Compound, curable composition, cured product, and electronic component

Abstract

To provide a new compound soluble in various solvents, a curable composition containing the compound, a cured product obtained by curing the curable composition, and an electronic component having the cured product.SOLUTION: The compound has a structure represented by the following formula (1). {wherein R1 and R3 are independently single bonds, ether bonds, or ester bonds; R2 is a divalent organic group having a phenyleneether structure; R4 are independently hydrogen atoms or organic groups; X is a divalent organic group having a cage silsesquioxane having two or more carbon-carbon double bonds as a basic structure; Y1 and Y2 are independently single bonds or the like} SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a compound, a curable composition, a cured product, and an electronic component. [Background technology]

[0002] In recent years, with the spread of high-capacity, high-speed communications such as fifth-generation communication systems (5G) and millimeter-wave radar for automotive ADAS (Advanced Driver Assistance Systems), signals from electronic devices are becoming increasingly high-frequency.

[0003] For the printed wiring boards built into such electronic devices, curable compositions mainly composed of epoxy resins have been used as interlayer insulating materials, but there is a demand for low-dielectric materials that are easier to process. For example, Non-Patent Document 1 proposes polyphenylene ether, which is one of the low-dielectric materials. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] J.Nunoshige, H.Akahoshi, Y.Shibasaki, M.Ueda, J.Polym.Sci.Part.A:Polym.Chem.2008,46,5278-5282. Summary of the Invention [Problem to be solved by the invention]

[0005] Such conventional polyphenylene ethers have low solvent solubility, which can cause problems in work. For example, the polyphenylene ethers described in Non-Patent Document 1 exhibit high solubility only in highly toxic solvents (chloroform, toluene, etc.), and have low solubility in other solvents. This has led to problems such as difficulty in handling the resin varnish and controlling solvent exposure in the process of forming a coating and curing it for wiring board applications.

[0006] Therefore, the problem to be solved by the present invention is to provide: a novel compound that is soluble in various solvents (solvents other than highly toxic organic solvents, such as cyclohexanone); a curable composition containing the compound; a cured product obtained by curing the curable composition; and an electronic component having the cured product. [Means for solving the problem]

[0007] One aspect of the present invention is a compound having a structure represented by the following formula (1): [ka] {In formula (1), R1 and R3 are each independently a single bond, an ether bond, or an ester bond. R2 is a divalent organic group having a phenylene ether structure. R4s are each independently a hydrogen atom or an organic group, and may be the same or different groups. X is a divalent organic group having a cage-shaped silsesquioxane basic structure having two or more carbon-carbon double bonds. Y1 and Y2 are each independently a single bond or any one selected from the following formula (2).} [ka] {In formula (2), R a are each independently a hydrogen atom or an organic group, and may be the same or different groups; R a When there are two or more R b is a single bond or a divalent organic group. * indicates a bonding site.}

[0008] In the compound of the above aspect, the X is preferably a divalent organic group having a cage silsesquioxane as a basic structure, as represented by the following formula (3). [ka] In formula (3), R5 and R6 are organic groups independent of each other and may be the same or different groups. * indicates a bonding site.

[0009] Another aspect of the present invention is a compound represented by the following formula (4): [ka] {In formula (4), R1 to R4, Y1, and Y2 are as defined above. Z's are each independently a bromo group, a chloro group, an iodo group, or a triflate group, and may be the same group or different groups.}

[0010] Another aspect of the present invention is a curable composition, the curable composition comprising a compound according to the above aspect.

[0011] Another aspect of the present invention is a cured product obtained by curing the curable composition of the above aspect.

[0012] Another aspect of the present invention is an electronic component, which has the cured product of the above aspect. [Effects of the Invention]

[0013] According to the present invention, it is possible to provide: a novel compound that is soluble in various solvents (solvents other than highly toxic organic solvents, such as cyclohexanone); a curable composition containing the compound; a cured product obtained by curing the curable composition; and an electronic component having the cured product. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 shows the results of 1H-NMR analysis of the compound (A1) of Example 1. [Figure 2] FIG. 2 shows the results of 1H-NMR analysis of the compound (A2) of Example 2. [Figure 3] FIG. 3 shows the results of 1H-NMR analysis of compound (B) of the synthesis example. DETAILED DESCRIPTION OF THE INVENTION

[0015] Hereinafter, embodiments of the present invention will be described in detail. In this specification, the expression "a to b" in the description of a numerical range means that the range is from a to b, unless otherwise specified.

[0016] In this specification, when the upper and lower limits of a numerical range are separately stated, all combinations of each lower limit and each upper limit are considered to be substantially stated within a consistent range.

[0017] In this specification, "(meth)acrylic" is meant to encompass both "acrylic" and "methacrylic." Also, "(meth)acrylate" is meant to encompass both "acrylate" and "methacrylate." Furthermore, "(meth)acryloyl group" is meant to encompass both "acryloyl group" and "methacryloyl group." Similarly, "(iso)cyanurate" is meant to encompass both "isocyanurate" and "cyanurate."

[0018] In the present specification, when isomers exist in the compounds described, all possible isomers can be used in the present invention unless otherwise specified.

[0019] In this specification, the term "substituent" is not particularly limited, and unless otherwise specified, examples thereof include a hydroxyl group, a phenoxy group, an alkoxy group, a phenyl group, a halogen group, a thiol group, a sulfo group, an amino group, an imino group, a hydroxyamino group, a nitro group, a nitroso group, a carboxy group, a thiocarboxy group, an ester group, a thioester group, an aldehyde group, an acetyl group, and the like.

[0020] In this specification, the term "solid content" is used to mean non-volatile content (components other than volatile components such as solvents).

[0021] 1. Compound A Compound A of this embodiment has a structure represented by the following formula (1). [ka] {In formula (1), R1 and R3 are each independently a single bond, an ether bond, or an ester bond. R2 is a divalent organic group having a phenylene ether structure. R4s are each independently a hydrogen atom or an organic group, and may be the same or different groups. X is a divalent organic group having a cage-shaped silsesquioxane basic structure having two or more carbon-carbon double bonds. Y1 and Y2 are each independently a single bond or any one selected from the following formula (2).} [ka] {In formula (2), R a are each independently a hydrogen atom or an organic group, and may be the same or different groups; R a When there are two or more R b is a single bond or a divalent organic group. * indicates a bonding site.}

[0022] Compound A of this embodiment is a novel compound, and X in the above formula (1) described below is a divalent organic group having a cage-shaped silsesquioxane structure having two or more carbon-carbon double bonds as a basic structure. Since X in the above formula (1) is a bulky silsesquioxane structure, it is presumed that this reduces the crystallinity of the phenylene ether, and therefore compound A is soluble in solvents other than highly toxic organic solvents, such as cyclohexanone. The above formulas (1) and (2) are described in detail below.

[0023] In formula (1), as described above, R1 and R3 are each independently a single bond, an ether bond, or an ester bond. Among these, an ether bond is preferred. When R1 and R3 are each an ester bond, it is preferred that the carbon atom in the ester bond is directly bonded to Y1 or Y2.

[0024] In formula (1), R2 is a divalent organic group having a phenylene ether structure, as described above. R2 is preferably a divalent organic group having a polyphenylene ether structure in which the phenylene ether structure is a repeating unit. R2 may further have a structure other than the phenylene ether structure (e.g., a biphenyl skeleton, a diphenylthioether skeleton, a benzophenone skeleton, a diphenylmethane skeleton, a 1,2-diphenylethane skeleton, a 1,3-diphenylpropane skeleton, a 2,2-diphenylpropane skeleton, a diphenylhexafluoropropane skeleton, a diphenyl sulfoxide skeleton, a diphenyl sulfone skeleton, or the like). The phenylene ether structure may have a substituent. The substituent is not particularly limited, and examples thereof include a methyl group, an allyl group, a vinyl group, a tert-butyl group, and a phenyl group.

[0025] In formula (1), R2 is particularly preferably represented by the following formula (1a). [ka] {In formula (1a), Y represents an oxygen atom or an alkylene group having 1 to 10 carbon atoms, n represents an integer of 1 to 100, and m represents an integer of 1 to 100. * represents a bonding site.}

[0026] In formula (1a), Y is preferably a methylene group or a dimethylmethylene group, and more preferably a dimethylmethylene group.

[0027] In formula (1), R4 is not limited as long as it is a hydrogen atom or an organic group that is independent of each other. Examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, and an alkanol group. Among these, R4 is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group.

[0028] In formula (1), Y1 and Y2 are, as described above, independent of each other, a single bond or any one selected from the above formula (2).

[0029] In formula (2), R a are not particularly limited as long as they are each independently a hydrogen atom or an organic group. Examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, and an alkanol group. Among these, R a is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group. In addition, * in formula (2) indicates a bonding site, and R b The * on one side indicates the bonding site to R1 or R3 in formula (1), and the * on the other side indicates the bonding site to X in formula (1).

[0030] In formula (2), R a If there are two or more, R a may form a ring together. In this case, R a The ring formed by is preferably, for example, a cycloalkene ring, an aromatic hydrocarbon ring, or an aromatic heterocyclic ring, and may have a substituent. It may also be a monocyclic ring or a polycyclic ring. Examples of the cycloalkene ring include a cyclopentene ring and a cyclohexene ring. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, a fluorene ring, a phenanthrene ring, and an anthracene ring. Examples of the aromatic heterocyclic ring include a furan ring, a thiophene ring, a pyrrole ring, and a pyridine ring.

[0031] In formula (2), R b is not particularly limited as long as it is a single bond or a divalent organic group. The divalent organic group may be, for example, a divalent organic group including an aromatic hydrocarbon group (arylene group), an aliphatic hydrocarbon group (alkylene group), an ether group, a ketone group, an ester group, a sulfonyl group, or the like.

[0032] In formula (2), R b is preferably a divalent organic group containing an aliphatic hydrocarbon group (alkylene group). Examples of divalent organic groups containing an alkylene group include divalent organic groups containing a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, etc. Among these, R bis preferably an alkylene group, more preferably a methylene group.

[0033] Compound A of this embodiment is preferably a compound having a structure represented by the following formula (1-1), for example. [ka] {In formula (1-1), R2 is as defined above. X is a divalent organic group having a cage-shaped silsesquioxane basic structure having two or more carbon-carbon double bonds.}

[0034] As described above, X in formula (1) or formula (1-1) has two or more carbon-carbon double bonds. The number of carbon-carbon double bonds is not particularly limited as long as it is two or more. It is preferably two or more and six or less, more preferably two or more and four or less, and even more preferably two.

[0035] X in formula (1) or formula (1-1) preferably has two or more carbon-carbon double bonds bonded to an atomic group other than X. For example, X preferably has at least a carbon-carbon double bond bonded to Y1. When the [ ] portion in formula (1) is a repeating structure, X preferably has at least a carbon-carbon double bond bonded to Y1 and a carbon-carbon double bond bonded to Y2.

[0036] When X in formula (1) or formula (1-1) has a carbon-carbon double bond bonded to an atomic group other than X, it is preferable that X contains a divalent organic group containing the carbon-carbon double bond. Examples of divalent organic groups containing a carbon-carbon double bond include a vinylene group, a propenylene group, a 1-butenylene group, a 2-butenylene group, a butadienylene group, a pentenylene group, a hexenylene group, a heptenylene group, and an octenylene group. Among the above, it is preferable that X contains a vinylene group.

[0037] The divalent organic group containing a carbon-carbon double bond that X in formula (1) or formula (1-1) has may be one type or two or more types.

[0038] As described above, X in formula (1) or formula (1-1) is a divalent organic group having a cage silsesquioxane as a basic structure. Cage silsesquioxane is a cage compound composed of siloxane bonds (Si-O-Si) obtained by hydrolyzing a silane compound.

[0039] Cage silsesquioxanes include those with a fully condensed structure and those with an incompletely condensed structure. A fully condensed structure is a structure surrounded by a ring structure composed of siloxane bonds. For example, the formula (RSiO 1.5 ) n Among structures having a skeleton represented by the formula (where R is an organic group and n is an integer), examples include a T8 structure (n=8), a T10 structure (n=10), and a T12 structure (n=12). An incomplete condensation structure is a structure in which a portion of the complete condensation structure is not siloxane bonded and is not closed.

[0040] The structure of the cage silsesquioxane of this embodiment is not particularly limited, but it is preferable that it does not have a silanol group.

[0041] X in formula (1) or formula (1-1) is more preferably a divalent organic group having a cage-shaped silsesquioxane as a basic structure, as represented by the following formula (3). [ka] In formula (3), R5 and R6 are each an organic group, and * indicates a bonding site.

[0042] R5 in formula (3) is not particularly limited as long as it is an organic group that is independent of each other, and examples thereof include linear, branched, and cyclic aliphatic groups, aromatic groups, etc. The aliphatic and aromatic groups may or may not have a substituent. R5 is preferably a phenyl group, an alkyl group having 1 to 20 carbon atoms, or an aryl group, and more preferably a phenyl group or a methyl group. When R5 is a phenyl group or a methyl group, higher heat resistance can be exhibited.

[0043] R6 in formula (3) is not particularly limited as long as it is an organic group that is independent of each other, and examples thereof include linear, branched, and cyclic aliphatic groups and aromatic groups. The aliphatic and aromatic groups may or may not have a substituent. R6 is preferably a phenyl group, an alkyl group having 1 to 20 carbon atoms, or an aryl group, and more preferably a phenyl group. When R6 is a phenyl group, higher heat resistance can be exhibited.

[0044] In formula (3), the divalent organic group in which R5 is a methyl group and R6 is a phenyl group is shown in the following formula (3-1): In formula (1), it is particularly preferable that X is shown in the following formula (3-1). [ka] {In the above formula (3-1), * indicates a binding site.}

[0045] 2. Compound B Compound B of this embodiment has a structure represented by the following formula (4). [ka] {In formula (4), R1 to R4, Y1, and Y2 are as defined above. Z's are each independently a bromo group, a chloro group, an iodo group, or a triflate group, and may be the same group or different groups.}

[0046] Compound B of this embodiment can be used in the synthesis of the above-mentioned compound A, and is an intermediate for synthesizing compound A. The above formula (4) will be described in detail below.

[0047] In formula (4), Z is not particularly limited as long as it is the above-mentioned group, and it is preferable that they are the same group. Furthermore, it is preferable that both Z are bromo groups. Compound B is preferably represented by the following formula (4-1). [ka] {In formula (4-1), R2 is as defined above.}

[0048] An example of a method for producing compound B is a method of reacting a compound represented by the following formula (5) with a compound represented by the following formula (6) or trifluoromethanesulfonic anhydride as a raw material. [ka] {In formula (5), R2 and R4 are as defined above.} [ka] {In formula (6), R a , R b and Z are as defined above. W is a bromo group, a chloro group, an iodo group, a triflate group, a mesyl group, a tosyl group, or a carboxyl group or a derivative thereof.}

[0049] The compound represented by formula (5) is not particularly limited, and known compounds can be used, for example, compounds represented by the following formula (5-1): [ka] {In formula (5-1), R2 is as defined above.}

[0050] The compound represented by formula (6) is not particularly limited, and known compounds can be used, for example, the compound represented by the following formula (6-1): [ka] {In formula (6-1), R b , Z, and W are as described above.}

[0051] When a compound of formula (6) in which W is a bromo group, a chloro group, an iodo group, a triflate group, a mesyl group, or a tosyl group is used, a compound B of formula (4) in which R1 and R3 are ether bonds can be obtained. When W of formula (6) is a carboxyl group or a derivative thereof, a compound B of formula (4) in which R1 and R3 are ester bonds can be obtained.

[0052] More specifically, the compound represented by formula (6) is preferably 4-bromobenzyl bromide, 4-bromobenzyl chloride, 4-iodobenzyl bromide, 4-iodobenzyl chloride, 4-chlorobenzyl bromide, 4-chlorobenzyl chloride, etc., which are represented by the following formula (6-2). Among the above, 4-bromobenzyl bromide represented by the following formula (6-2) is more preferred. [ka]

[0053] In the reaction of the compound represented by formula (5) with the compound represented by formula (6), an organic solvent may be used, if necessary.

[0054] The organic solvent is not particularly limited, and known organic solvents can be used. Examples include amide organic solvents such as pyridine, N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), and N,N-dimethylformamide (DMF); alcohol organic solvents such as methanol, ethanol, isopropanol, butanol, and octanol; ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester organic solvents such as ethyl acetate, butyl acetate, and ethyl lactate; ether organic solvents such as ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and tetrahydrofuran (THF); and aromatic hydrocarbon compound organic solvents such as benzene, toluene, and xylene. Among the above, amide organic solvents are preferred.

[0055] The amount of organic solvent is not particularly limited as long as it allows the reaction to proceed efficiently, and is preferably about 50 to 500 parts by mass per 100 parts by mass of the total amount of the compound represented by formula (5) above and the compound represented by formula (6) above.

[0056] In the case where a compound in which W is a bromo group, a chloro group, an iodo group, a triflate group, a mesyl group, or a tosyl group is used in the formula (6), the reaction between the compound represented by the formula (5) and the compound represented by the formula (6) is S N Since the reaction proceeds by two reactions, S N Conventional reaction conditions used in reaction 2 can be used. For example, the reaction can be carried out in the presence of a base at 25°C to 100°C for 1 to 25 hours. Examples of the base include alkali metal hydroxides (e.g., sodium hydroxide, potassium hydroxide), alkali metal phosphates (e.g., potassium phosphate), alkali metal carbonates (e.g., sodium carbonate, potassium carbonate, cesium carbonate), alkali metal acetates (e.g., sodium acetate), and tertiary amines (e.g., triethylamine).

[0057] When a compound represented by formula (6) in which W is a carboxyl group or a derivative thereof is used, the reaction between the compound represented by formula (5) and the compound represented by formula (6) proceeds by a condensation reaction, and therefore, conventionally known reaction conditions used for condensation reactions can be used.

[0058] When the compound represented by formula (5) is reacted with trifluoromethanesulfonic anhydride under basic conditions, a compound B represented by formula (4) can be obtained, in which R1, R3, Y1, and Y2 are all single bonds and Z is a triflate group.

[0059] 3. Method for producing compound A Compound A of this embodiment can be produced by reacting the above-mentioned compound B with a compound having a cage-shaped silsesquioxane basic structure having two or more carbon-carbon double bonds.

[0060] More specifically, there can be mentioned a method in which the above-mentioned compound B and a cage silsesquioxane represented by the following formula (7) are subjected to a cross-coupling polymerization reaction as raw materials. [ka] {In formula (7), R5 and R6 are as defined above.}

[0061] In formula (7), it is preferable that R5 is a methyl group and R6 is a phenyl group. A cage silsesquioxane in which R5 is a methyl group and R6 is a phenyl group is shown in the following formula (7-1). [ka]

[0062] The above-mentioned cross-coupling polymerization reaction proceeds in the presence of a catalyst, a base, and an organic solvent. Examples of catalysts include compounds containing palladium, nickel, etc. Examples of bases include alkali metal hydroxides (e.g., sodium hydroxide, potassium hydroxide), alkali metal phosphates (e.g., potassium phosphate), alkali metal carbonates (e.g., sodium carbonate, potassium carbonate, cesium carbonate), alkali metal acetates (e.g., sodium acetate), and tertiary amines (e.g., triethylamine). Furthermore, phosphorus compounds (e.g., triphenylphosphine) may be used as ligands to activate the catalyst, if necessary.

[0063] The organic solvent is not particularly limited, and known organic solvents can be used. Examples include amide organic solvents such as pyridine, N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), and N,N-dimethylformamide (DMF); alcohol organic solvents such as methanol, ethanol, isopropanol, butanol, and octanol; ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester organic solvents such as ethyl acetate, butyl acetate, and ethyl lactate; ether organic solvents such as ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and tetrahydrofuran (THF); and aromatic hydrocarbon compound organic solvents such as benzene, toluene, and xylene.

[0064] The reaction temperature and reaction time for the coupling polymerization reaction can be appropriately selected from conventionally known reaction conditions, and for example, the reaction can be carried out at 25° C. to 130° C. for 3 to 48 hours.

[0065] 4. Physical properties of compound A The weight average molecular weight (Mw) of compound A can be set to 1,000 to 300,000, preferably 5,000 to 250,000, more preferably 8,000 to 200,000, and even more preferably 10,000 to 150,000.

[0066] The number average molecular weight (Mn) of the compound A is preferably from 3,000 to 100,000, more preferably from 4,000 to 50,000, and even more preferably from 5,000 to 30,000.

[0067] The molecular weight dispersity index (PDI) of the compound A is preferably from 1.0 to 25.0, more preferably from 1.0 to 10.0. The molecular weight dispersity index (PDI) is calculated by the following formula. PDI=Mw / Mn

[0068] In particular, Compound A of the present embodiment has excellent solvent solubility, and therefore can be made into a high molecular weight while maintaining its solubility in various solvents, making it possible to obtain a cured product with excellent mechanical properties.

[0069] In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured by gel permeation chromatography (GPC) (Waters e2695) and converted into standard polystyrene. Specific measurement conditions are as follows:

[0070] Column: Shodex K-805L (Waters) Column temperature: 40℃ Eluent composition: 100mmol / L CHCl3 Eluent flow rate: 1.0mL / min Calibration standard: Polystyrene RI detector: 2414 (Waters) Detector wavelength: 410 nm Detector temperature: 40℃ Baseline range during analysis: 15 to 40 minutes Molecular weight calculation range during analysis: 20 to 35 minutes

[0071] 5.Curable composition The curable composition of the present embodiment contains the above-described compound A and preferably further contains a polymerization initiator. The curable composition may also contain other components, such as a crosslinking agent, within a range that does not impair the effects of the present invention.

[0072] 5-1.Compound A The compound A of this embodiment is as described above. Only one type of compound A may be used, or two or more types may be used.

[0073] In the curable composition of the present embodiment, the content of compound A is preferably from 10 to 80 mass %, more preferably from 20 to 70 mass %, based on the total solid content of the composition.

[0074] 5-2. Polymerization initiator A polymerization initiator is a compound that has the effect of generating radicals when irradiated with heat or light such as ultraviolet light. As such a polymerization initiator, either a thermal polymerization initiator (thermal radical initiator) that generates radicals when heated, or a photopolymerization initiator (photoradical initiator) that generates radicals when irradiated with light may be used depending on the application of the curable composition. The curable composition of this embodiment becomes a thermosetting composition when a thermal polymerization initiator is used, and becomes a photocurable composition when a photopolymerization initiator is used.

[0075] (thermal polymerization initiator) Examples of the thermal polymerization initiator include peroxides, such as methyl ethyl ketone peroxide, methyl acetoacetate peroxide, acetylacetonperoxide, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, and 2,5-di Examples of peroxyl groups include methyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-butene, acetyl peroxide, octanoyl peroxide, lauroyl peroxide, benzoyl peroxide, m-toluyl peroxide, diisopropyl peroxydicarbonate, t-butylene peroxybenzoate, di-t-butyl peroxide, t-butylperoxyisopropyl monocarbonate, and α,α'-bis(t-butylperoxy-m-isopropyl)benzene.

[0076] Among these, from the viewpoints of ease of handling and reactivity, peroxides having a one-minute half-life temperature of 130° C. to 180° C. are desirable. Such peroxides have a relatively high reaction initiation temperature, and therefore do not readily promote curing when curing is not required, such as during drying, and do not impair the shelf life of the curable composition. In addition, due to their low volatility, they do not volatilize during drying or storage, resulting in good stability.

[0077] As the thermal polymerization initiator, an azo compound such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), or 2,2'-azobis(4-methoxy-2'-dimethylvaleronitrile) may be used.

[0078] These may be used alone or in combination.

[0079] (Photopolymerization initiator) Examples of photopolymerization initiators include benzoin ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one; α-hydroxyketones such as 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one; α-amino ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one and 1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; Oxime esters such as 1-[4-(phenylthio)phenyl]-1,2-octadione-2-(benzoyl)oxime; Phosphine oxides such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 2,4,5-triarylimidazole dimers such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer; Benzophenone, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone, N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone, 4-methylbenzophenone benzophenone compounds such as 4'-dimethylaminobenzophenone; quinone compounds such as 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin; benzyl compounds such as benzyl dimethyl ketal; Acridine compounds such as 9-phenylacridine and 1,7-bis(9,9'-acridinylheptane); N-phenylglycine; Coumarin; and the like.

[0080] These may be used alone or in combination.

[0081] In the curable composition of the present embodiment, the solid content of the polymerization initiator is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the content of compound A in the curable composition.

[0082] 5-3.Other ingredients The curable composition may contain components other than the above-mentioned components within the range that does not impair the effects of the present invention.

[0083] Other components include known and commonly used components, such as fillers (inorganic fillers and organic fillers such as PTFE powder), flame retardancy improvers (phosphorus compounds, etc.), cellulose nanofibers, cyanate ester resins, epoxy resins, phenol novolac resins, elastomers, dispersants, curing accelerators, crosslinking agents, adhesion promoters, and solvents.

[0084] 5-3-1.Crosslinking agent The crosslinking agent is one that crosslinks Compound A of this embodiment or crosslinks with other crosslinking agents. The crosslinking agent is preferably one that has good compatibility with Compound A. Examples of suitable crosslinking agents include polyfunctional vinyl compounds such as divinylbenzene, divinylnaphthalene, and divinylbiphenyl; vinylbenzyl ether compounds synthesized by the reaction of phenol with vinylbenzyl chloride; allyl ether compounds synthesized by the reaction of styrene monomer, phenol with allyl chloride; and trialkenyl isocyanurates. The crosslinking agent is preferably trialkenyl (iso)cyanurate, and more specifically, triallyl isocyanurate (hereinafter, TAIC®) and triallyl cyanurate (hereinafter, TAC) are preferred. These exhibit low dielectric properties and can enhance heat resistance. TAIC® is particularly preferred because of its excellent compatibility with Compound A. Alternatively, a (meth)acrylate compound may be used as the crosslinking agent. One or more crosslinking agents may be used.

[0085] Compound A of this embodiment can be cured with a crosslinking agent to give a cured product with excellent low dielectric properties.

[0086] In the curable composition of the present embodiment, the solid content of the crosslinking agent is preferably 1 to 100 parts by mass, more preferably 20 to 80 parts by mass, relative to 100 parts by mass of the content of compound A in the curable composition.

[0087] 5-3-2.Solvent The curable composition is usually provided or used in a state in which the compound A is dissolved in a solvent. The compound A of the present embodiment has higher solvent solubility than conventional polyphenylene ethers, and therefore, a wider range of solvents can be selected depending on the application of the curable composition.

[0088] Examples of solvents that can be used in the curable composition of this embodiment include conventionally usable solvents such as chloroform, methylene chloride, and toluene, as well as relatively safe solvents such as N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), tetrahydrofuran (THF), cyclohexanone, propylene glycol monomethyl ether acetate (PMA), diethylene glycol monoethyl ether acetate (CA), methyl ethyl ketone, and ethyl acetate. Only one type of solvent may be used, or two or more types may be used.

[0089] The content of the solvent in the curable composition is not particularly limited and can be adjusted appropriately depending on the application of the curable composition.

[0090] Such a curable composition can be obtained by appropriately mixing the components.

[0091] 6.Cured product The cured product of the present embodiment is obtained by curing the above-described curable composition.

[0092] The method for obtaining a cured product from the curable composition is not particularly limited and can be appropriately changed depending on the composition of the curable composition. As an example, after performing the step of applying the curable composition to a substrate as described above (e.g., applying using an applicator, etc.), a drying step of drying the curable composition may be performed as needed, and a curing step of crosslinking the curable composition by heating (e.g., heating using an inert gas oven, hot plate, vacuum oven, vacuum press, etc.) or exposure to light may be performed. The conditions for performing each step (e.g., coating thickness, drying temperature and time, heating temperature and time, exposure dose, etc.) may be appropriately changed depending on the composition and application of the curable composition, etc.

[0093] 7. Electronic Components The electronic component of this embodiment has the cured product described above. The curable composition described above is soluble in solvents other than toxic solvents and has excellent handleability. Therefore, the cured product obtained by curing the curable composition can be suitably used for electronic components, etc.

[0094] The electronic component having the cured product according to this embodiment is not particularly limited, and preferred examples include millimeter-wave radar for high-capacity, high-speed communications such as the fifth-generation communication system (5G) and automotive ADAS (Advanced Driver Assistance Systems). [Example]

[0095] Next, the present embodiment will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0096] <Synthesis Example: Synthesis of Compound (B)> In a 100 mL two-necked eggplant flask, a polyphenylene ether compound (SHPP Japan, LLC, Noryl SA90) (10.00 g, 6.25 mmol) was mixed with N,N-dimethylformamide (DMF) (20 mL) and stirred at 80 °C while blowing in nitrogen to dissolve the polyphenylene ether compound. Potassium carbonate (1.53 g, 11.1 mmol) was then added and stirred at 80 °C for 1 hour. After cooling to 55 °C, 4-bromobenzyl bromide (3.24 g, 13.0 mmol) and cesium carbonate (3.48 g, 10.7 mmol) were added and stirred at 90 °C for 4 hours. The reaction solution was diluted with tetrahydrofuran (THF) (50 mL) and then reprecipitated with Alcosol K / ion-exchanged water (200 mL / 100 mL). After suction filtration, the precipitate was washed with ion-exchanged water and then with Alcosol K, and dried in a vacuum oven at 80° C. for 3 hours to obtain a compound (B) represented by the following formula. [ka]

[0097] Example 1: Synthesis of compound (A1) In a 100 mL two-necked flask, the above-mentioned compound (B) (1.99 g, 1.03 mmol), cage silsesquioxane (JNC Corporation, XQ1089) (1.23 g, 1.02 mmol), catalyst palladium acetate {Pd(OAc)} (24.6 mg, 0.11 mmol), and triphenylphosphine (58.0 mg, 0.22 mmol) were dissolved in toluene (7 mL) and mixed. Triethylamine (2 mL, 14.3 mmol) was added, and nitrogen gas was purged for 30 minutes. The reaction was then carried out at 100 °C for 29 hours. Palladium acetate {Pd(OAc)} (51.7 mg, 0.23 mmol) and triphenylphosphine (127.4 mg, 0.486 mmol) were added, and the reaction was continued for an additional 44 hours at 100 °C. After removing the solvent from the reaction solution using an evaporator, the reaction solution was dissolved in a toluene / tetrahydrofuran mixed solution (1:1 mixed solution, 60 mL) and reprecipitated with methanol. After suction filtration, the solution was washed with methanol and dried in a vacuum oven at 50°C for 3.5 hours to obtain compound (A1) of Example 1 (Mn: 5,900, Mw: 12,000).

[0098] [ka]

[0099] Example 2: Synthesis of compound (A2) In a 100 mL two-necked flask, the above-mentioned compound (B) (2.01 g, 1.03 mmol), cage silsesquioxane (JNC Corporation, XQ1089) (1.24 g, 1.03 mmol), and catalyst [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) {Pd(dppf)Cl} (78.6 mg, 0.107 mmol) were dissolved in toluene (7 mL) and mixed. Triethylamine (2 mL, 14.3 mmol) was added, and nitrogen gas was sparged by bubbling for 30 minutes. The mixture was then reacted at 100 °C for 29 hours, and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) {Pd(dppf)Cl} (78.3 mg, 0.107 mmol) was added, followed by an additional reaction at 100 °C for 39 hours. After removing the solvent from the reaction solution using an evaporator, the reaction solution was dissolved in a mixed solution of toluene / tetrahydrofuran (1:1 mixed solution, 40 mL) and reprecipitated with methanol. After suction filtration, the mixture was washed with methanol and dried in a vacuum oven at 50°C for 4 hours to obtain compound (A2) (Mn: 15,000, Mw: 94,800).

[0100] Comparative Example 1: Synthesis of Compound (C1) 2,6-dimethylphenol (26DMP) (8.91 g, 72.9 mmol) was added to a 250 mL single-necked round flask and dissolved in 56.7 g of toluene. Di-μ-hydroxo-bis[(N,N,N',N'-tetramethylethylenediamine)copper(II)] chloride (Cu / TMEDA) (0.222 g, 0.478 mmol) and tetramethylethylenediamine (TMEDA) (0.202 g, 1.74 mmol) were then added and stirred. The reaction mixture was stirred at 40°C for 4 hours while blowing dry air into the reaction solution. After the reaction was completed, the mixture was reprecipitated with methanol, suction filtered, washed with methanol, and dried in a vacuum oven at 80°C for 16 hours to obtain Compound (C1) (Mn: 4,500, Mw: 8,700) of Comparative Example 1.

[0101] Comparative Example 2: Synthesis of Compound (C2) Compound (C2) of Comparative Example 2 (Mn: 16,700, Mw: 87,400) was obtained in the same manner as compound (C1) of Comparative Example 1, except that the reaction time was 23 hours.

[0102] [Evaluation of Solubility (1)] Solubility evaluation samples were obtained by adding cyclohexanone to the compounds (A1) and (A2) of each example and the compounds (C1) and (C2) of each comparative example to concentrations of 20 mass%, 15 mass%, 10 mass%, 5 mass%, and 2 mass%. The solubility evaluation samples were shaken at room temperature and then allowed to stand. After 17 hours and 6 days, the solubility in cyclohexanone at each concentration was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1 below. (Evaluation criteria) A: It was dissolved after 17 hours and after 6 days. B: Not dissolved after 17 hours but dissolved after 6 days, or dissolved after 17 hours but precipitated after 6 days C: Not dissolved after 17 hours and not dissolved after 6 days [Table 1]

[0103] [Evaluation of Solubility (2)] Tetrahydrofuran (THF), chloroform, and toluene were added to compound (A1) of Example 1 and compound (A2) of Example 2 so that the concentration was 20% by mass, and the mixture was shaken at room temperature and then allowed to stand, and it was visually confirmed whether the mixture had dissolved.

[0104] (Evaluation results) Both the compound (A1) of Example 1 and the compound (A2) of Example 2 were rapidly dissolved in all of the above-mentioned solvents.

[0105] These solubility evaluation results revealed that the compounds of Examples 1 and 2 had excellent solubility in solvents. In particular, compound (A2) of Example 2, despite being a high molecular weight compound with a relatively large weight average molecular weight, was mostly dissolved in cyclohexanone within several tens of minutes, demonstrating excellent solvent solubility.

[0106] ( 1 H-NMR measurement) Regarding the compound (A1) of Example 1, the compound (A2) of Example 2, and the compound (B) obtained in the synthesis example, 1 H-NMR measurement was carried out. A nuclear magnetic resonance spectrometer (JNM-ECA400II, manufactured by JEOL Ltd.) was used for the measurement. Figures 1 to 3 show the NMR spectra of Compound (A1), Compound (A2), and Compound (B). 1 The H-NMR measurement results (NMR chart) and the hydrogen positions corresponding to the peaks in the NMR chart are shown.

[0107] As shown in Figures 1 to 3 1 From the results of H-NMR measurement, it was possible to confirm that compound (A1), compound (A2), and compound (B) were compounds having the structures of the respective chemical formulas.

[0108] <Preparation of Curable Composition> (Example 2-1, Example 2-2) For the compound (A2) of Example 2, the components were blended in the amounts shown in Table 2 below, followed by dispersion and stirring to obtain curable resin compositions of Examples 2-1 and 2-2.

[0109] (Comparative Example 3) A curable composition of Comparative Example 3 was obtained in the same manner as in Example 2-1 and Example 2-2, except that a polyphenylene ether compound (Noryl SA90, manufactured by SHPP Japan LLC) was used instead of compound (A2) to achieve the components and blending amounts shown in Table 2 below.

[0110] [Table 2] *1: TAIC (manufactured by Mitsubishi Chemical Corporation) *2: PERBUTYL P40 (NOF Corporation)

[0111] (Preparation of cured film) The resulting curable composition was applied to the shine side of 18 μm thick copper foil using a dumbbell coater with a gap of 200 μm, and then dried in a hot air circulation drying oven at 90°C for 5 minutes. Next, the temperature was raised to 200°C in a nitrogen atmosphere using an inert oven, and heat treatment was performed for 60 minutes. The copper foil was then removed by etching to obtain a cured product (cured film).

[0112] [evaluation] The cured products of Examples 2-1 and 2-2 were evaluated as follows, and the evaluation results are shown in Table 3 below.

[0113] The cured product of Comparative Example 3 was not evaluated below because cracks occurred in the cured product after heat treatment and a cured film could not be obtained by etching the copper foil. This indicates that the cured products of Examples 2-1 and 2-2 also have excellent mechanical strength.

[0114] (Dielectric properties) The dielectric properties, ie, the relative permittivity Dk and the dielectric loss tangent Df, were measured according to the following method. The cured film was cut into a length of 80 mm and a width of 45 mm and used as a test piece for measurement using the SPDR (Split Post Dielectric Resonator) resonator method. The measuring equipment used was a Keysight Technologies, LLC Vector Network Analyzer E5071C, an SPDR resonator, and a calculation program manufactured by QWED. The conditions were a frequency of 10 GHz and a measurement temperature of 25°C.

[0115] (Measurement of coefficient of linear thermal expansion (CTE)) The coefficient of linear thermal expansion (CTE) was measured according to the following method. The cured film was cut into test pieces measuring 3 mm x 30 mm. The CTE of each test piece was measured using a TA Instruments TMAQ400. The measurement conditions were a test load of 30 mN, a temperature rise / fall rate of 10 K / min, and a tensile mode in a nitrogen atmosphere (100 mL / min), with the temperature cycle increasing and decreasing from 30°C to 300°C, -55°C, and then back to 300°C. The linear thermal expansion coefficient was calculated from the measurement results of the first heat from 30°C to 100°C.

[0116] [Table 3]

[0117] It was found that both the cured products of Examples 2-1 and 2-2 had good low dielectric properties. [Industrial Applicability]

[0118] The compound of the present invention is soluble in various solvents (solvents other than highly toxic organic solvents, such as cyclohexanone), and therefore, a cured product obtained by curing a curable composition containing the compound can be used for electronic components to be built into electronic devices.

Claims

1. A compound having a structure represented by the following formula (1): 【Chemistry 1】 {In formula (1), R １ , R ３ are each independently a single bond, an ether bond, or an ester bond. ２ is a divalent organic group having a phenylene ether structure. ４ are each independently a hydrogen atom or an organic group, and may be the same or different groups. X is a divalent organic group having a cage-shaped silsesquioxane structure having two or more carbon-carbon double bonds. Y １ , Y ２ are each independently a single bond or any one selected from the following formula (2): 【Chemistry 2】 {In formula (2), R ａ are each independently a hydrogen atom or an organic group, and may be the same or different groups; R ａ When two or more R ｂ is a single bond or a divalent organic group. * indicates a bonding site.

2. The compound according to claim 1, wherein X is a divalent organic group having a cage-shaped silsesquioxane as a basic structure, represented by the following formula (3): 【Transformation 3】 {In formula (3), R ５ , R ６ are each an independent organic group. * indicates a bonding site.

3. A compound represented by the following formula (4): 【Chemistry 4】 {In formula (4), R 1 ~R ４ , Y １ , Y ２ is as defined above. Z's are each independently a bromo group, a chloro group, an iodo group, or a triflate group, and may be the same group or different groups.

4. A curable composition comprising the compound of claim 1 or 2.

5. A cured product obtained by curing the curable composition according to claim 4.

6. An electronic component comprising the cured product according to claim 5 .

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