; (meth)acrylate compounds having an isocyanate group such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate; (meth)acrylate monomers having a glycidyl group such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; and (meth)acrylate compounds having an epoxy group such as mono(meth)acrylates of diglycidyl ether compounds of droxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. The (meth)acrylate compound (B0) may be used alone or in combination of two or more types.

[0075] As the resin having the polymerizable unsaturated group, any polymer material having a polymerizable unsaturated group in the resin may be used. For example, the following [1] to [6]: 〔1〕Epoxy resin (B1) having a polymerizable unsaturated group, 〔2〕Urethane resin (B2) having a polymerizable unsaturated group, 〔3〕Acrylic resin (B3) having a polymerizable unsaturated group, 〔4〕Amide-imide resin (B4) having a polymerizable unsaturated group, 〔5〕Acrylamide resin (B5) having a polymerizable unsaturated group, 〔6〕Ester resin (B6) having a polymerizable unsaturated group, and the like can be mentioned.

[0076] <Epoxy resin (B1) having a polymerizable unsaturated group> As the epoxy resin (B1) having a polymerizable unsaturated group in the present embodiment (hereinafter, also referred to as resin (B1)), for example, an epoxy (meth) acrylate resin obtained by reacting an epoxy resin, an unsaturated monobasic acid, and, if necessary, a polybasic acid anhydride; a urethane group-containing epoxy (meth) acrylate resin obtained by reacting an epoxy resin, an unsaturated monobasic acid, a polyisocyanate compound, and a (meth) acrylate compound having a hydroxyl group, and, if necessary, a polybasic acid anhydride; and the like can be mentioned. In addition, although the polybasic acid anhydride can be used as a reaction raw material of the resin (B1) as described above, it is preferably not used. The resin (B1) preferably has a polymerizable unsaturated group but no acid group.

[0077] Examples of the epoxy resins mentioned above include bisphenol-type epoxy resins, hydrogenated bisphenol-type epoxy resins, biphenol-type epoxy resins, hydrogenated biphenol-type epoxy resins, phenylene ether-type epoxy resins, naphthylene ether-type epoxy resins, biphenyl-type epoxy resins, triphenylmethane-type epoxy resins, phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol novolac-type epoxy resins, naphthol novolac-type epoxy resins, naphthol-phenol copolymer novolac-type epoxy resins, naphthol-cresol copolymer novolac-type epoxy resins, phenol aralkyl-type epoxy resins, naphthol aralkyl-type epoxy resins, dicyclopentadiene-phenol addition reaction-type epoxy resins, biphenyl aralkyl-type epoxy resins, fluorene-type epoxy resins, xanthene-type epoxy resins, dihydroxybenzene-type epoxy resins, trihydroxybenzene-type epoxy resins, oxazolidone-type epoxy resins, and the like. These epoxy resins may be used individually or in combination of two or more types.

[0078] Examples of the bisphenol-type epoxy resins mentioned above include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. Examples of the above-mentioned hydrogenated bisphenol type epoxy resins include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol B type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol F type epoxy resin, and hydrogenated bisphenol S type epoxy resin.

[0079] Examples of the above-mentioned biphenol-type epoxy resins include 4,4'-biphenol-type epoxy resin, 2,2'-biphenol-type epoxy resin, tetramethyl-4,4'-biphenol-type epoxy resin, and tetramethyl-2,2'-biphenol-type epoxy resin. Examples of the above-mentioned hydrogenated biphenol-type epoxy resins include hydrogenated 4,4'-biphenol-type epoxy resin, hydrogenated 2,2'-biphenol-type epoxy resin, hydrogenated tetramethyl-4,4'-biphenol-type epoxy resin, and hydrogenated tetramethyl-2,2'-biphenol-type epoxy resin.

[0080] Furthermore, examples of the above unsaturated monobasic acids include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, β-furfurylacrylic acid, etc. Esters, acid halides, acid anhydrides, etc. of the above unsaturated monobasic acids can also be used. In addition, the above unsaturated monobasic acid can be expressed by the following general formula (6): [ka] (In the above general formula (6), X 61 X represents an alkylene chain, polyoxyalkylene chain, (poly)ester chain, aromatic hydrocarbon chain, or (poly)carbonate chain having 1 to 10 carbon atoms. 61 The hydrogen atoms in the structure may be substituted with halogen atoms or alkoxy groups, Y 61 Compounds represented by (where is a hydrogen atom or a methyl group) can also be used.

[0081] Examples of the polyoxyalkylene chains mentioned above include polyoxyethylene chains and polyoxypropylene chains. Examples of the above (poly)ester chain include the following general formula (7): [ka] (In the above general formula (7), R 71 and R 72 This represents an alkylene group with 1 to 10 carbon atoms, n 71 ∫ represents an integer from 1 to 5. Examples include (poly)ester chains represented by ∫. These unsaturated monobasic acids may be used individually or in combination of two or more.

[0082] Examples of the above-mentioned aromatic hydrocarbon chains include phenylene chains, naphthylene chains, biphenylene chains, phenylnaphthylene chains, or binaphthylene chains. In addition, hydrocarbon chains having aromatic rings such as benzene rings, naphthalene rings, anthracene rings, and phenanthrene rings as partial structures can also be used.

[0083] Examples of the above (poly)carbonate chains include the following general formula (8): [ka] (In the above general formula (8), R 81 This represents an alkylene group with 1 to 10 carbon atoms, n 81 represents an integer from 1 to 5. An example is a (poly)carbonate chain represented by ).

[0084] Examples of the polybasic anhydrides mentioned above include aliphatic polybasic anhydrides, alicyclic polybasic anhydrides, and aromatic polybasic anhydrides.

[0085] Examples of the above-mentioned aliphatic polybasic acid anhydrides include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, and acid anhydrides of 1,2,3,4-butanetetracarboxylic acid. Furthermore, the aliphatic hydrocarbon group in the aliphatic polybasic acid anhydride may be either linear or branched, and may have unsaturated bonds in its structure.

[0086] In the present invention, as the alicyclic polybasic acid anhydride, an acid anhydride group is bonded to an alicyclic structure, and the presence or absence of an aromatic ring in other structural sites is not considered. Examples of the alicyclic polybasic acid anhydride include anhydrides of tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, etc.

[0087] Examples of the aromatic polybasic acid anhydride include anhydrides of phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, etc. These polybasic acid anhydrides may be used alone or in combination of two or more.

[0088] Examples of the above polyisocyanate compounds include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; and tolylene diisocyanate, Aromatic diisocyanate compounds such as silylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate; polymethylene polyphenyl polyisocyanates having a repeating structure represented by the following general formula (9); and isocyanurate modified, biuret modified, allophanate modified, etc. of these compounds. These polyisocyanate compounds may be used individually or in combination of two or more. [ka] (In the above general formula (9), R 92 and R 93 Each of these independently represents either a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R 91 Each of these independently represents an alkyl group with 1 to 4 carbon atoms, and k 91 n is an integer between 0 and 3, and n 91 (This is an integer greater than or equal to 1.)

[0089] Examples of (meth)acrylate compounds having a hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. Furthermore, polyoxyalkylene modified compounds, in which polyoxyalkylene chains such as polyoxyethylene chains, polyoxypropylene chains, and polyoxytetramethylene chains are introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds, and lactone modified compounds, in which a polylactone structure is introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds, can also be used.

[0090] The method for producing the epoxy resin (B1) having the polymerizable unsaturated group described above is not particularly limited and can be any method. In producing the epoxy resin (B1) having the polymerizable unsaturated group described above, the process may be carried out in an organic solvent as needed, and a basic catalyst may also be used as needed.

[0091] Examples of the above organic solvents include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and mineral spirits; ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, cyclohexanone, and dimethylacetamide; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; and carbitol, cellosolve, methanol, ethanol, propanol, isopropanol, butanol, and cyclohexanone. Examples of organic solvents include alcohol solvents such as propylene glycol monomethyl ether; ether solvents such as propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, and methyl carbitol; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; vegetable oils such as soybean oil, linseed oil, rapeseed oil, and safflower oil; and methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These organic solvents may be used individually or in combination of two or more.

[0092] Furthermore, commercially available organic solvents can also be used, such as ENEOS Corporation's "Spindle Oil No. 1", "Solvent No. 3", "Solvent No. 4", "Solvent No. 5", "Solvent No. 6", "Naphthezol H", "Alken 56NT", "AF Solvent No. 4", "AF Solvent No. 5", "AF Solvent No. 6", "AF Solvent No. 7", Mitsubishi Chemical Corporation's "Diadol 13", "Dialen 168"; Nissan Chemical Corporation's "F Oxocol", "F Oxocol 180"; Idemitsu Kosan Co., Ltd.'s "Supersol LA35", "Supersol LA38"; ExxonMobil Examples include Chemical's "Exsol D80," "Exsol D110," "Exsol D120," "Exsol D130," "Exsol D160," "Exsol D100K," "Exsol D120K," "Exsol D130K," "Exsol D280," "Exsol D300," and "Exsol D320."

[0093] Examples of basic catalysts include amine compounds such as N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, tetramethylammonium hydroxide, etc.; trioctylmethylammonium chloride, trio Examples include quaternary ammonium salts such as ctylmethylammonium acetate; phosphines such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxylpropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; organotin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dianeodecanoate, dibutyltin diacetate, tin octyolate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistanoxane; organometallic compounds such as zinc octyolate and bismuth octyoate; inorganic tin compounds such as tin octanoate; and inorganic metal compounds. Alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides can also be used. The basic catalysts described above may be used individually or in combination of two or more.

[0094] <Urethane resin having polymerizable unsaturated groups (B2)> Examples of the polymerizable unsaturated urethane resin (B2) of this embodiment (hereinafter also referred to as resin (B2)) include those obtained by reacting polyisocyanate compounds, (meth)acrylate compounds having hydroxyl groups, and, if necessary, polyol compounds and / or polybasic acid anhydrides. Although polybasic acid anhydrides can be used as reaction raw materials for resin (B2) as described above, it is preferable not to use them. It is preferable that the above resin (B2) has polymerizable unsaturated groups but does not have acid groups.

[0095] With regard to polyisocyanate compounds, (meth)acrylate compounds having hydroxyl groups, and polybasic acid anhydrides, the same applies as previously described with respect to the resin (B1), etc.

[0096] Examples of the polyol compounds mentioned above include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; aromatic polyol compounds such as biphenol and bisphenol; (poly)oxyalkylene modified compounds obtained by introducing (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains into the molecular structure of the various polyol compounds; lactone modified compounds obtained by introducing (poly)lactone structures into the molecular structure of the various polyol compounds, such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid. The polyol compounds may be used individually or in combination of two or more.

[0097] The method for producing the urethane resin (B2) having the polymerizable unsaturated group described above is not particularly limited and can be produced by any method. In producing the urethane resin (B2) having the polymerizable unsaturated group described above, the process may be carried out in an organic solvent as necessary, and a basic catalyst may also be used as necessary. In that case, the organic solvent and basic catalyst are the same as those described above for the resin (B1), etc.

[0098] <Acrylic resin with polymerizable unsaturated groups (B3)> Examples of the polymerizable unsaturated acrylic resin (B3) of this embodiment (hereinafter also referred to as resin (B3)) include a reaction product obtained by introducing a (meth)acryloyl group by further reacting an acrylic resin intermediate obtained by polymerizing an acrylic resin intermediate having a reactive functional group such as a hydroxyl group, carboxyl group, isocyanate group, or glycidyl group with an acrylic resin intermediate having a reactive functional group that can react with these functional groups, with an acrylic resin intermediate having a reactive functional group (β), or by reacting a polybasic acid anhydride with the hydroxyl group in the reaction product as needed. As mentioned above, polybasic acid anhydrides can be used as reaction raw materials for resin (B3), but it is preferable not to use them. It is preferable that the above resin (B3) has polymerizable unsaturated groups but does not have acid groups.

[0099] The above acrylic resin intermediate may be copolymerized with other polymerizable unsaturated compounds in addition to the (meth)acrylate compound (α) as needed. Examples of other polymerizable unsaturated compounds include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobolonyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; aromatic ring-containing (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. Other compounds having polymerizable unsaturated groups may be used individually or in combination of two or more.

[0100] The above (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group of the (meth)acrylate compound (α), but from the viewpoint of reactivity, the following combinations are preferred. That is, when water (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having an isocyanate group as the (meth)acrylate compound (β). When a (meth)acrylate having a carboxyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a glycidyl group as the (meth)acrylate compound (β). When a (meth)acrylate having an isocyanate group is used as the (meth)acrylate compound (α), it is preferable to use water (meth)acrylate as the (meth)acrylate compound (β). When a (meth)acrylate having a glycidyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a carboxyl group as the (meth)acrylate compound (β). The (meth)acrylate compound (β) may be used alone or in combination of two or more types.

[0101] The polybasic acid anhydride is the same as described above for resin (B1), etc.

[0102] The method for producing the acrylic resin (B3) having the polymerizable unsaturated group described above is not particularly limited and can be any method. In producing the acrylic resin (B3) having the polymerizable unsaturated group described above, the process may be carried out in an organic solvent as needed, and a basic catalyst may also be used as needed. In that case, the organic solvent and basic catalyst are the same as those described above for the resin (B1), etc.

[0103] <Amido-imide resin with polymerizable unsaturated groups (B4)> Examples of the polymerizable unsaturated amide-imide resin (B4) of this embodiment (hereinafter also referred to as resin (B4)) include those obtained by reacting an amide-imide resin having an acid group and / or an acid anhydride group with a (meth)acrylate compound having a hydroxyl group and / or an epoxy group with a compound having one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group. The compound having the reactive functional group may or may not have a (meth)acryloyl group. It is preferable that the above resin (B4) has polymerizable unsaturated groups but does not have acid groups.

[0104] The polymerizable unsaturated amide-imide resin (B4) may have only an acid group or an acid anhydride group, or both. However, from the viewpoint of reactivity and reaction control with (meth)acrylate compounds having hydroxyl groups and epoxy compounds having (meth)acryloyl groups, it is preferable that the polymerizable unsaturated amide-imide resin (B4) has an acid anhydride group, and more preferably that it has both an acid group and an acid anhydride group. The solid content acid value of the amide-imide resin is preferably in the range of 60 to 350 mgKOH / g when measured under neutral conditions, i.e., conditions in which the acid anhydride group is not ring-opened. On the other hand, it is preferable that the measured value is in the range of 61 to 360 mgKOH / g when measured under conditions in which the acid anhydride group is ring-opened, such as in the presence of water.

[0105] Examples of the polymerizable unsaturated group-containing amide-imide resin (B4) include those obtained using a polyisocyanate compound and a polybasic acid anhydride as reaction raw materials. In this case, the polyisocyanate compound and polybasic acid anhydride are the same as those previously described for resin (B1), etc. Although the polybasic acid anhydride can be used as a reaction raw material for resin (B4) as described above, it is preferable not to use it.

[0106] Furthermore, as a reaction raw material for the amide-imide resin (B4) having the polymerizable unsaturated group described above, polybasic acids may be used in combination with the polyisocyanate compound and polybasic acid anhydride as needed.

[0107] As the aforementioned polybasic acid, any compound having two or more carboxyl groups in one molecule can be used. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3 Examples of polybasic acids include dicarboxylic acids, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalentricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and the like. In addition, as the polybasic acid, for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile having a carboxyl group in its molecule can also be used. These polybasic acids may be used individually or in combination of two or more.

[0108] The (meth)acrylate compounds having hydroxyl groups are the same as those previously described for resins (B1), etc.

[0109] Examples of epoxy-group-containing (meth)acrylate compounds include glycidyl-group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; and mono(meth)acrylates of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. These epoxy-group-containing (meth)acrylate compounds may be used individually or in combination of two or more.

[0110] The method for producing the above-mentioned polymerizable unsaturated amide-imide resin (B4) is not particularly limited and may be produced by any method. In the production of the above-mentioned polymerizable unsaturated amide-imide resin (B4), the process may be carried out in an organic solvent as necessary, and a basic catalyst may also be used as necessary. In that case, the organic solvent and basic catalyst are the same as those previously described for resin (B1), etc.

[0111] <Acrylamide resin with polymerizable unsaturated groups (B5)> Examples of the polymerizable unsaturated acrylamide resin (B5) of this embodiment (hereinafter also referred to as resin (B5)) include those obtained by reacting a compound having a phenolic hydroxyl group with an alkylene oxide or alkylene carbonate, an N-alkoxyalkyl (meth)acrylamide compound, and, if necessary, a polybasic acid anhydride and an unsaturated monobasic acid. Although polybasic acid anhydrides can be used as reaction raw materials for resin (B5) as described above, it is preferable not to use them. It is preferable that the above resin (B5) has polymerizable unsaturated groups but does not have acid groups.

[0112] The aforementioned compound having a phenolic hydroxyl group refers to a compound having at least one phenolic hydroxyl group in its molecule. Examples of compounds having at least one phenolic hydroxyl group in its molecule include those represented by the following general formulas (10.1) to (10.5). [ka] (In the above general formulas (10.1) to (10.5), R 101 ~R 104 and R 107 Each of these independently represents one of the following: an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom. 105 and R 106 Each of these independently represents a hydrogen atom or a methyl group, and j 101 ~j 105 Each of these independently represents an integer of 0 or 1 or more, preferably an integer between 0 and 3, and more preferably 0 or 1. 101 ~k 105 Each of these independently represents an integer greater than or equal to 1, preferably 2 or 3. Furthermore, the positions of substituents on the aromatic rings in the above general formulas (10.1) to (10.5) are arbitrary. For example, in the naphthalene ring of general formula (10.2), the substituent may substitute for any hydrogen atom on the ring; in general formula (10.3), it may substitute for any hydrogen atom on the benzene ring present in one biphenyl molecule; in general formula (10.4), it may substitute for any hydrogen atom on the benzene ring present in one aralkyl molecule; and in general formula (10.5), it may substitute for any hydrogen atom on the benzene ring present in one molecule. The number of substituents in one molecule is j. 101 ~j 105 and k 101 ~k 105 This indicates that...

[0113] Furthermore, examples of compounds having phenolic hydroxyl groups include reaction products that require a compound having at least one phenolic hydroxyl group in its molecule, a compound represented by any of the following general formulas (11.1) to (11.5), and / or formaldehyde as essential reaction raw materials. In addition, novolac-type phenolic resins that use one or more compounds having at least one phenolic hydroxyl group in their molecule as reaction raw materials can also be used. [ka] (In the above general formulas (11.1) to (11.5), h 111 represents 0 or 1, R 111 ~R 116 Each of these independently represents one of the following: a monovalent aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group, k 111 ~k 116 Each of these independently represents either 0 or an integer from 1 to 4, and Z 111 ~Z 116 Each of these independently represents one of the following: a vinyl group, a halomethyl group, a hydroxymethyl group, or an alkyloxymethyl group, Y 111 n represents one of the following: an alkylene group with 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group. 111 (This represents an integer between 1 and 4.)

[0114] Specific examples of the above compounds include phenol, cresol, xylenol; dialkylphenols such as dimethylphenol and diethylphenol; trialkylphenols such as trimethylphenol and triethylphenol; diphenylphenol, triphenylphenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, tetramethylbisphenol A, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1-naphthol, 2-naphthol, 1,3-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, polyphenylene ether type diol, polynaphthylene ether type diol, phenol novolac resin, cresol novolac resin, bisphenol novolac type resin, naphthol novolac type resin, phenol aralkyl type resin, naphthol aralkyl type resin, and phenol resins having a cyclocyclic structure. The compounds having the phenolic hydroxyl group described above may be used individually or in combination of two or more.

[0115] Examples of the alkylene oxides mentioned above include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. The alkylene oxide may be used alone or in combination of two or more types. Among these, ethylene oxide or propylene oxide is preferred as the alkylene oxide.

[0116] Examples of the alkylene carbonates mentioned above include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. The alkylene carbonate may be used alone or in combination of two or more types. Among these, ethylene carbonate or propylene carbonate is preferred as the alkylene carbonate.

[0117] Examples of the above N-alkoxyalkyl(meth)acrylamide compounds include N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, and N-butoxyethyl(meth)acrylamide. The above N-alkoxyalkyl(meth)acrylamide compounds may be used individually or in combination of two or more.

[0118] The same applies to polybasic anhydrides and unsaturated monobasic acids as previously described for resins (B1), etc.

[0119] The method for producing the acrylamide resin (B5) having polymerizable unsaturated groups is not particularly limited and can be any method. In producing the acrylamide resin (B5) having polymerizable unsaturated groups, the process may be carried out in an organic solvent as needed, and a basic catalyst and an acidic catalyst may also be used as needed. In that case, the organic solvent and basic catalyst are the same as those previously described for resin (B1), etc.

[0120] Examples of the above-mentioned acidic catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid; and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Solid acid catalysts having strong acids such as sulfonyl groups can also be used. These acidic catalysts may be used individually or in combination of two or more types.

[0121] <Ester resin (B6) having polymerizable unsaturated groups> Examples of the polymerizable unsaturated ester resin (B6) of this embodiment (hereinafter also referred to as resin (B6)) include those obtained by reacting a compound having a phenolic hydroxyl group with an alkylene oxide or alkylene carbonate, an unsaturated monobasic acid, and, if necessary, a polybasic acid anhydride. As mentioned above, polybasic acid anhydrides can be used as reaction raw materials for resin (B6), but it is preferable not to use them. It is preferable that the above resin (B6) has polymerizable unsaturated groups but does not have acid groups.

[0122] The same applies to compounds having phenolic hydroxyl groups, alkylene oxides, alkylene carbonates, unsaturated monobasic acids, and polybasic acid anhydrides as previously described for resins (B1) and resins (B5), etc.

[0123] The method for producing the ester resin (B6) having polymerizable unsaturated groups described above is not particularly limited and can be any method. In producing the ester resin (B6) having polymerizable unsaturated groups described above, the process may be carried out in an organic solvent as needed, and a basic catalyst and an acidic catalyst may also be used as needed. In that case, the organic solvent, basic catalyst and acidic catalyst are the same as those described above for resins (B1) and resins (B5), etc.

[0124] (Photopolymerization initiator) The resin composition according to this embodiment contains a photopolymerization initiator. The photopolymerization initiator in this embodiment can be selected and used appropriately depending on the type of active energy ray to be irradiated, etc. It may also be used in combination with a photosensitizer such as an amine compound, urea compound, sulfur-containing compound, phosphorus-containing compound, chlorine-containing compound, or nitrile compound. Because the resin composition of this embodiment contains a photopolymerization initiator, the reaction proceeds efficiently regardless of temperature, and the time required for the resin composition to harden can be shortened. Furthermore, since the resin composition of this embodiment hardens with light, the retention of unexposed areas after development due to heating during drying is less likely to occur, and as a result, it is considered to have better developability than systems using thermal polymerization initiators. Furthermore, the photopolymerization initiator is preferably a photoradical polymerization initiator. Specific examples of such photopolymerization initiators include alkylphenone-based photopolymerization initiators such as 1-hydroxycyclohexylphenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, and 1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; acylphosphine oxide-based photopolymerization initiators such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; and intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds. Furthermore, specific examples of photopolymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthones and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethane-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one. Furthermore, commercially available photopolymerization initiators that can be used in this embodiment include, for example, "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", "Omnirad-379", "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", "Omnirad-754", "Omnirad-784", and "Omnirad-50 Examples include "0", "Omnirad-81" (manufactured by IGM), "KayaCure-DETX", "KayaCure-MBP", "KayaCure-DMBI", "KayaCure-EPA", "KayaCure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "ByCure-10", "ByCure-55" (manufactured by Stauffa Chemical), "Trigonal P1" (manufactured by Akzo), "Sandoz 1000" (manufactured by Sandoz), "Deep" (manufactured by Apjohn), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (manufactured by Ward Blenkinsop), and "Runtecure-1104" (manufactured by Runtec).

[0125] The above describes the essential components contained in the resin composition of this embodiment. The method for producing the resin composition of this embodiment is not particularly limited, and it can be produced by kneading the various components described above using a kneader such as a roller.

[0126] (Optional addition ingredient) In addition to the indan ring-containing compound (A), the polymerizable unsaturated group compound (B), and the photopolymerization initiator described above, the resin composition in this embodiment may optionally contain various known stabilizers such as UV stabilizers and preservation stabilizers, other resins, solvents, or additives. More specifically, a preferred resin composition of this embodiment may contain the above-mentioned essential components (essentially including an indan ring-containing compound (A), a polymerizable unsaturated group compound (B), and a photopolymerization initiator), and optionally, a curing agent, a solvent, other resins, and additives. Examples of the curing agents mentioned above include epoxy resins and other curing agents other than epoxy resins (hereinafter also referred to as "other curing agents"). Examples of other resins include resins other than indan ring-containing compounds (A) and compounds having polymerizable unsaturated groups (B). Furthermore, examples of additives include curing accelerators, flame retardants, fillers, pigments, defoamers, viscosity modifiers, leveling agents, preservation stabilizers, antioxidants, or UV inhibitors.

[0127] The resin composition of this embodiment may also be a so-called curable composition. In the resin composition of this embodiment, the content of the indan ring-containing compound (A) is preferably in the range of 5 to 95% by mass, and more preferably in the range of 20 to 80% by mass, in the solid content of the resin composition. In the resin composition of this embodiment, the content of compound (B) having polymerizable unsaturated groups is preferably in the range of 5 to 95% by mass, and more preferably in the range of 20 to 80% by mass, in the solid content of the resin composition.

[0128] In the resin composition of this embodiment, the content of the above-mentioned essential components is preferably 10 to 95% by mass, and more preferably 20 to 80% by mass, based on the total amount (100% by mass) of the resin composition. In the resin composition of this embodiment, the content of the curing agent is preferably 0 to 50% by mass, and more preferably 5 to 40% by mass, based on the total amount (100% by mass) of the resin composition. In the resin composition of this embodiment, the content of the additive is preferably 0 to 10% by mass, and more preferably 0.1 to 5% by mass, based on the total amount (100% by mass) of the resin composition. The following describes in detail the components that may be included in the resin composition of this embodiment, including the photopolymerization initiator, curing agent, solvent, other resins, and additives.

[0129] <Hardening agent> Examples of curing agents in this embodiment include epoxy resins and other curing agents (amine curing agents, acid anhydride curing agents, phenolic resin curing agents, etc.), with epoxy resins being preferred.

[0130] <<Epoxy resin>> The epoxy resin that is a suitable curing agent in this embodiment is not particularly limited, but it is preferably a curable resin that contains two or more epoxy groups in its molecule and can be cured by forming a crosslinked network with the epoxy groups. The epoxy resin in this embodiment is not particularly limited, but may include novolac-type epoxy resins such as phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, α-naphthol novolac-type epoxy resin, β-naphthol novolac-type epoxy resin, bisphenol A novolac-type epoxy resin, and biphenyl novolac-type epoxy resin; Aralkyl epoxy resins such as phenol aralkyl epoxy resins, naphthol aralkyl epoxy resins, and phenol biphenyl aralkyl epoxy resins; Bisphenol-type epoxy resins such as bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and tetrabromobisphenol A type epoxy resin; Biphenyl-type epoxy resins, tetramethylbiphenyl-type epoxy resins, and epoxy resins having a biphenyl skeleton and a diglycidyloxybenzene skeleton, etc. Naphthalene-type epoxy resin; Binaphthol-type epoxy resin; Binaphthyl-type epoxy resin; Dicyclopentadiene-type epoxy resins, such as dicyclopentadienephenol-type epoxy resins; Glycidylamine-type epoxy resins such as tetraglycidyldiaminodiphenylmethane-type epoxy resins, triglycidyl-p-aminophenol-type epoxy resins, and diaminodiphenylsulfone-type glycidylamine-type epoxy resins; Diglycidyl ester type epoxy resins such as 2,6-naphthalenedicarboxylic acid diglycidyl ester type epoxy resins and hexahydrophthalic anhydride glycidyl ester type epoxy resins; Examples include benzopyran-type epoxy resins such as dibenzopyran, hexamethyldibenzopyran, and 7-phenylhexamethyldibenzopyran. Of these epoxy resins, so-called glycidyl ether type epoxy resins obtained by epoxidizing phenol compounds are preferred, and among these, novolac type epoxy resins, aralkyl type epoxy resins, and dicyclopentadiene type epoxy resins are more preferred from the viewpoint of dielectric properties. The above epoxy resins may be used individually or in combination of two or more types.

[0131] The epoxy equivalent of the epoxy resin in this embodiment is preferably 120 to 400 g / eq, and more preferably 150 to 300 g / eq. A epoxy equivalent of 120 g / eq or more is preferable because it results in superior dielectric properties of the resulting cured product. On the other hand, a epoxy equivalent of 400 g / eq or less is preferable because it provides an excellent balance between adhesion and low dielectric properties of the resulting cured product.

[0132] The softening point of the epoxy resin in this embodiment is preferably 20 to 200°C, and more preferably 40 to 150°C, from the viewpoint of improving adhesion and low dielectric properties in a balanced manner.

[0133] In this embodiment, regarding the amount of epoxy resin used, when the acidic groups in compound (B) having polymerizable unsaturated groups are considered as the (total) functional groups, the functional group equivalent ratio of the amount of epoxy resin used ((compound (B) having polymerizable unsaturated groups) / epoxy resin) is more preferably 0.2 to 2, and more preferably 0.4 to 1.5. A functional group equivalent ratio of 0.2 or higher is preferable because the resulting cured product may have a lower dielectric loss tangent and higher flexibility. If the functional group equivalent ratio exceeds 2, the heat resistance and curability decrease, so it is preferable to use it within the above range.

[0134] <Other hardeners> The resin composition of this embodiment may contain, together with or in place of the epoxy resin, another curing agent. The other curing agent is not particularly limited, but examples include amine curing agents, acid anhydride curing agents, phenol resin curing agents, and the like. The above-mentioned amine curing agents are not particularly limited, but examples include aliphatic amines such as diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), diproprendiamine (DPDA), diethylaminopropylamine (DEAPA), N-aminoethylpiperazine, mensendiamine (MDA), isophoronediamine (IPDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), piperidine, N,N,-dimethylpiperazine, and triethylenediamine; and aromatic amines such as m-xylenediamine (XDA), methanephenylenediamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), benzylmethylamine, 2-(dimethylaminomethyl)phenol, and 2,4,6-tris(dimethylaminomethyl)phenol.

[0135] Examples of the above-mentioned acid anhydride curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol trimellitate, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, and methylcyclohexenedicarboxylic anhydride.

[0136] Examples of the phenol resin curing agents mentioned above include phenol novolac resin, cresol novolac resin, naphthol novolac resin, bisphenol novolac resin, biphenyl novolac resin, dicyclopentadiene-phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, triphenolmethane type resin, tetraphenolethane type resin, aminotriazine modified phenol resin, and the like. The other curing agents mentioned above may be used individually or in combination of two or more.

[0137] In this embodiment, regarding the amount of other curing agents used (amine curing agent, acid anhydride curing agent, phenol resin curing agent), when the acid groups in compound (B) having polymerizable unsaturated groups are considered as functional groups (total), the functional group equivalent ratio ((compound (B) having polymerizable unsaturated groups) / other curing agents) is more preferably 0.2 to 2, and more preferably 0.4 to 1.5. A functional group equivalent ratio of 0.2 or higher is preferable because the resulting cured product may have a lower dielectric loss tangent and higher flexibility. If the functional group equivalent ratio exceeds 2, the heat resistance and curability decrease, so it is preferable to use it within the above range.

[0138] <Other resins> The resin composition of this embodiment may contain, in addition to or in place of the epoxy resin or other curing agent, another resin. Specific examples of the aforementioned other resins are not particularly limited, but include maleimide resins, bismaleimide resins, polymaleimide resins, polyphenylene ether resins, polyimide resins, cyanate ester resins, benzoxazine resins, triazine-containing cresol novolac resins, cyanate ester resins, styrene-maleic anhydride resins, allyl group-containing resins such as diallylbisphenol and triallyl isocyanurate, polyphosphate esters, phosphate ester-carbonate copolymers, and the like. These other resins may be used individually or in combination of two or more. The content of other resins in the resin composition of this embodiment is preferably 50% by mass or less of the total.

[0139] <Solvent> The resin composition of this embodiment may be prepared without a solvent, or it may contain a solvent. The solvent has a function such as adjusting the viscosity of the resin composition. Specific examples of the aforementioned solvent are not particularly limited, but include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether and tetrahydrofuran; ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, mesitylene, 1,2,3-trimethylbenzene, and 1,2,4-trimethylbenzene; and amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These solvents may be used individually or in combination of two or more. The solvent content in the resin composition of this embodiment is preferably 0 to 90% by mass, more preferably 10 to 90% by mass, and even more preferably 20 to 80% by mass, based on the total amount (100% by mass) of the resin composition. A solvent content of 10% by mass or more is preferable because it provides excellent handling properties. On the other hand, a solvent content of 90% by mass or less is preferable from an economic standpoint.

[0140] <Additives> The resin composition of this embodiment may contain additives. Examples of such additives include curing accelerators, flame retardants, fillers, pigments, defoamers, viscosity modifiers, leveling agents, preservation stabilizers, polymerization inhibitors, antioxidants, or UV inhibitors. In other words, the resin composition of this embodiment may, as necessary and without departing from its purpose, contain appropriate amounts of other resins, solvents, curing agents, curing accelerators, flame retardants, fillers, pigments, defoamers, viscosity modifiers, leveling agents, preservation stabilizers, antioxidants, or UV inhibitors.

[0141] <<Curing accelerator>> The curing accelerator in this embodiment is not particularly limited, but examples include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, urea-based curing accelerators, and the like. The above-mentioned curing accelerators may be used individually or in combination of two or more.

[0142] Examples of the phosphorus-based curing accelerators mentioned above include organophosphine compounds such as triphenylphosphine, tributylphosphine, triparatlylphosphine, diphenylcyclohexylphosphine, and tricyclohexylphosphine; organophosphine compounds such as trimethylphosphine and triethylphosphine; and phosphonium salts such as ethyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylphosphinetriphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, butylphenylphosphonium dicyanamide, and tetrabutylphosphonium decanoate.

[0143] Examples of the above-mentioned amine-based curing accelerators include triethylamine, tributylamine, N,N-dimethyl-4-aminopyridine (DMAP), 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5,4,0]-undecene-7 (DBU), and 1,5-diazabicyclo[4,3,0]-nonene-5 (DBN).

[0144] The above imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole. Examples include ethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, and 2-methylimidazoline.

[0145] Examples of the above-mentioned guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-butylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, and 1-phenylbiguanide.

[0146] Examples of the above-mentioned urea-based curing accelerators include 3-phenyl-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, chlorophenylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, and 3-(3,4-dichlorophenyl)-1,1-dimethylurea. Of the curing accelerators mentioned above, it is preferable to use 2-ethyl-4-methylimidazole or N,N-dimethyl-4-aminopyridine (DMAP).

[0147] The content of the curing accelerator in the resin composition of this embodiment can be adjusted as appropriate to obtain the desired curability, but it is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the total amount of components (A) and (B). A curing accelerator content of 0.01 parts by mass or more is preferable because it provides excellent curability. On the other hand, a curing accelerator content of 5 parts by mass or less is preferable because it provides excellent insulation reliability. From a similar viewpoint, the curing accelerator content is more preferably 0.1 parts by mass or more, and more preferably 3 parts by mass or less, based on 100 parts by mass of the total amount of components (A) and (B).

[0148] <<Polymerization inhibitor>> The polymerization inhibitor in this embodiment is not particularly limited, but may include p-methoxyphenol (methoquinone), p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyroyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecanedihydrazide, styrene-phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, 6-ethoxy-2,2 Phenolic compounds such as 4-trimethyl-1,2-dihydroquinoline; quinone compounds such as hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, and diphenoquinone; melamine, p-phenylenediamine, 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N-(1.Amine compounds such as 3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrene-diphenylamine, reaction products of styrene-diphenylamine and 2,4,4-trimethylpentene, reaction products of diphenylamine and 2,4,4-trimethylpentene; phenothiazine, distearylthiodipropionate, 2,2-bis({[3-(dodecyl Thioether compounds such as ruthio)propionyl]oxy}methyl)-1,3-propanediyl=bis[3-(dodecylthio)propionate], ditridecane-1-yl=3,3'-sulfandiyldipropanoate; N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethylp-nitrosoaniline, p-nitrosodiphenylamine, p-nitronedimethylamine, p-nitrone -N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, nitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-Nn Nitroso compounds such as propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 1-nitroso-2-naphthol-3,6-sulfonate sodium, 2-nitroso-1-naphthol-4-sulfonate sodium, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride; esters of phosphoric acid and octadecane-1-ol, triphenyl phosphite, 3,9-dioctadecane-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5] Phosphate compounds such as undecane, trisnonylphenyl phosphite, phosphite-(1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl=diphenyl=phosphite, diphenylisodecyl phosphite, triisodecyl=phosphite, and tris(2,4-di-tert-butylphenyl) phosphite; bis(dimethyldithiocarbamato-κ(2)S,S')zinc, and diethyldithiocarbamate zinc Examples include zinc compounds such as zinc dibutyldithiocarbamate; nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel; and sulfur compounds such as 1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilaurylthiodipropionate, and 3,3'-distearyl thiodipropionate. Polymerization inhibitors may be used individually or in combination of two or more.

[0149] <<Antioxidant>> The antioxidant in this embodiment is not particularly limited, but compounds similar to those exemplified for polymerization inhibitors can be used. The antioxidant may be used alone or in combination of two or more. Examples of commercially available polymerization inhibitors and antioxidants include "Q-1300" and "Q-1301" from Wako Pure Chemical Industries, Ltd., and "Sumiriser BBM-S" and "Sumiriser GA-80" from Sumitomo Chemical Co., Ltd.

[0150] <<Flame retardant>> The flame retardant in this embodiment is not particularly limited, but examples include inorganic phosphorus-based flame retardants, organophosphorus-based flame retardants, halogen-based flame retardants, and the like. The inorganic phosphorus-based flame retardant is not particularly limited, but examples include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and polyammonium phosphate; and phosphate amides.

[0151] The above organophosphorus flame retardants are not particularly limited, but include methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, monoisodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, and stearyl acid phosphate. Phosphate esters such as isostearyl acid phosphate, oleyl acid phosphate, butyl pyrophosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, and (2-hydroxyethyl) methacrylate acid phosphate; diphenylphosphine such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and diphenylphosphine oxide; and 10-(2,5-dihydroxyphenyl)-10H-9-oxa Phosphorus-containing phenols such as -10-phosphaphenanthrene-10-oxide, 10-(1,4-dioxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinnylhydroquinone, diphenylphosphenyl-1,4-dioxynaphthalene, 1,4-cyclooctylenephosphinnyl-1,4-phenyldiol, and 1,5-cyclooctylenephosphinnyl-1,4-phenyldiol; 9,10-dihydro-9-oxa-10-phos Examples include cyclic phosphorus compounds such as phaphenanthrene-10-oxide, 10-(2,5-dihydrooxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(2,7-dihydrooxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; and compounds obtained by reacting the aforementioned phosphate esters, diphenylphosphine, or phosphorus-containing phenols with epoxy resins, aldehyde compounds, or phenolic compounds. The halogenated flame retardants mentioned above are not particularly limited, but examples include brominated polystyrene, bis(pentabromophenyl)ethane, tetrabromobisphenol A bis(dibromopropyl ether), 1,2-bis(tetrabromophthalimide), 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, and tetrabromophthalic acid. The flame retardants mentioned above may be used individually or in combination of two or more.

[0152] The amount of flame retardant in this embodiment is preferably 0.1 to 50 parts by mass, and more preferably 1 to 30 parts by mass, based on 100 parts by mass of the total amount of component (A) and component (B). An amount of flame retardant of 0.1 parts by mass or more is preferable because it can impart flame retardancy. On the other hand, an amount of flame retardant of 50 parts by mass or less is preferable because it can impart flame retardancy while maintaining dielectric properties. From a similar viewpoint, the amount of flame retardant is more preferably 1 part by mass or more, and more preferably 30 parts by mass or less, based on 100 parts by mass of the total amount of component (A) and component (B).

[0153] <<Filler>> Examples of fillers in this embodiment include organic fillers and inorganic fillers. Organic fillers have functions such as improving elongation and improving mechanical strength. Inorganic fillers have functions such as reducing the coefficient of thermal expansion and providing flame retardancy. The aforementioned organic filler is not particularly limited, but examples include polyamide particles. The inorganic fillers mentioned above are not particularly limited, but include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, carbon black, etc. Of these, silica is preferred. In this case, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. can be used as silica.

[0154] Furthermore, the above-mentioned fillers may be surface-treated as needed. In this case, there are no particular limitations on the surface treatment agents that can be used, but aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents, etc. Specific examples of surface treatment agents include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, hexamethyldisilazane, etc. The above-mentioned fillers may be used individually or in combination of two or more types.

[0155] The filler content in this embodiment is preferably 0.5 to 95 parts by mass, and more preferably 5 to 80 parts by mass, based on 100 parts by mass of the total amount of components (A) and (B). A filler content of 0.5 parts by mass or more is preferable because it allows for sufficient impartment of the filler's effect. On the other hand, to avoid increasing the viscosity of the compound and impairing moldability, the filler content is preferably 95 parts by mass or less. From a similar viewpoint, the filler content is more preferably 5 parts by mass or more, and more preferably 80 parts by mass or less, based on 100 parts by mass of the total amount of components (A) and (B). The method for producing the resin composition of this embodiment is not particularly limited, and it can be produced by kneading the various components described above using a kneader such as a roller.

[0156] [Cured product] The cured product in this embodiment is obtained by curing the resin composition described above. That is, the resin composition of this embodiment can also be used as a so-called curable composition. Since the indan ring-containing compound (A) contained in the resin composition itself has substantially no polar functional groups and therefore has a low dielectric loss tangent, the cured product obtained from the resin composition also has a low dielectric loss tangent, and the resulting cured product can exhibit flexibility, adhesion to metals such as copper foil due to its flexibility, and low dielectric properties, which is a desirable embodiment. The cured product of this embodiment can be obtained by irradiating the resin composition with active energy rays. Examples of active energy rays include ionizing radiation such as ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays. When ultraviolet rays are used as the active energy rays, the irradiation may be carried out under an inert gas atmosphere such as nitrogen gas, or under an air atmosphere, in order to efficiently carry out the curing reaction by ultraviolet rays.

[0157] In this embodiment, ultraviolet lamps are generally used as ultraviolet light sources for practical and economic reasons. Specifically, examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs. The integrated light intensity of the aforementioned active energy rays is not particularly limited, but is between 0.1 and 50 kJ / m 2 Preferably, it is 0.5 to 10 kJ / m³. 2 It is more preferable that the cumulative light amount is within the above range, as this can prevent or suppress the occurrence of uncured areas. The irradiation of the active energy ray may be performed in one stage or in two or more stages.

[0158] Applications for the resin composition or cured product in this embodiment include printed circuit board materials, resin compositions for flexible wiring boards, interlayer insulating materials for build-up substrates, insulating materials for circuit boards such as build-up adhesive films, resin casting materials, adhesives, semiconductor encapsulation materials, semiconductor devices, prepregs, conductive pastes, build-up films, build-up substrates, fiber-reinforced composite materials, and molded products obtained by curing the above composite materials. Among these various applications, in the applications of printed circuit board materials, insulating materials for circuit boards, and build-up adhesive films, the resin composition of the present invention can be used as an insulating material for so-called electronic component-embedded substrates in which passive components such as capacitors and active components such as IC chips are embedded within the substrate. Furthermore, among the above, taking advantage of the excellent flexibility, adhesion, low dielectric properties, and heat resistance of the cured product, the resin composition of the present invention is preferably used in semiconductor encapsulation materials, semiconductor devices, prepregs, flexible wiring boards, circuit boards, build-up films, build-up substrates, multilayer printed circuit boards, fiber-reinforced composite materials, and molded products obtained by curing the above composite materials.

[0159] [Goods] The article of this embodiment is characterized by having a coating made of the cured material described above. In the article of this embodiment, the coating can function as an insulating material with excellent heat resistance and coating appearance.

[0160] The article of this embodiment is typically a printed circuit board or a substrate for a semiconductor package, wherein a solder resist film (the coating film described above) is formed in appropriate locations on the surface.

[0161] [Insulating materials] The insulating material in this embodiment consists of the resin composition described above. Examples of such insulating materials include the interlayer insulating material for build-up substrates, insulating materials for circuit boards such as build-up adhesive films, insulating materials for circuit boards, and insulating materials for substrates for embedding electronic components. For example, a method for manufacturing a build-up substrate from the above resin composition consists of the following three steps. The first step is to apply the above resin composition, which is appropriately blended with rubber, fillers, etc., to a circuit board on which circuits have been formed, using a spray coating method, a curtain coating method, etc., and then cure it. The second step is to then drill holes such as predetermined through-holes as needed, treat with a roughening agent, wash the surface with hot water to form irregularities, and then plate with a metal such as copper. The third step is to repeat these operations sequentially as desired to alternately build up and form a resin insulating layer and a conductor layer of a predetermined circuit pattern. It is preferable to drill the through-holes after the formation of the outermost resin insulating layer. The first step can be carried out not only by the solution coating method described above, but also by laminating a build-up film that has been pre-coated to a desired thickness and dried. Furthermore, the build-up substrate of the present invention can also be manufactured by forming a roughened surface and omitting the plating process by heating and pressing a resin-coated copper foil, on which the resin composition has been semi-cured, onto a wiring board on which a circuit has been formed, at 170-250°C.

[0162] [Resist material] The resist member in this embodiment consists of the resin composition described above. The resist member can be obtained, for example, by coating the resin composition onto a substrate, volatilizing and drying the organic solvent in a temperature range of about 60 to 100°C, exposing it to active energy rays through a photomask on which a desired pattern has been formed, developing the unexposed areas with an alkaline aqueous solution, and further heating and curing it in a temperature range of about 140 to 180°C if necessary. The resist member of this embodiment has excellent low dielectric properties and elongation. [Examples]

[0163] Examples are given below to explain the present invention in more detail, but the present invention is not limited to the following examples. In the following, "parts" and "%" are based on mass unless otherwise specified. In addition, for GPC measurement, 1 1H-NMR measurement, 13 13C-NMR measurement, FD-MS spectrum measurement, the measurements were carried out under the following conditions and the like.

[0164] (Evaluation method) <GPC measurement> Using the following measuring apparatus and measuring conditions, GPC charts of the indane ring-containing compound (A) and the compound (B) having a polymerizable unsaturated group obtained in the following synthesis examples, examples, etc. were obtained. From the results of the GPC chart, it was confirmed that the target products (the indane ring-containing compound (A) and the compound (B) having a polymerizable unsaturated group) were produced from the decrease and disappearance of the raw material peaks. Measuring apparatus: "HLC-8320 GPC" manufactured by Tosoh Corporation Column: Guard column "HXL-L" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation Detector: RI (differential refractometer) Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation Measuring conditions: Column temperature 40°C Developing solvent: Tetrahydrofuran Flow rate: 1.0 ml / min Standard: In accordance with the measurement manual of the "GPC Workstation EcoSEC-WorkStation", the following monodisperse polystyrene with a known molecular weight was used. (Polystyrene used) "A-500" manufactured by Tosoh Corporation "A-1000" manufactured by Tosoh Corporation "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation "F-80" manufactured by Tosoh Corporation "F-128" manufactured by Tosoh Corporation Sample: A 50 μl solution of indane ring-containing compounds (A-1) to (A-5), condensed ring compounds (C-1), and compounds (B-1) having a polymerizable unsaturated group, each obtained in the following synthesis examples, examples, etc., in tetrahydrofuran at 1.0% by mass on a solid content basis, filtered through a microfilter, was used.

[0165] <FD-MS Spectrum Measurement> The FD-MS spectrum was measured using the following measuring apparatus and measurement conditions. From this result, mass peaks corresponding to the target products (indane ring-containing compounds (A-1) to (A-5) and condensed ring compounds (C-1)) were confirmed. Measuring apparatus: JMS-T100GC AccuTOF Measurement conditions Measurement range: m / z = 4.00 to 2000.00 Rate of change: 51.2 mA / min Final current value: 45 mA Cathode voltage: -10 kV Recording interval: 0.07 sec

[0166] < 1 <1H-NMR Measurement> 1 1H-NMR: "JNM-ECA600" manufactured by JEOL RESONANCE Magnetic field strength: 600 MHz Number of integrations: 32 times Solvent: DMSO-d6 Sample concentration: 30% by mass The above 1The results of the 1H-NMR chart confirmed the presence of peaks originating from the target product, thus confirming that the target product was obtained in each reaction. < 13 C-NMR measurement> 13 C-NMR: “JNM-ECA600” manufactured by JEOL RESONANCE Magnetic field strength: 150MHz Total number of times: 320 Solvent: DMSO-d6 Sample concentration: 30% by mass The aforementioned 13 The results of the 1C-NMR chart confirmed the presence of peaks originating from the target product, thus confirming that the target product was obtained in each reaction.

[0167] <Quantitative determination of unsaturated bonds> The amount of unsaturated bonds was calculated using the method for quantifying unsaturated bonds described in Japanese Patent Publication No. 2012-214728.

[0168] <Preparation of test specimens and measurement of peel strength (evaluation of adhesion)> -Preparation of test specimens- The resin compositions obtained in each example and comparative example were applied to copper foil (Furukawa Sangyo Co., Ltd., electrolytic copper foil "F2-WS", 18 μm) using a 50 μm applicator and dried at 80°C for 30 minutes. Then, 1000 mJ / cm² was measured using a metal halide lamp. 2 After irradiating the coating with ultraviolet light, it was heated at 160°C for 1 hour to obtain test piece 1. - Peel strength measurement (evaluation of adhesion) - Adhesion was evaluated by measuring the peel strength as described below. The above test piece 1 was cut to a size of 1 cm in width and 12 cm in length, and the 90° peel strength (N / cm) was measured using a peel tester (A&D Tensilon, manufactured by A&D Corporation, with a peeling speed of 50 mm / min).

[0169] <Measurement of dielectric constant and dielectric loss tangent (evaluation of dielectric properties)> The resin compositions obtained in each example and comparative example were applied to a glass substrate to a thickness of 50 μm using an applicator and dried at 80°C for 30 minutes. Then, a metal halide lamp was used to measure 1000 mJ / cm². 2 After irradiation with ultraviolet light, the material was heated at 160°C for 1 hour to obtain a cured coating. Next, the cured coating was peeled off the glass substrate to obtain a cured product. Then, the cured product was stored in a room at 23°C and 50% humidity for 24 hours to obtain test piece 2, and the dielectric constant and dielectric loss tangent of the test piece at 1 GHz were measured using the cavity resonance method with an Agilent Technologies, Inc. network analyzer "4291B RF Impedance Material Analyzer, 16453A".

[0170] (Synthesis Example 1) Synthesis of indane ring-containing compound (A-1) In a 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer, 40.6g (0.30mol) of 2,4,6-trimethylaniline, 582.8g (3.0mol) of α,α'-dihydroxy-1,3-diisopropylbenzene, 600.0g of xylene, and 62.3g of activated clay were charged and heated to 120°C while stirring. The mixture was then heated to 200°C while removing the distillate using a Dean-Stark tube, and the reaction was allowed to proceed for 8 hours. After the reaction, the mixture was air-cooled to room temperature, diluted with 500g of toluene, and the activated clay was removed by filtration. Low molecular weight substances such as solvent and unreacted materials were then removed under reduced pressure to obtain 384g of indan ring-containing compound (A-1). The chemical structure and characterization of the indan ring-containing compound (A-1) were analyzed by GPC, FD-MS, and 13 This was confirmed using 1C-NMR. As a result, the number-average molecular weight (Mw) of the indan ring-containing compound (A-1) was 845. Furthermore, the FD-MS spectral results of the indan ring-containing compound (A-1) showed M + Peaks at =316, 474, and 632 were observed. Furthermore, in the FD-MS spectral results of the indan ring-containing compound (A-1), M +Peaks at 293, 451, and 610 were also observed, confirming that the indan ring-containing compound (A-1) contains a compound with an aniline skeleton (corresponding to general formula (2) or general formula (3)). Furthermore, the indan ring-containing compound (A-1) exhibited UV curability. In addition, it was confirmed that the number of alkenyl groups (unsaturated bonds) per molecule of the obtained indan ring-containing compound (A-1) was in the range of 1 to 10 on average. For reference, the GPC chart (Figure 1), FD-MS chart (Figure 6), and 13 The 1C-NMR chart (Figure 7) is shown. Therefore, based on the MS and NMR measurement results, the indan ring-containing compound (A-1) obtained in Synthesis Example 1 is considered to be a mixture of the compound represented by the following formula (A-1.1) and the compound represented by the above general formula (1c). [ka]

[0171] (Synthesis Example 2) Synthesis of indane ring-containing compound (A-2) 56.7 g (0.40 mol) of 2,4,6-trimethylaniline, 666.7 g (4.20 mol) of diisopropenylbenzene, 700.0 g of xylene, and 133.3 g of activated clay were charged into a 2 L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer, and heated to 120°C while stirring. The temperature was further increased to 180°C while removing the distillate using a Dean-Stark tube, and the reaction was carried out for 5 hours. After the reaction, the mixture was air-cooled to room temperature, diluted with xylene, the activated clay was removed by filtration, and the solvent and low molecular weight substances such as unreacted materials were removed under reduced pressure to obtain the indan ring-containing compound (A-2). The chemical structure and characterization of the indan ring-containing compound (A-2) were analyzed by GPC, FD-MS, and 13 This was confirmed using 1C-NMR. As a result, the number-average molecular weight (Mw) of the indan ring-containing compound (A-2) was 814. The FD-MS spectral results of the indan ring-containing compound (A-2) showed M +Peaks at =316, 474, and 632 were observed. Furthermore, in the FD-MS spectral results of the indan ring-containing compound (A-2), M + Peaks at 293, 451, and 610 were also observed, confirming that the indan ring-containing compound (A-2) contains a compound with an aniline skeleton (corresponding to general formula (2) or general formula (3)). Furthermore, the indan ring-containing compound (A-2) exhibited UV curability. In addition, it was confirmed that the number of alkenyl groups (unsaturated bonds) per molecule of the obtained indan ring-containing compound (A-2) was in the range of 1 to 10 on average. For reference, Figure 2 shows the GPC chart of the indan ring-containing compound (A-2) obtained in synthesis example 2. Furthermore, the indane ring-containing compound (A-2) obtained in Synthesis Example 2 was obtained in the same manner as in Synthesis Example 1. 13 ¹¹C-NMR measurements revealed a peak chart similar to that of the indan ring-containing compound (A-1) in Synthesis Example 1. Therefore, it is considered that the indan ring-containing compound (A-2) is a mixture of the compound represented by the following formula (A-2.1) and the compound represented by the above general formula (1c). [ka]

[0172] (Synthesis Example 3) Synthesis of an indane ring-containing compound (A-3) In a 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer, 25.3g (0.13mol) of 2-trifluoromethylaniline, 333.3g (1.73mol) of α,α'-dihydroxy-1,3-diisopropylbenzene, 340.0g of xylene, and 66.7g of activated clay were charged and heated to 120°C while stirring. The mixture was then heated to 180°C while removing the distillate using a Dean-Stark tube, and the reaction was allowed to proceed for 5 hours. After the reaction, the mixture was air-cooled to room temperature, diluted with xylene, the activated clay was removed by filtration, and the solvent and other low molecular weight substances such as unreacted materials were removed under reduced pressure to obtain the indan ring-containing compound (A-3). The chemical structure and characterization of the indan ring-containing compound (A-3) were performed by GPC, FD-MS, and 13This was confirmed using 1C-NMR. As a result, the number-average molecular weight (Mw) of the indan ring-containing compound (A-3) was 689. The FD-MS spectral result of the indan ring-containing compound (A-3) showed M + Peaks at =316, 474, and 632 were observed. Furthermore, in the FD-MS spectral results of the indan ring-containing compound (A-3), M + Peaks at 319, 478, and 636 were also observed, confirming that the indan ring-containing compound (A-3) contains a compound with an aniline skeleton (corresponding to general formula (2) or general formula (3)). Furthermore, the indan ring-containing compound (A-3) exhibited UV curability. In addition, it was confirmed that the number of alkenyl groups (unsaturated bonds) per molecule of the obtained indan ring-containing compound (A-3) was in the range of 1 to 10 on average. For reference, Figure 3 shows the GPC chart of the indan ring-containing compound (A-3) obtained in synthesis example 3. Furthermore, the indane ring-containing compound (A-3) obtained in Synthesis Example 3 was obtained in the same manner as in Synthesis Example 1. 13 ¹¹C-NMR measurements revealed a peak chart similar to that of the indan ring-containing compound (A-1) in Synthesis Example 1. Therefore, it is considered that the indan ring-containing compound (A-3) is a mixture of the compound represented by the following formula (A-3.1) and the compound represented by the above general formula (1c). [ka]

[0173] (Synthesis Example 4) Synthesis of an indane ring-containing compound (A-4) In a 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer, 31.4g (0.20mol) of diethyltoluenediamine, 333.3g (1.73mol) of α,α'-dihydroxy-1,3-diisopropylbenzene, 340.0g of xylene, and 66.7g of activated clay were charged and heated to 120°C while stirring. The temperature was further increased to 180°C while removing the distillate using a Dean-Stark tube, and the reaction was allowed to proceed for 5 hours. After the reaction, the mixture was air-cooled to room temperature, diluted with xylene, the activated clay was removed by filtration, and the solvent and low molecular weight substances such as unreacted materials were removed under reduced pressure to obtain the indan ring-containing compound (A-4). The chemical structure and characterization of the indan ring-containing compound (A-4) were analyzed by GPC, FD-MS, and 13 This was confirmed using 1C-NMR. As a result, the number-average molecular weight (Mw) of the indan ring-containing compound (A-4) was 393. The FD-MS spectral result of the indan ring-containing compound (A-4) showed M + Peaks at =316, 474, and 632 were observed. Furthermore, in the FD-MS spectral results of the indan ring-containing compound (A-4), M + Peaks at 337, 494, and 653 were also observed, confirming that the indan ring-containing compound (A-4) contains a compound with an aniline skeleton (corresponding to general formula (2) or general formula (3)). Furthermore, the indan ring-containing compound (A-4) exhibited UV curability. In addition, it was confirmed that the number of alkenyl groups (unsaturated bonds) per molecule of the obtained indan ring-containing compound (A-4) was in the range of 1 to 10 on average. For reference, Figure 4 shows the GPC chart of the indan ring-containing compound (A-4) obtained in synthesis example 4. Furthermore, the indane ring-containing compound (A-4) obtained in Synthesis Example 4 was obtained in the same manner as in Synthesis Example 1. 13 ¹¹C-NMR measurements revealed a peak chart similar to that of the indan ring-containing compound (A-1) in Synthesis Example 1. Therefore, it is considered that the indan ring-containing compound (A-4) is a mixture of the compound represented by the following formula (A-4.1) and the compound represented by the above general formula (1c). [ka]

[0174] (Synthesis Example 5) Synthesis of an indan ring-containing compound (A-5) In a 2L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer, 10.2g (0.07mol) of 2,4,6-trimethylaniline, 100.0g (0.51mol) of α,α'-dihydroxy-1,4-diisopropylbenzene, 300.0g of xylene, and 23.5g of activated clay were charged and heated to 120°C while stirring. The mixture was then heated to 180°C while removing the distillate using a Dean-Stark tube, and the reaction was allowed to proceed for 5 hours. After the reaction, the mixture was air-cooled to room temperature, diluted with xylene, the activated clay was removed by filtration, and the solvent and low molecular weight substances such as unreacted materials were removed under reduced pressure to obtain the indan ring-containing compound (A-5). The chemical structure and characterization of the indan ring-containing compound (A-5) were performed by GPC, FD-MS, and 13 This was confirmed using 1C-NMR. As a result, the number-average molecular weight (Mw) of the indan ring-containing compound (A-5) was 1142. The FD-MS spectral result of the indan ring-containing compound (A-5) showed M + Peaks at =316, 474, and 632 were observed. Furthermore, in the FD-MS spectral results of the indan ring-containing compound (A-5), M + Peaks at 293, 451, and 610 were also observed, confirming that the indan ring-containing compound (A-5) contains a compound with an aniline skeleton (corresponding to general formula (2) or general formula (3)). Furthermore, the indan ring-containing compound (A-5) exhibited UV curability. In addition, it was confirmed that the number of alkenyl groups (unsaturated bonds) per molecule of the obtained indan ring-containing compound (A-5) was in the range of 1 to 10 on average. For reference, Figure 5 shows the GPC chart of the indan ring-containing compound (A-5) obtained in synthesis example 5. Furthermore, the indane ring-containing compound (A-5) obtained in Synthesis Example 5 was obtained in the same manner as in Example 1. 13¹¹C-NMR measurements revealed a peak chart similar to that of the indan ring-containing compound (A-1) in Synthesis Example 1. Therefore, it is considered that the indan ring-containing compound (A-5) is a mixture of the compound represented by the following formula (A-5.1) and the compound represented by the above general formula (1c). [ka]

[0175] (Synthesis Example 6) Synthesis of an indane ring-containing compound (A-6) By purifying the indan ring-containing compound (A-1) using a silica gel column, the indan ring-containing compound (A1) having an aniline skeleton represented by the general formula (1c) was adsorbed, and the indan ring-containing compound (A-6) represented by the general formula (A-1.1) was prepared. As the developing solvent for the silica gel column, a mixed solvent of hexane and ethyl acetate in a volume ratio of 30:1 was used. When the obtained indan ring-containing compound (A-6) was measured by FD-MS, no peak originating from the indan ring-containing compound (A1) having an aniline skeleton represented by the general formula (1c) could be confirmed.

[0176] (Synthesis Example 7) Synthesis of Compound (B-1) Having Polymerizable Unsaturated Groups In a flask equipped with a thermometer, stirrer, and reflux condenser, 188 parts by mass of bisphenol A type epoxy resin (DIC Corporation's "EPICLON 850-S", epoxy equivalent 188 g / equivalent) was charged. After adding 0.3 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone as a thermal polymerization inhibitor, 72 parts by mass of acrylic acid and 1.3 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120°C for 8 hours while blowing in air to obtain compound (B-1) having polymerizable unsaturated groups.

[0177] (Comparative synthesis example 1) Synthesis of condensed ring compound (C1) In a flask equipped with a thermometer, condenser, and stirrer, 72.0 parts by mass of norbornene, 25.0 parts by mass of DVB-810 (manufactured by Nippon Steel Chemical & Material Co., Ltd., containing 81% by mass of divinylbenzene and 19% by mass of ethylstyrene), and 75.0 parts by mass of DVB-570 (manufactured by Nippon Steel Chemical & Material Co., Ltd., containing 57% by mass of divinylbenzene and 43% by mass of ethylstyrene) were charged to adjust the charge amount to 0.63 moles of divinylbenzene and 0.37 moles of ethylstyrene per mole of norbornene. Subsequently, 35.6 parts by mass of butyl acetate and 114.7 parts by mass of toluene were charged, and the temperature was raised to 70°C while stirring. The trifluoroborane diethyl ether complex was added, and the reaction was carried out at the same temperature for 6 hours to obtain the reaction solution. After the reaction was complete, the solution was neutralized with an aqueous sodium bicarbonate solution, the catalyst residue was removed by washing with water, and volatile components were removed under reduced pressure at 60°C to obtain the condensed ring compound (C1).

[0178] (Examples 1-6: Preparation and evaluation of resin compositions) The indene ring compounds (A-1) to (A-6) obtained in the above synthesis example, a compound having a polymerizable unsaturated group (B-1), a photopolymerization initiator ("Omnirad 907" from IGM Resins), an organic solvent (methyl ethyl ketone), and 2-ethyl-4-methylimidazole as a curing accelerator were mixed in the compositional ratios shown in Table 1 to obtain resin compositions (1) to (6). Then, following the procedure of the evaluation method described in the (Evaluation Method) section above, the peel strength (adhesion) and dielectric properties (dielectric constant and dielectric loss tangent) of the resin compositions (1) to (6) were evaluated. The results are shown in Table 1 below.

[0179] (Comparative Example 1: Preparation and Evaluation of Composition) Similar to Examples 1-6, each component was mixed in the composition ratios shown in Table 1 to obtain comparative resin composition (C1) for Comparative Example 1. Then, the peel strength (adhesion), dielectric constant, and dielectric loss tangent of comparative resin composition (C1) for Comparative Example 1 were evaluated according to the evaluation method procedure described in the (Evaluation Method) section above. The results are shown in Table 1 below.

[0180] [Table 1]

[0181] The results in Table 1 confirm that the resin composition of the example exhibits superior adhesion and low dielectric properties in the resulting cured product compared to the comparative resin composition of the comparative example. [Industrial applicability]

[0182] According to this disclosure, it is possible to provide a resin composition that can exhibit excellent adhesion and low dielectric properties in the resulting cured product, and a cured product and article obtained using the resin composition.

Claims

1. An indane-based mixture comprising an indane ring-containing compound (A) having a structural unit represented by the following general formula (1a), wherein at least one of the terminal sites bonded to the structural unit is an alkenyl group, and an indane ring-containing compound (A1) having an aniline skeleton, Compound (B) having a polymerizable unsaturated group, A resin composition containing a photopolymerization initiator. 【Chemistry 1】 (In the above general formula (1a), R １１ , R １２ and R １３ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n １２ (This represents the number of repeating units.)

2. The resin composition according to claim 1, wherein the mass ratio of the solid content of the indan ring-containing compound (A) and the polymerizable unsaturated group-containing compound (B) [(A) / (B)] is in the range of 1 / 100 to 100 / 100.

3. The indane ring-containing compound (A) is given by the following general formula (1b): 【Chemistry 2】 (In the above general formula (1b), R １１ , R １２ and R １３ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Q １１ 、 Q １２ 、 L １１ 及び L １２ each independently represents a single bond or an alkylene group having 1 to 8 carbon atoms, P １１ and P １２ Each of these independently represents a hydrogen atom, a polar group, an alkyl group having 1 to 6 carbon atoms which may be substituted with the polar group, an alkenyl group having 2 to 10 carbon atoms, or the following general formula (2), M １１ and M １２ Each of these independently represents a single bond or the following general formula (3): n １２ represents the average number of repeating units, n １１ and n １３ Each of these independently represents a number from 0 to 20. However, P １１ and P １２ At least one of them is an alkenyl group having 2 to 10 carbon atoms. 【Transformation 3】 [In the above general formula (2), R １５ Each of these independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms, n ２ This represents an integer between 0 and 4 (inclusive). [In the above general formula (3), R １６ Each of these independently represents an amino group, a fluoroalkyl group, or an alkyl group having 1 to 3 carbon atoms, n ３ This represents an integer between 0 and 4 (inclusive). The resin composition according to claim 1 or 2, represented by the general formulas (2) and (3), wherein the asterisk (*) in the general formulas (2) and (3) represents bonding with other atoms.

4. A cured product of the resin composition according to claim 1 or 2.

5. An article characterized by having a coating film made of the cured product described in claim 4.

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