Triphenylalkane compounds having a hydroxyalkoxy group

Abstract

The present application provides a functional compound exhibiting excellent dielectric properties and flexibility of a cured product. As a solution, the present application provides a triphenylalkane compound characterized by being represented by general formula (1), wherein R1 each independently represents a hydrogen atom or an alkenyl group having 2 to 4 carbon atoms, R2 represents an alkylene group having 1 to 4 carbon atoms, R3 each independently represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom, R4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m and n each independently represent 0, 1, 2, or 3.[Chem. 1]

Description

Technical Field

[0001] This invention relates to a triphenylalkane compound having a hydroxyalkoxy group. More specifically, it relates to bisphenol compounds with a triphenylalkane backbone having a hydroxyalkoxy group, diene ether compounds with a triphenylalkane backbone having a hydroxyalkoxy group, and curable resin compositions using the same. Background Technology

[0002] Examples of bisphenol compounds with a triphenylalkane backbone include bis(4-hydroxyphenyl)phenylmethane or 1,1-bis(4-hydroxyphenyl)-1-phenylethane. Similarly, examples of triphenol compounds with a triphenylalkane backbone include tris(4-hydroxyphenyl)methane or 1,1,1-tris(4-hydroxyphenyl)ethane. These compounds are modified with reactive groups such as glycidyl ethers or unsaturated groups and used as raw materials for various resins.

[0003] Triallyl ether compounds having a triphenylalkane skeleton and incorporating an allyl ether group as an unsaturated group are known, for example, tris(4-allyloxyphenyl)methane or bis(4-allyloxy-3,5-dimethylphenyl)(4-allyloxyphenyl)methane represented by chemical formula (A-2) described later in the examples (Patent Document 1).

[0004] As one of the bisphenol compounds containing hydroxyalkoxy groups, such as 1,2-bis(4-hydroxyphenyl)-2-hydroxypropane, compounds obtained by glycidyl etherification or epoxy acrylate esterification are known to be used as raw materials for phenoxy resins or curable resins. Literature records that such compounds containing hydroxyl groups maintain high reactivity even when using conventional curing agents or catalysts, and that the curing process can be controlled (Patent Document 2).

[0005] Patent documents Patent Document 1: International Publication No. 2022 / 176753 Patent Document 2: Japanese Patent Publication No. 2003-506507 Summary of the Invention In further exploring triphenylalkanes that exhibit excellent functional properties, the inventors discovered that the previously known compound represented by chemical formula (A-1), bis(4-hydroxy-3,5-dimethylphenyl)(4-hydroxyphenyl)methane, has a high refractive index, and according to Maxwell's equation "ε=n²" which describes the relationship between the refractive index (n) and dielectric constant (ε) of this substance, its dielectric constant is also high.

[0006] Furthermore, it was found that when bis(4-allyloxy-3,5-dimethylphenyl)(4-allyloxyphenyl)methane, represented by formula (A-2), obtained by allyl etherification of the compound represented by formula (A-1), is used as a curing agent for polyphenylene ether resin, the resulting cured product has a high dielectric constant and a large storage modulus. However, if such cured products are used in the structural components of electronic parts, there are problems with high dielectric loss or insufficient flexibility.

[0007] Against the backdrop of the above-mentioned events, the present invention aims to provide compounds that further exhibit superior functional properties.

[0008] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that by using a triphenylalkane compound having a hydroxyalkoxy group as a curing agent for a curable resin composition, the softness of the cured resin composition can be improved and the dielectric properties can be improved, thus completing the present invention.

[0009] The present invention is as follows.

[0010] 1. A triphenylalkane compound, characterized by being represented by the general formula (1), [Chemistry 1]

[0011] In the formula, R1 independently represents a hydrogen atom or an alkenyl group having 2 to 4 carbon atoms, R2 represents an alkylene group having 1 to 4 carbon atoms, R3 independently represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom, R4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m and n independently represent 0, 1, 2, or 3.

[0012] 2. The compound according to 1, characterized in that R4 in the general formula (1) is a hydrogen atom or a methyl group.

[0013] 3. The compound according to 1, characterized in that R1 in the general formula (1) is each independently a hydrogen atom, vinyl, allyl or 1-propenyl, and R2 is 1,2-ethylene.

[0014] 4. The compound according to 1, characterized in that the triphenylalkane compound represented by general formula (1) is a compound represented by any one of chemical formulas (1A-1) to (1A-24) and chemical formulas (1B-1) to (1B-24), [Chemistry 2]

[0015] [Chemistry 3]

[0016] [Chemistry 4]

[0017] [Chemistry 5]

[0018] [Chemistry 6]

[0019] [Chemistry 7]

[0020] [Chemistry 8]

[0021] [Chemistry 9] .

[0022] 5. A curable resin composition, characterized in that component A contains a polyphenylene ether resin, and component B contains a compound represented by general formula (1B). [Chemistry 10]

[0023] In the formula, R 1a Each of the alkenyl groups with 2 to 4 carbon atoms is represented independently, and R2 to R4, m and n are defined in the same way as in general formula (1).

[0024] 6. The curable resin composition according to 5, characterized in that it contains 100 parts by weight of component A and 1.0 to 10.0 parts by weight of component B.

[0025] 7. The curable resin composition according to 6, characterized in that the curable resin composition further contains a curing reaction initiator as component C.

[0026] 8. The curable resin composition according to 7, characterized in that the curable resin composition further contains a filler as component D.

[0027] 9. A prepreg, characterized in that it is obtained by semi-curing the curable resin composition described in 5.

[0028] 10. A cured product of a fiber-reinforced curable resin composition, characterized in that it is obtained by mixing the curable resin composition of 5. with reinforcing fibers as component E and then curing the mixture.

[0029] 11. A crystal of a compound represented by chemical formula (1A-3), characterized in that, in differential scanning calorimetry analysis, it exhibits an endothermic peak in the range of 142-146°C onset temperature. [Chemistry 11] .

[0030] 12. The crystal of the compound represented by the chemical formula (1A-3) according to 11, characterized in that it further has diffraction peaks at diffraction angles 2θ of 14.4±0.2°, 17.2±0.2° and 21.8±0.2° in a powder X-ray diffraction pattern using Cu-Kα rays.

[0031] 13. The crystal of the compound represented by chemical formula (1A-3) according to 12, characterized in that it further has diffraction peaks at 22.2±0.2° and 23.3±0.2° in the powder X-ray diffraction peak pattern using Cu-Kα rays.

[0032] 14. The crystal of the compound represented by chemical formula (1A-3) according to 13, characterized in that it further has diffraction peaks at 8.6±0.2°, 9.4±0.2° and 12.9±0.2° in the powder X-ray diffraction peak pattern using Cu-Kα rays.

[0033] 15. The crystal of the compound represented by chemical formula (1A-3) according to 11, characterized in that, as the purity of the crystal of the compound represented by chemical formula (1A-3), in high performance liquid chromatography (HPLC) analysis, the peak area of ​​compound (1A-3) is 95.0% or more relative to the peak area of ​​all components detected at a wavelength of 280 nm.

[0034] 16. A method for manufacturing crystals of the compound represented by chemical formula (1A-3) as described in 11, characterized in that it includes a crystallization step of precipitating crystals by means of a crystallization solution containing the compound represented by chemical formula (1A-3) and an aromatic hydrocarbon solvent having 7 to 9 carbon atoms.

[0035] 17. The method for manufacturing crystals according to 16, characterized in that the aromatic hydrocarbon solvent with 7 to 9 carbon atoms is any one solvent selected from toluene, o-xylene, m-xylene, p-xylene, and mesitylene.

[0036] 18. A crystal of a compound represented by chemical formula (1A-4), characterized in that, in differential scanning calorimetry analysis, it exhibits an endothermic peak in the range of 202~210°C. [Chemistry 12] .

[0037] 19. A crystal of the compound represented by chemical formula (1A-4) according to 18, characterized in that, in the differential scanning calorimetry analysis, it displays an endothermic peak in the range of 202~210°C and an endothermic peak in the range of 120~130°C.

[0038] 20. The crystal of the compound represented by chemical formula (1A-4) according to 19, characterized in that it further has diffraction peaks at diffraction angles 2θ of 13.4±0.2° and 16.0±0.2° in a powder X-ray diffraction pattern using Cu-Kα rays.

[0039] 21. The crystal of the compound represented by chemical formula (1A-4) according to 20, characterized in that it further has diffraction peaks at 6.7±0.2° and 18.2±0.2° in a powder X-ray diffraction pattern using Cu-Kα rays.

[0040] 22. The crystal of the compound represented by chemical formula (1A-4) according to 21, characterized in that it further has diffraction peaks at 5.4±0.2°, 13.7±0.2° and 20.1±0.2° in a powder X-ray diffraction pattern using Cu-Kα rays.

[0041] 23. A crystal of the compound represented by chemical formula (1A-4) according to 19, characterized in that it contains methyl isobutyl ketone in the range of 4 to 15% by weight.

[0042] 24. The crystal of the compound represented by the chemical formula (1A-4) according to 18, characterized in that, in the differential scanning calorimetry analysis, only an endothermic peak is shown in the range of 202~210°C.

[0043] 25. The crystal of the compound represented by chemical formula (1A-4) according to 24, characterized in that it further has diffraction peaks at diffraction angles 2θ of 13.9±0.2°, 16.8±0.2° and 24.0±0.2° in a powder X-ray diffraction pattern using Cu-Kα rays.

[0044] 26. The crystal of the compound represented by chemical formula (1A-4) according to 25, characterized in that it further has diffraction peaks at 12.0±0.2° and 16.4±0.2° in the powder X-ray diffraction peak pattern using Cu-Kα rays.

[0045] 27. The crystal of the compound represented by chemical formula (1A-4) according to 26, characterized in that it further has diffraction peaks at 17.9±0.2°, 19.2±0.2° and 19.6±0.2° in the powder X-ray diffraction peak pattern using Cu-Kα rays.

[0046] 28. A crystal of the compound represented by chemical formula (1A-4) according to 18, characterized in that, in the differential scanning calorimetry analysis, it displays an endothermic peak in the range of 202~210°C and an endothermic peak in the range of 194~200°C.

[0047] 29. The crystal of the compound represented by chemical formula (1A-4) according to 28, characterized in that it further has diffraction peaks at diffraction angles 2θ of 12.1±0.2°, 13.9±0.2° and 21.8±0.2° in a powder X-ray diffraction pattern using Cu-Kα rays.

[0048] 30. The crystal of the compound represented by the chemical formula (1A-4) according to 29, characterized in that it further has a diffraction peak at 24.1 ± 0.2° in a powder X-ray diffraction pattern using Cu-Kα rays.

[0049] 31. The crystal of the compound represented by chemical formula (1A-4) according to 30, characterized in that it further has diffraction peaks at 18.5±0.2° and 20.9±0.2° in the powder X-ray diffraction peak pattern using Cu-Kα rays.

[0050] 32. The crystal of the compound represented by chemical formula (1A-4) according to 18, characterized in that, as the purity of the crystal of the compound represented by chemical formula (1A-4), in high performance liquid chromatography (HPLC) analysis, the peak area of ​​compound (1A-4) is 95.0% or more relative to the peak area of ​​all components detected at a wavelength of 280 nm.

[0051] 33. A method for manufacturing crystals of the compound represented by chemical formula (1A-4) as described in 18, characterized in that it includes a crystallization step of precipitating crystals by means of a crystallization solution containing the compound represented by chemical formula (1A-4) and a chain aliphatic ketone solvent with a total carbon number of 4 to 8.

[0052] 34. The method for manufacturing crystals according to 33, characterized in that the chain aliphatic ketone solvent with a total number of carbon atoms of 4 to 8 is a solvent selected from any one of methyl ethyl ketone, diethyl ketone, 2-pentanone, isopropyl methyl ketone, methyl isobutyl ketone, isopentyl methyl ketone, 2-heptanone, and methyl hexyl ketone.

[0053] 35. The method for manufacturing crystals according to 24, characterized in that the crystal (α crystal) of the compound represented by chemical formula (1A-4) that exhibits endothermic peaks in the range of 202~210℃ and endothermic peaks in the range of 120~130℃ in differential scanning calorimetry analysis is heated to the range of 120~200℃ under normal or reduced pressure.

[0054] 36. A crystal of a compound represented by chemical formula (1B-4), characterized in that, in differential scanning calorimetry analysis, it exhibits an endothermic peak in the range of 116~124°C. [Chemistry 13] .

[0055] 37. The crystal of the compound represented by chemical formula (1B-4) according to 36, characterized in that it further has diffraction peaks at diffraction angles 2θ of 17.2±0.2°, 18.3±0.2° and 23.9±0.2° in a powder X-ray diffraction pattern using Cu-Kα rays.

[0056] 38. The crystal of the compound represented by chemical formula (1B-4) according to 37, characterized in that it further has diffraction peaks at diffraction angles 2θ of 12.7±0.2° and 15.9±0.2° in a powder X-ray diffraction peak pattern using Cu-Kα rays.

[0057] 39. The crystal of the compound represented by chemical formula (1B-4) according to 38, characterized in that it further has diffraction peaks at 14.1±0.2° and 24.7±0.2° in the powder X-ray diffraction peak pattern using Cu-Kα rays.

[0058] 40. The crystal of the compound represented by chemical formula (1B-4) according to 36, characterized in that, as the purity of the crystal of the compound represented by chemical formula (1B-4), in high performance liquid chromatography (HPLC) analysis, the peak area of ​​compound (1B-4) is 95.0% or more relative to the peak area of ​​all components detected at a wavelength of 280 nm.

[0059] 41. A method for manufacturing crystals of the compound represented by chemical formula (1B-4) as described in 36, characterized in that it includes a crystallization step of precipitating crystals by means of a crystallization solution containing the compound represented by chemical formula (1B-4) and a chain aliphatic carboxylic acid ester solvent with a total carbon number of 6 to 8.

[0060] 42. The method for manufacturing crystals according to 41, characterized in that the chain aliphatic carboxylic acid ester solvent with a total carbon number of 6 to 8 is a solvent selected from any one of n-butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, n-amyl acetate, isoamyl acetate, and n-hexyl acetate.

[0061] The triphenylalkane compound of the present invention, having a hydroxyalkoxy group, is useful when used as a curing agent for curable resin compositions, as it improves the flexibility and dielectric properties of the resulting cured product. Attached Figure Description

[0062] Figure 1 A graph showing the differential scanning calorimetry (DSC) data of the crystals of the compound (1A-3) obtained in Example 1.

[0063] Figure 2 A graph showing the powder X-ray diffraction (PXRD) measurements of the crystals of the compound (1A-3) obtained in Example 1.

[0064] Figure 3 A graph showing the differential scanning calorimetry (DSC) data of the crystals (α crystals) of the compound (1A-4) obtained in Example 2.

[0065] Figure 4 A graph showing the powder X-ray diffraction (PXRD) measurements of the crystals (α crystals) of the compound (1A-4) obtained in Example 2.

[0066] Figure 5 A graph showing the thermogravimetric analysis (TG) data of the crystals (α crystals) of the compound (1A-4) obtained in Example 2.

[0067] Figure 6 A graph showing the differential scanning calorimetry (DSC) data of the crystals (β crystals) of the compound (1A-4) obtained in Example 3.

[0068] Figure 7 A graph showing the powder X-ray diffraction (PXRD) measurements of the crystals (β crystals) of the compound (1A-4) obtained in Example 3.

[0069] Figure 8 A graph showing the differential scanning calorimetry (DSC) data of the crystals (γ crystals) of the compound (1A-4) obtained in Example 4.

[0070] Figure 9 A graph showing the powder X-ray diffraction (PXRD) measurements of the crystals (γ crystals) of the compound (1A-4) obtained in Example 4.

[0071] Figure 10 A graph showing the differential scanning calorimetry (DSC) data of the crystals (α crystals) of the compound (1A-4) obtained in Example 5.

[0072] Figure 11 A graph showing the thermogravimetric analysis (TG) data of the crystals (α crystals) of the compound (1A-4) obtained in Example 5.

[0073] Figure 12 A graph showing the differential scanning calorimetry (DSC) data of the crystals of the compound (1B-4) obtained in Example 7.

[0074] Figure 13 A graph showing the powder X-ray diffraction (PXRD) measurements of the crystals of the compound (1B-4) obtained in Example 7. Detailed Implementation

[0075] The present invention will now be described in detail.

[0076] <Triphenylalkane compounds represented by general formula (1)> In general formula (1), R1 independently represents an alkenyl group with 2 to 4 hydrogen atoms or carbon atoms.

[0077] As an alkenyl group having 2 to 4 carbon atoms, examples include vinyl, allyl (2-propenyl), 1-propenyl, and 2-methyl-2-propenyl, preferably selected from any one of these groups, more preferably vinyl, allyl, or 1-propenyl, further preferably allyl or 1-propenyl, and particularly preferably allyl. Additionally, R in the general formula (1B) described later... 1a The preferred method is the same.

[0078] In general formula (1), when R1 are all hydrogen atoms, it is represented by general formula (1A). The triphenylalkane compound represented by general formula (1A) is a bisphenol compound with hydroxyalkoxy groups having two hydroxyphenyl sites and one hydroxyalkoxyphenyl site.

[0079] [Chemistry 14]

[0080] (In the formula, R2~R4, m and n are defined in the same way as in general formula (1).) In general formula (1), when each R1 is an alkenyl group with 2 to 4 carbon atoms, it is represented by general formula (1B). The triphenylalkane compound represented by general formula (1B) is a compound containing a hydroxyalkoxy group and a bifunctional unsaturated group, having two alkenyl ether phenyl sites and one hydroxyalkoxy phenyl site.

[0081] [Chemistry 15]

[0082] (where R) 1a The alkenyl group represents 2 to 4 carbon atoms, and R2 to R4, m, and n are defined in the same way as in general formula (1). In general formulas (1), (1A), and (1B), R2 represents an alkylene group having 1 to 4 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, further preferably 1,2-ethylene or 1,2-propylene, and particularly preferably 1,2-ethylene.

[0083] In general formulas (1), (1A), and (1B), R3 independently represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom, preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a straight-chain alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms or a cyclic alkyl group having 3 to 6 carbon atoms, even more preferably a straight-chain alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, and particularly preferably an alkyl group having 1 carbon atom, i.e., a methyl group.

[0084] Alkyl groups having 1 to 6 carbon atoms include straight-chain alkyl groups having 1 to 6 carbon atoms, branched alkyl groups having 3 to 6 carbon atoms, and cyclic alkyl groups having 3 to 6 carbon atoms.

[0085] Alkoxy groups with 1 to 6 carbon atoms include straight-chain alkoxy groups with 1 to 6 carbon atoms, branched alkoxy groups with 3 to 6 carbon atoms, and cyclic alkoxy groups with 3 to 6 carbon atoms.

[0086] Halogen atoms include, for example, fluorine, chlorine, bromine and iodine atoms, with bromine being preferred.

[0087] In general formulas (1), (1A), and (1B), R4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms includes straight-chain alkyl groups having 1 to 6 carbon atoms, branched alkyl groups having 3 to 6 carbon atoms, and cyclic alkyl groups having 3 to 6 carbon atoms. Preferably, it is a hydrogen atom or a methyl group, more preferably a hydrogen atom.

[0088] In general formulas (1), (1A), and (1B), m independently represents 0, 1, 2, or 3. Preferably, each independently represents 0, 1, or 2, more preferably 0 or 1, and particularly preferably 0.

[0089] In general formulas (1), (1A), and (1B), n independently represents 0, 1, 2, or 3. Preferably, each independently represents 0, 1, or 2, and more preferably, each independently represents 1 or 2.

[0090] When n is 1, the bonding position of R3 is preferably adjacent to the oxygen atom bonded to the benzene ring. When n is 2, the bonding position of R3 is preferably at positions 2 and 6 or 2 and 5 relative to the oxygen atom bonded to the benzene ring. When n is 3, the bonding position of R3 is preferably at positions 2, 3, and 6 relative to the oxygen atom bonded to the benzene ring.

[0091] <Triphenylalkane compounds represented by general formula (1A)> The triphenylalkane compound represented by general formula (1A) can be used as a raw material for the triphenylalkane compound represented by general formula (1B) containing a difunctional unsaturated group, as described later. Furthermore, it can be used as a raw material for polymerizable compounds in which other polymerizable groups are modified on the two hydroxyphenyl sites and one hydroxyalkoxyphenyl site of the compound, or as a raw material for resin materials obtained by polycondensation of the two hydroxyphenyl sites with a compound having two functional groups that react with hydroxyl groups.

[0092] As specific examples of triphenylalkane compounds represented by general formula (1A), compounds represented by chemical formulas (1A-1) to (1A-24) can be listed (hereinafter sometimes referred to as compound (1A-1), etc.).

[0093] Among them, compounds (1A-1) to (1A-6) and (1A-13) to (1A-18) are preferred, compounds (1A-2), (1A-3), (1A-4), (1A-14), (1A-15) and (1A-16) are more preferred, compounds (1A-2), (1A-3) and (1A-4) are even more preferred, and compounds (1A-3) and (1A-4) are particularly preferred.

[0094] [Chemistry 16]

[0095] [Chemistry 17]

[0096] [Chemistry 18]

[0097] [Chemistry 19]

[0098] <Triphenylalkane compounds represented by general formula (1B)> The triphenylalkane compound represented by general formula (1B) can be used as a raw material for the curable resin composition with polyphenylene ether resin described later, or as a curing agent for polyphenylene ether resin. In addition, since it has two alkenyl groups, it can also be used as a raw material for bismaleimide resin, a raw material for curable resin cured by reaction with polythiol compounds via enylthiol, etc.

[0099] As specific examples of triphenylalkane compounds represented by general formula (1B), compounds represented by chemical formulas (1B-1) to (1B-24) can be listed (hereinafter, sometimes referred to as compound (1B-1), etc.).

[0100] Among them, compounds (1B-1) to (1B-6) and (1B-13) to (1B-18) are preferred, compounds (1B-2), (1B-3), (1B-4), (1B-14), (1B-15) and (1B-16) are more preferred, compounds (1B-2), (1B-3) and (1B-4) are even more preferred, and compounds (1B-3) and (1B-4) are particularly preferred.

[0101] [Chemistry 20]

[0102] [Chemistry 21]

[0103] [Chemistry 22] [Chemistry 23]

[0104] <Method for manufacturing triphenylalkane compounds represented by general formula (1)> There are no limitations on the method of manufacturing the triphenylalkane compound represented by the general formula (1) of the present invention.

[0105] One method for producing a triphenylalkane compound represented by general formula (1A) is, for example, a method in which 2 moles of a phenolic compound represented by general formula (2) and 1 mole of a carbonyl compound represented by general formula (3) undergo a condensation reaction in the presence of an acid catalyst.

[0106] [Chemistry 24]

[0107] (The definitions of R2, R3, R4, m, and n in general formulas (2) and (3) are the same as those in general formula (1).) Furthermore, as a method for producing the triphenylalkane compound represented by general formula (1B), for example, a method of reacting the triphenylalkane compound represented by general formula (1A) with the haloalkene represented by general formula (4) in the presence of a base can be cited.

[0108] [Chemistry 25]

[0109] (R in general formula (4)) 1a The definition is the same as in general formula (1B), where X is a halogen atom. The manufacturing method of the above example will be described in detail below.

[0110] <Method for manufacturing triphenylalkane compounds represented by general formula (1A): reaction steps> The reaction step in the method for manufacturing the triphenylalkane compound represented by general formula (1A) is a step in which a condensation reaction is carried out between a phenolic compound represented by general formula (2) (hereinafter, sometimes referred to as "phenolic compound (2)") and a carbonyl compound represented by general formula (3) (hereinafter, sometimes referred to as "carbonyl compound (3)") in the presence of an acid catalyst.

[0111] <Phenolic compounds represented by general formula (2)> The definitions of R3 and n in general formula (2) are the same as those in general formula (1), and the preferred method is also the same.

[0112] As a phenolic compound represented by general formula (2), specifically, examples include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 2,3,6-trimethylphenol, 2-isopropylphenol, 2,6-diisopropylphenol, 2-tert-butylphenol, 2,6-di-tert-butylphenol, 2-cyclohexylphenol, 2-cyclohexyl-5-methylphenol, and 2-phenylphenol, preferably selected from any one of these.

[0113] More preferably, it is selected from any one of phenol, o-cresol, 2,5-xylenol, 2,6-xylenol, 2,3,6-trimethylphenol, 2-cyclohexylphenol, 2-cyclohexyl-5-methylphenol, and 2-phenylphenol; even more preferably, it is selected from any one of o-cresol, 2,5-xylenol, 2,6-xylenol, 2-cyclohexylphenol, and 2-cyclohexyl-5-methylphenol; and particularly preferably, 2,5-xylenol or 2,6-xylenol.

[0114] <Carbonyl compounds represented by general formula (3)> The definitions of R2, R3, R4 and m in general formula (3) are the same as those in general formula (1), and the preferred method is also the same.

[0115] As a carbonyl compound represented by general formula (3), specifically, compounds represented by chemical formulas (3-1) to (3-8) can be listed, preferably any one of them. Among them, compounds represented by chemical formulas (3-1) or (3-2) are preferred, and compounds represented by chemical formula (3-1) are particularly preferred.

[0116] [Chemistry 26]

[0117] The amount of phenolic compound (2) used in the reaction process is preferably 2 to 20 moles relative to 1 mole of carbonyl compound (3), more preferably 2 to 15 moles, even more preferably 2 to 10 moles, and particularly preferably 2 to 5 moles.

[0118] The reaction temperature depends on the boiling point of the reaction solvent used, and is preferably within the range of 10 to 80°C, and more preferably within the range of 30 to 50°C.

[0119] Regarding reaction pressure, it is usually carried out at atmospheric pressure. Depending on the boiling point of the reaction solvent used, it can also be carried out under pressure or reduced pressure when the reaction temperature reaches the aforementioned range. Furthermore, when hydrogen chloride gas is used as an acid catalyst, it can also be carried out under pressure.

[0120] There are no particular limitations on the mixing method of the raw materials in the reaction process. For example, one method is to add all the raw materials to the reaction vessel at once for mixing, or to add a carbonyl compound (3) to a solution containing a portion of the phenolic compound (2) and acid catalyst, a co-catalyst or reaction solvent as needed, and the remaining amount of phenolic compound (2), and further containing a reaction solvent as needed. From the viewpoint of reaction selectivity and the ability to adjust the amount of reaction per unit time, the latter mixing method is preferred. When using this mixing method, it is preferable that the mixing time is in the range of 0.5 to 5 hours, so that the reaction is carried out in a way that the amount of raw materials used after mixing is achieved.

[0121] The reaction time also depends on the raw materials, amount of catalyst, reaction temperature and other conditions used, and is usually in the range of 0.5 to 48 hours, preferably in the range of 0.5 to 24 hours.

[0122] The endpoint of the reaction can be confirmed, for example, by liquid chromatography or gas chromatography. Preferably, the endpoint of the reaction is defined as the point at which the carbonyl compound (3) disappears or the addition of the triphenylalkane compound represented by general formula (1A) is no longer confirmed.

[0123] (Acid catalyst) Acid catalysts can be used in the reaction process; any acid catalyst, whether inorganic or organic, can be used. Examples of inorganic acids include hydrogen chloride gas, hydrochloric acid, sulfuric acid, phosphoric acid, and anhydrous sulfuric acid. Examples of organic acids include aromatic sulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acid, alkyl sulfonic acids with 1 to 4 carbon atoms such as methanesulfonic acid and ethanesulfonic acid, trifluoromethanesulfonic acid, and trichloroacetic acid. In addition, solid acids such as aluminum chloride, ferric chloride, and cation exchange resins can be used as acid catalysts.

[0124] Inorganic acids are preferred. Among the inorganic acids, hydrogen chloride gas or hydrochloric acid is preferred, and hydrochloric acid is particularly preferred. The amount of the inorganic acid used is preferably 0.50 moles or less, more preferably 0.25 moles or less, even more preferably 0.10 moles or less, and particularly preferably 0.05 moles or less, relative to 1 mole of the carbonyl compound (3).

[0125] (Reaction solvent) In the reaction process, the reaction solvent is not necessary when there are no operational problems, but it may be used to ensure good operability in industrial production. The reaction solvent used is preferably selected appropriately based on the solubility of the triphenylalkane compound represented by the general formula (1A) used in the reaction process or as a product. Furthermore, in the reaction for producing the triphenylalkane compound represented by general formula (1A), it is preferable that the solvent does not distill off the reaction vessel at the reaction temperature and is inert to the reaction.

[0126] Examples of solvents that can be used include lower alcohols such as methanol, ethanol, and isopropanol, or aromatic hydrocarbon solvents with 7 to 9 carbon atoms such as toluene, ethylbenzene, and xylene; these solvents are preferred.

[0127] The amount of solvent used, relative to the amount of carbonyl compound (3) used in the reaction, is preferably in the range of 0.1 to 2.0 times by weight, more preferably in the range of 0.1 to 1.0 times by weight, even more preferably in the range of 0.1 to 0.5 times by weight, and particularly preferably in the range of 0.1 to 0.3 times by weight.

[0128] (co-catalyst) In the reaction process, thiols can also be used as co-catalysts in conjunction with acid catalysts, as needed.

[0129] As a thiol compound, it is a compound containing a thiol group, and there are no particular limitations as long as it does not adversely affect the reaction selectivity, etc. Examples of such compounds include carboxylic acids containing thiol groups such as 3-mercaptopropionic acid and mercaptoacetic acid; alkyl thiols with 1 to 12 carbon atoms such as methanethiol, 1-octylthiol, and 1-dodecylthiol; and thiol alcohols such as mercaptoethanol and mercaptobutanol. Among these, alkyl thiols with 1 to 12 carbon atoms such as 1-octylthiol are preferred, methanethiol, 1-octylthiol, and 1-dodecylthiol are more preferred, and 1-dodecylthiol is particularly preferred. These compounds can also be used in the form of aqueous solutions such as sodium salts.

[0130] The amount of thiol compound used is preferably in the range of 0.01 to 0.50 moles relative to 1 mole of carbonyl compound (3), and more preferably in the range of 0.01 to 0.10 moles.

[0131] <Preparation method of triphenylalkane compound represented by general formula (1A): post-reaction treatment> For reaction solutions containing triphenylalkanes represented by general formula (1A) after the reaction process, the following treatments are preferred, for example: neutralizing the acid catalyst used in the reaction with an alkaline aqueous solution such as sodium hydroxide solution, removing the separated water layer, washing the oil layer containing crystals with water as needed, and removing the solvent used in the reaction process or oil-water separation and washing operation, or the phenol used in excess in the reaction, by distillation.

[0132] Alternatively, a solution can be prepared by mixing and dissolving the target compound represented by the general formula (1A) in the reaction solution and separating it from water in an organic solvent, followed by a water washing operation.

[0133] Then, separation operations based on crystallization or column chromatography can be performed to separate the triphenylalkane compound represented by general formula (1A).

[0134] <Crystals of compounds represented by chemical formulas (1A-3) of the present invention and their manufacturing methods> (Crystals of the compound represented by chemical formula (1A-3)) Among the triphenylalkane compounds represented by general formula (1A) of the present invention, the compound represented by chemical formula (1A-3) (hereinafter, sometimes referred to as "compound (1A-3)") can be manufactured as a crystal that exhibits an endothermic peak in the range of 142 to 146 °C in differential scanning calorimetry analysis. The range of said onset temperature is preferably the range of 143 to 145 °C.

[0135] [Chemistry 27]

[0136] The crystal of the compound (1A-3) of the present invention further exhibits diffraction peaks at diffraction angles 2θ of 14.4±0.2°, 17.2±0.2° and 21.8±0.2° in the powder X-ray diffraction peak pattern using Cu-Kα rays.

[0137] In the powder X-ray diffraction peak pattern using Cu-Kα rays, in addition to the peaks mentioned above, it is more preferable to have diffraction peaks at diffraction angles 2θ of 22.2±0.2° and 23.3±0.2°. In addition to these peaks, it is even more preferable to have diffraction peaks at 8.6±0.2°, 9.4±0.2° and 12.9±0.2°.

[0138] In addition, the peaks of powder X-ray diffraction using Cu-Kα rays are based on the peak with the maximum intensity (relative intensity is 100), and the relative intensity is preferably 15 or more, more preferably 25 or more. The relative intensity may vary depending on the measuring device or conditions or when it is a mixture with other crystals, so the crystal phase can be identified based on the analytical methods of conventional powder X-ray diffraction analysis.

[0139] Regarding the purity of the crystals of the compound (1A-3) of the present invention, in high-performance liquid chromatography (HPLC) analysis, the peak area of ​​compound (1A-3) is preferably 95.0% or more, more preferably 97.0% or more, further preferably 98.0% or more, and particularly preferably 99.0% or more, relative to the peak areas of all components detected at a wavelength of 280 nm. Furthermore, the HPLC analysis method for determining the purity of the crystals of the present invention is the HPLC analysis method according to the analytical methods described in the embodiments below.

[0140] (Method for manufacturing crystals of the compound represented by chemical formula (1A-3)) The method for manufacturing crystals of compound (1A-3) is characterized by a crystallization step that precipitates crystals by means of a crystallization solution containing compound (1A-3) and an aromatic hydrocarbon solvent having 7 to 9 carbon atoms.

[0141] In the crystallization process for manufacturing crystals of the compound (1A-3) of the present invention, a liquid after the reaction solution containing the compound (1A-3) has been treated as described above and after post-treatment, or crystals of the compound (1A-3) of the present invention, etc., can be used.

[0142] As an aromatic hydrocarbon solvent with 7 to 9 carbon atoms used in the crystallization process of the present invention, examples include toluene, o-xylene, m-xylene, p-xylene, and mesitylene, and preferably a solvent selected from any one of these. Aromatic hydrocarbon solvents with 7 or 8 carbon atoms are more preferably solvents selected from any one of toluene, o-xylene, m-xylene, and p-xylene, and toluene, an aromatic hydrocarbon solvent with 7 carbon atoms, is particularly preferred.

[0143] The amount of aromatic hydrocarbon solvent with 7 to 9 carbon atoms used is preferably 0.5 to 6.0 times the weight of the compound (1A-3) used, more preferably 1.5 to 5.5 times the weight, even more preferably 2.0 to 5.5 times the weight, and particularly preferably 2.5 to 5.5 times the weight.

[0144] The crystallization solution may contain water or other organic solvents (such as phenol or methanol, ethanol or other lower alcohols, benzene, toluene, xylene or other aromatic hydrocarbon solvents used in the raw materials) as long as it does not impair the effect of the present invention. The total amount of compound (1A-3) and crystallization solvent in the crystallization solution is preferably 80% by weight or more, more preferably 90% by weight or more, and even more preferably 95% by weight or more, relative to the total weight of the crystallization solution. It is particularly preferred to prepare a crystallization solution without containing other organic solvents for compound (1A-3).

[0145] Before crystallizing compound (1A-3) through the crystallization process, the crystallization solution may be treated as needed, such as by mixing water and removing the separated water layer to remove water-soluble impurities such as metals, salts, and organic matter, or by washing the oil layer with water, or by vacuum distillation or steam distillation to remove the solvent or phenol used in the reaction. Such treatment is preferred.

[0146] When precipitating crystals, seed crystals may not be used, but it is preferable to use seed crystals. There are no restrictions on the crystals used as seed crystals; crystals of the compound (1A-3) obtained initially without seed crystals can be used. The amount of seed crystal used is preferably in the range of 0.1 to 1.0% by weight relative to the precipitated compound (1A-3).

[0147] The temperature at which crystals precipitate from the crystallization solution prepared above depends on the boiling point of the crystallization solvent used, and is preferably within a range of 5 to 60°C, more preferably within a range of 5 to 40°C, even more preferably within a range of 10 to 40°C, and particularly preferably within a range of 15 to 40°C.

[0148] It is preferable to maintain the same temperature after crystal precipitation begins to increase the amount of crystal precipitation. There is no particular limitation on the holding time, which is usually in the range of 1 to 48 hours, preferably in the range of 3 to 24 hours.

[0149] After increasing the amount of crystal precipitation, the liquid containing the crystals can be cooled, with a final cooling temperature preferably between 10 and 30°C. The cooling rate is preferably in the range of 3 to 20°C / hour, more preferably in the range of 5 to 15°C / hour. To dissolve the fine crystals and improve the slurry properties or particle size distribution, the precipitated crystals can be further heated to the crystal dissolution temperature and then cooled again. Separation can be achieved through filtration.

[0150] The filtered crystals are preferably washed with water or an organic solvent. As the organic solvent used, an aromatic hydrocarbon solvent with 7 to 9 carbon atoms, which is used in the crystallization process, is preferred. The amount of this aromatic hydrocarbon solvent with 7 to 9 carbon atoms used for washing is preferably 0.5 to 10.0 times the weight of the crystals of compound (1A-3), more preferably 0.5 to 5.0 times the weight, even more preferably 1.0 to 5.0 times the weight, and particularly preferably 1.0 to 3.0 times the weight.

[0151] (Post-isolation treatment of crystals of compound (1A-3)) The crystals of the filtered and separated compound (1A-3) can be dried to remove the solvent adhering to the crystals by performing a drying process under specified conditions.

[0152] The drying temperature is preferably in the range of 20~100℃, and more preferably in the range of 30~80℃.

[0153] Drying can be carried out under normal pressure or under reduced pressure. When carried out industrially, since the solvent used can be removed, it is preferred to be carried out under reduced pressure of 20 kPa or less, more preferably under reduced pressure of 10 kPa or less, even more preferably under reduced pressure of 5 kPa or less, and particularly preferably under reduced pressure of 2 kPa or less.

[0154] <Crystals of compounds represented by chemical formulas (1A-4) of the present invention and their manufacturing methods> (Crystals of the compound represented by chemical formula (1A-4)) Among the triphenylalkane compounds represented by general formula (1A) of the present invention, the compound represented by chemical formula (1A-4) (hereinafter, sometimes referred to as "compound (1A-4)") can be manufactured as a crystal that exhibits an endothermic peak in the range of 202 to 210°C in differential scanning calorimetry analysis. The range of said onset temperature is preferably 203 to 209°C, more preferably 203 to 208°C, and particularly preferably 203 to 207°C.

[0155] [Chemistry 28]

[0156] The crystals of the compounds (1A-4) of the present invention can be manufactured as (i) crystals exhibiting an endothermic peak in the range of 202 to 210°C and an endothermic peak in the range of 120 to 130°C in differential scanning calorimetry analysis (sometimes called "α crystals"), (ii) crystals exhibiting only an endothermic peak in the range of 202 to 210°C in differential scanning calorimetry analysis (sometimes called "β crystals"), and (iii) crystals exhibiting an endothermic peak in the range of 202 to 210°C and an endothermic peak in the range of 194 to 200°C in differential scanning calorimetry analysis (sometimes called "γ crystals"), preferably any one of these methods.

[0157] In the crystal configuration (i), the range of the starting temperature is preferably 203~209°C and 121~129°C, more preferably 203~208°C and 122~128°C, and particularly preferably 203~207°C and 123~127°C.

[0158] In the crystal method (ii), the range of the starting temperature is preferably 203 to 209°C, more preferably 203 to 208°C, and particularly preferably 203 to 207°C.

[0159] In the crystal configuration (iii), the range of the starting temperature is preferably 203~209°C and 195~199°C, more preferably 203~208°C and 196~199°C, and particularly preferably 203~207°C and 196~198°C.

[0160] The crystal form (i) (α crystal) of the compound (1A-4) of the present invention further preferably has diffraction peaks at diffraction angles 2θ of 13.4±0.2° and 16.0±0.2° in the powder X-ray diffraction peak pattern using Cu-Kα rays.

[0161] In the powder X-ray diffraction peak pattern using Cu-Kα rays, in addition to the peaks mentioned above, it is more preferable to have diffraction peaks at diffraction angles 2θ of 6.7±0.2° and 18.2±0.2°. In addition to these peaks, it is even more preferable to have diffraction peaks at 5.4±0.2°, 13.7±0.2° and 20.1±0.2°.

[0162] The crystalline form (ii) (β crystal) of the compound (1A-4) of the present invention further preferably has diffraction peaks at diffraction angles 2θ of 13.9±0.2°, 16.8±0.2° and 24.0±0.2° in the powder X-ray diffraction peak pattern using Cu-Kα rays.

[0163] In the powder X-ray diffraction peak pattern using Cu-Kα rays, in addition to the peaks mentioned above, it is more preferable to have diffraction peaks at diffraction angles 2θ of 12.0±0.2° and 16.4±0.2°. In addition to these peaks, it is even more preferable to have diffraction peaks at 17.9±0.2°, 19.2±0.2° and 19.6±0.2°.

[0164] The crystal form (iii) (γ crystal) of the compound (1A-4) of the present invention further preferably has diffraction peaks at diffraction angles 2θ of 12.1±0.2°, 13.9±0.2° and 21.8±0.2° in the powder X-ray diffraction peak pattern using Cu-Kα rays.

[0165] In the powder X-ray diffraction peak pattern using Cu-Kα rays, in addition to the peaks mentioned above, it is more preferable to have a diffraction peak at a diffraction angle 2θ of 24.1±0.2°. In addition to these peaks, it is even more preferable to have diffraction peaks at 18.5±0.2° and 20.9±0.2°.

[0166] Furthermore, regardless of the crystal type, the peaks of powder X-ray diffraction using Cu-Kα rays are taken as the reference peak with the maximum intensity (relative intensity of 100), preferably with a relative intensity of 15 or more, more preferably 25 or more. The relative intensity may vary depending on the measuring device or conditions, or when it is a mixture with other crystals, so the crystal phase can be identified based on the analytical methods of conventional powder X-ray diffraction analysis.

[0167] The crystals of the compound (1A-4) of the present invention can be prepared into easily manipulated crystalline powders in any manner, and are therefore very useful.

[0168] The crystal form (i) (α crystal) of the compound (1A-4) of the present invention is presumably a crystal of compound (1A-4) encapsulated with methyl isobutyl ketone. The crystal (α crystal) of form (i) contains 4 to 15% by weight of methyl isobutyl ketone. The crystal (α crystal) of form (i) can be used to produce the crystal (β crystal) of form (ii) which has the usefulness described later.

[0169] The organic solvent content in the crystallization (ii) (β crystal) and (iii) (γ crystal) forms of the compound (1A-4) of the present invention is low. In addition to being useful in the manufacture of derivatives or resin materials using the compound (1A-4), it can reduce the risk of workers being exposed to organic solvents in industrial operations. It is more preferred because it contributes to workplace safety or health.

[0170] Regarding the purity of the crystals of the compound (1A-4) of the present invention, in any manner, during high-performance liquid chromatography (HPLC) analysis, the ratio of the peak area of ​​compound (1A-4) to the peak area of ​​all components detected at a wavelength of 280 nm is preferably 95.0% or more, more preferably 97.0% or more, further preferably 98.0% or more, and particularly preferably 99.0% or more. Furthermore, the HPLC analysis method for determining the purity of the crystals of the present invention is the HPLC analysis method according to the analytical methods described in the examples below.

[0171] (Method for manufacturing crystals of the compound represented by chemical formula (1A-4)) The method for manufacturing crystals of compound (1A-4) is characterized by a crystallization step that precipitates crystals by means of a crystallization solution containing compound (1A-4) and a chain-like aliphatic ketone solvent with a total carbon number of 4 to 8.

[0172] In the crystallization process for manufacturing crystals of the compound (1A-4) of the present invention, as in the reaction process and post-processing described above, a liquid after treating a reaction solution containing the compound (1A-4), or crystals of the compound (1A-4) of the present invention, may be used.

[0173] As a chain aliphatic ketone solvent with a total carbon number of 4 to 8 used in the crystallization process of the present invention, examples include methyl ethyl ketone (4 carbon atoms), diethyl ketone, 2-pentanone, isopropyl methyl ketone (5 carbon atoms), methyl isobutyl ketone (6 carbon atoms), isopentyl methyl ketone, 2-heptanone (7 carbon atoms), and methyl hexyl ketone (8 carbon atoms). One solvent selected from these can be used. Among the chain aliphatic ketone solvents with a total carbon number of 5 to 7, diethyl ketone, methyl isobutyl ketone, isopentyl methyl ketone, or 2-heptanone are preferred. Among the chain aliphatic ketone solvents with a total carbon number of 6 or 7, methyl isobutyl ketone, isopentyl methyl ketone, or 2-heptanone are more preferred. A chain aliphatic ketone solvent with a total carbon number of 6 is particularly preferred. Among the chain aliphatic ketone solvents with a total carbon number of 6, methyl isobutyl ketone is particularly preferred.

[0174] In the crystals of the present invention, the crystals of method (i) (α crystals) are manufactured by using methyl isobutyl ketone in a chain-like aliphatic ketone solvent with a total number of carbon atoms through a crystallization process performed in the following manner.

[0175] The amount of a chain aliphatic ketone solvent with a total carbon number of 4 to 8 is preferably 0.5 to 6.0 times the weight of the compound (1A-4) used, more preferably 1.5 to 5.5 times the weight, even more preferably 2.0 to 5.5 times the weight, and particularly preferably 2.5 to 5.5 times the weight.

[0176] The crystallization solution may contain water or other organic solvents (such as phenol or methanol, ethanol or other lower alcohols, benzene, toluene, xylene or other aromatic hydrocarbon solvents used in the raw materials) as long as it does not impair the effect of the present invention. The total amount of compound (1A-4) and crystallization solvent in the crystallization solution is preferably 90% by weight or more, more preferably 95% by weight or more, and even more preferably 98% by weight or more, relative to the total weight of the crystallization solution. It is particularly preferred to prepare a crystallization solution without containing other organic solvents for compound (1A-4).

[0177] Before crystallizing compound (1A-4) through the crystallization process, the crystallization solution may be treated as needed, such as by mixing water and removing the separated water layer to remove water-soluble impurities such as metals, salts, and organic matter, or by washing the oil layer with water, or by vacuum distillation or steam distillation to remove the solvent or phenol used in the reaction. Such treatment is preferred.

[0178] When precipitating crystals, seed crystals may not be used, but it is preferable to use seed crystals. There are no restrictions on the crystals used as seed crystals; crystals of the compound (1A-4) obtained initially without seed crystals can be used. The amount of seed crystals used is preferably in the range of 0.1 to 1.0% by weight relative to the precipitated compound (1A-4).

[0179] The temperature at which crystals precipitate from the crystallization solution prepared above depends on the boiling point of the crystallization solvent used, and is preferably within the range of 5 to 80°C, not exceeding that range.

[0180] In the crystal of the present invention, when manufacturing the crystal (α crystal) of method (i), the temperature at which the crystal precipitates is preferably in the range of 5 to 45°C, more preferably in the range of 10 to 40°C, and even more preferably in the range of 15 to 40°C.

[0181] In the crystal of the present invention, when manufacturing the crystal (γ crystal) of method (iii), the temperature at which the crystal precipitates is preferably in the range of 55 to 80°C, more preferably in the range of 60 to 80°C, and even more preferably in the range of 65 to 75°C.

[0182] It is preferable to maintain the same temperature after crystal precipitation begins to increase the amount of crystal precipitation. There is no particular limitation on the holding time, which is usually in the range of 1 to 48 hours, preferably in the range of 3 to 24 hours.

[0183] After increasing the amount of crystal precipitation, the liquid containing the crystals can be cooled, with a final cooling temperature preferably between 10 and 30°C. The cooling rate is preferably in the range of 3 to 20°C / hour, more preferably in the range of 5 to 15°C / hour. To dissolve the fine crystals and improve the slurry properties or particle size distribution, the precipitated crystals can be further heated to the crystal dissolution temperature and then cooled again. Separation can be achieved through filtration.

[0184] The filtered crystals are preferably washed with water or an organic solvent. As the organic solvent used, a chain-like aliphatic ketone solvent with 4 to 8 total carbon atoms, used in the crystallization process, is preferred. The amount of this chain-like aliphatic ketone solvent with 4 to 8 total carbon atoms used for washing is preferably 0.5 to 10.0 times the weight of the crystals of compound (1A-4), more preferably 0.5 to 5.0 times the weight, even more preferably 1.0 to 5.0 times the weight, and particularly preferably 1.0 to 3.0 times the weight.

[0185] (Post-isolation treatment of crystals of compound (1A-4)) The crystals (α crystals) of compound (1A-4) separated by filtration using the above method (i) can have the solvent adhering to the crystals removed by drying in the range of 20 to 110°C. The temperature range is preferably 30 to 100°C, and more preferably 30 to 90°C.

[0186] When drying the crystals (α crystals) by method (i), the process can be carried out under normal pressure or under reduced pressure. In industrial applications, since the solvent used can be removed, it is preferable to use a reduced pressure of 20 kPa or less, more preferably 10 kPa or less, even more preferably 5 kPa or less, and particularly preferably 2 kPa or less.

[0187] The crystals (γ crystals) of compound (1A-4) separated by filtration using the above method (iii) can have the solvent adhering to the crystals removed by drying in the range of 20 to 180°C. The preferred temperature range is 60 to 160°C, and more preferably 80 to 150°C.

[0188] When drying crystals (γ crystals) in method (iii), the process can be carried out under normal pressure or under reduced pressure. In industrial applications, since the solvent used can be removed, it is preferable to use a reduced pressure of 20 kPa or less, more preferably 10 kPa or less, even more preferably 5 kPa or less, and particularly preferably 2 kPa or less.

[0189] (Method for manufacturing crystal (β crystal) of method (ii)) In the crystals of compound (1A-4), the crystal of manner (ii) (β crystal) can be manufactured by heating the crystal of manner (i) (α crystal) obtained by the above method to a temperature range of 120-200°C. The temperature range is preferably 130-195°C, more preferably 135-180°C. By heating to the temperature range, the methyl isobutyl ketone encapsulated in the crystal of manner (i) (α crystal) is decoupled, thus producing the crystal of manner (ii) (β crystal).

[0190] Drying can be carried out under normal pressure or under reduced pressure. When carried out industrially, since the solvent used can be removed, it is preferred to be carried out under reduced pressure of 20 kPa or less, more preferably under reduced pressure of 10 kPa or less, even more preferably under reduced pressure of 5 kPa or less, and particularly preferably under reduced pressure of 2 kPa or less.

[0191] <Method for manufacturing triphenylalkane compounds represented by general formula (1B): reaction steps> The reaction step in the method for manufacturing the triphenylalkane compound represented by general formula (1B) is a step of reacting the triphenylalkane compound represented by general formula (1A) with the haloalkene represented by general formula (4) in the presence of a base.

[0192] <Halogenated alkenes represented by general formula (4)> R in general formula (4) 1a The definition is the same as that of general formula (1B), and the preferred method is also the same.

[0193] In general formula (4), X is a halogen atom, specifically fluorine atom, chlorine atom, bromine atom, and iodine atom. Among them, chlorine atom or bromine atom is preferred from the viewpoint of reactivity and availability of raw materials.

[0194] As a haloalkene represented by general formula (4), specifically, compounds represented by chemical formulas (4-1) to (4-6) can be listed, and any one of these is preferred. Among them, compounds represented by chemical formulas (4-1) to (4-4) are more preferred, and allyl chloride represented by chemical formula (4-3) or allyl bromide represented by chemical formula (4-4) is even more preferred.

[0195] [Chemistry 29]

[0196] In this manufacturing method, the amount of haloolefin used as represented by general formula (4) is preferably in the range of 1 to 10 equivalents relative to one hydroxyphenyl group of the triphenylalkane compound represented by general formula (1A), more preferably in the range of 1 to 5 equivalents, and even more preferably in the range of 1 to 3 equivalents.

[0197] (Alkali) In the reaction process, to capture the generated hydrogen halides, it is preferable to carry out the reaction in the presence of a base. Besides inorganic bases such as sodium hydride, sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide, the reaction can also be carried out in the presence of alkali metal bromide salts such as sodium bromide and potassium bromide, alkali metal iodide salts such as sodium iodide and potassium iodide, ammonium bromide, and ammonium iodide, depending on the requirements. The alkaline catalyst or co-catalyst is not limited to these.

[0198] The amount of base used is preferably in the range of 1 to 10 equivalents relative to one hydroxyphenyl group of the triphenylalkane compound represented by general formula (1A), more preferably in the range of 1 to 5 equivalents, and even more preferably in the range of 1 to 3 equivalents.

[0199] (Reaction solvent) In the reaction process, it is usually carried out in the presence of a solvent. There are no particular restrictions on the reaction solvent as long as it does not hinder the reaction; examples include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and sec-butanol; cyclic alkanes such as cyclopentane, cyclohexane, and cycloheptane; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, and dioxane; ketones such as acetone, diethyl ketone, methyl n-butyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, and isobutyl acetate; nitriles such as acetonitrile; and amides such as N,N-dimethylformamide and N-methylpyrrolidone. These reaction solvents can be used alone or in combination.

[0200] There are no particular restrictions on the amount of reaction solvent used, as long as it does not hinder the reaction. Generally, it is preferred to be 0.5 to 5 times the weight of the triphenylalkane compound represented by general formula (1A), and more preferably 1 to 3 times the weight.

[0201] (Reaction conditions) The reaction process is typically carried out within a temperature range of 0–120°C, preferably 10–80°C, and even more preferably 20–70°C. Excessive reaction temperature increases byproducts and decreases yield, while excessively low reaction temperature slows down the reaction rate.

[0202] Regarding the reaction pressure, it can be carried out under normal pressure, or under pressure or pressure.

[0203] Regarding the reaction solution containing the triphenylalkane compound of general formula (1B) after the reaction is completed, the triphenylalkane compound represented by general formula (1B) can be obtained from the mixture by known methods after the reaction. For example, after the reaction, an organic solvent such as toluene, xylene, or methyl isobutyl ketone that can dissolve the reaction product and separate it from water can be mixed, and residual raw materials and solvents can be removed by washing the oil phase solution with water or by distillation from the reaction mixture, so that the triphenylalkane compound of general formula (1B) as the target product can be obtained in the form of a residual liquid.

[0204] <Crystals of compounds represented by chemical formulas (1B-4) of the present invention and their manufacturing methods> (Crystals of the compound represented by chemical formula (1B-4)) Among the triphenylalkane compounds represented by general formula (1B) of the present invention, the compound represented by chemical formula (1B-4) (hereinafter, sometimes referred to as "compound (1B-4)") can be manufactured as crystals with an initial temperature in the range of 116 to 124 °C based on differential scanning calorimetry analysis.

[0205] [Chemistry 30]

[0206] The crystal of the compound (1B-4) of the present invention further exhibits diffraction peaks at diffraction angles 2θ of 17.2±0.2°, 18.3±0.2° and 23.9±0.2° in the powder X-ray diffraction peak pattern using Cu-Kα rays.

[0207] In the powder X-ray diffraction peak pattern using Cu-Kα rays, in addition to the peaks mentioned above, it is more preferable to have diffraction peaks at diffraction angles 2θ of 12.7±0.2° and 15.9±0.2°, and even more preferably, diffraction peaks at 14.1±0.2° and 24.7±0.2°.

[0208] In addition, the peaks of powder X-ray diffraction using Cu-Kα rays are taken as the reference with the peak of maximum intensity (relative intensity is 100). The relative intensity is preferably 15 or more, more preferably 25 or more. The relative intensity may vary depending on the measuring device or conditions or when it is a mixture with other crystals. Therefore, the crystal phase can be identified based on the analytical method of conventional powder X-ray diffraction analysis.

[0209] Regarding the purity of the crystals of compound (1B-4) of the present invention, in high-performance liquid chromatography (HPLC) analysis, the peak area of ​​compound (1B-4) is preferably 95.0% or more, more preferably 97.0% or more, further preferably 98.0% or more, and particularly preferably 99.0% or more, relative to the peak areas of all components detected at a wavelength of 280 nm. Furthermore, the HPLC analysis method for determining the purity of the crystals of compound (1B-4) is the HPLC analysis method according to the analytical method described in the examples below.

[0210] (Method for manufacturing crystals of the compound represented by chemical formula (1B-4)) The method for manufacturing crystals of compound (1B-4) is characterized by a crystallization step in which crystals are precipitated by means of a crystallization solution containing a compound (1B-4) obtained by the above method and a chain aliphatic carboxylic acid ester solvent with a total carbon number of 6 to 8.

[0211] In the crystallization process for manufacturing crystals of the compound (1B-4) of the present invention, a liquid after the reaction solution containing the compound (1B-4) has been treated as described above and after post-treatment, or crystals of the compound (1B-4) of the present invention, etc., can be used.

[0212] As a solvent for a chain-like aliphatic carboxylic acid esters with a total carbon number of 6 to 8 used in the crystallization process of the present invention, examples include butyl acetate (n-butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate), amyl acetate (n-amyl acetate (also known as amyl acetate), isoamyl acetate, etc.), and hexyl acetate (n-hexyl acetate, etc.). Any solvent selected from these can be used. Preferably, a chain-like aliphatic carboxylic acid ester solvent with a total carbon number of 6 or 7 is used. More preferably, a chain-like aliphatic acetate solvent with a total carbon number of 6 or 7 is used. Butyl acetate or amyl acetate is more preferred. A chain-like aliphatic acetate solvent with a total carbon number of 6 is even more preferred. Butyl acetate is particularly preferred. Among butyl acetate, n-butyl acetate is the most preferred.

[0213] The amount of aliphatic carboxylic acid ester solvent with a total carbon number of 6 to 8 relative to the amount of compound (1B-4) used can be appropriately adjusted based on the solubility of compound (1B-4) in the solvent. Preferably, the amount used is in the range of 0.3 to 3.0 times by weight; more preferably, in the range of 0.5 to 2.0 times by weight; even more preferably, in the range of 0.5 to 1.5 times by weight; and particularly preferably, in the range of 0.6 to 1.3 times by weight. The amount of aliphatic carboxylic acid ester solvent with a total carbon number of 6 to 8 can be adjusted by the amount added or by removing it from the system by distillation.

[0214] The crystallization solution may contain water or other organic solvents (such as phenol or methanol, ethanol, or aromatic hydrocarbon solvents such as benzene, toluene, and xylene used in the raw materials) as long as it does not impair the effect of the present invention. The total amount of compound (1B-4) and crystallization solvent in the crystallization solution is preferably 80% by weight or more, more preferably 90% by weight or more, and even more preferably 95% by weight or more, relative to the total weight of the crystallization solution. It is particularly preferred to prepare a crystallization solution without containing other organic solvents for compound (1B-4).

[0215] Before crystallizing compound (1B-4) through the crystallization process, the crystallization solution may be treated as needed, such as by mixing water and removing the separated water layer to remove water-soluble impurities such as metals, salts, and organic matter, or by washing the oil layer with water, or by vacuum distillation or steam distillation to remove the solvent or phenol used in the reaction. Such treatment is preferred.

[0216] When precipitating crystals, seed crystals may not be used, but it is preferable to use seed crystals. There are no restrictions on the crystals used as seed crystals; the crystals of the present invention obtained initially without seed crystals may be used. The amount of seed crystals used is preferably in the range of 0.1 to 1.0% by weight relative to the precipitated compound (1B-4).

[0217] The temperature at which crystals precipitate from the crystallization solution prepared above depends on the boiling point of the crystallization solvent used, and is preferably within a range of 5 to 60°C, more preferably within a range of 5 to 40°C, even more preferably within a range of 10 to 40°C, and particularly preferably within a range of 15 to 40°C.

[0218] It is preferable to maintain the same temperature after crystal precipitation begins to increase the amount of crystal precipitation. There is no particular limitation on the holding time, which is usually in the range of 1 to 48 hours, preferably in the range of 3 to 24 hours.

[0219] After increasing the amount of crystal precipitation, the liquid containing the crystals can be cooled, with a final cooling temperature preferably between 10 and 30°C. The cooling rate is preferably in the range of 3 to 20°C / hour, more preferably in the range of 5 to 15°C / hour. To dissolve the fine crystals and improve the slurry properties or particle size distribution, the precipitated crystals can be further heated to the crystal dissolution temperature and then cooled again. Separation can be achieved through filtration.

[0220] The filtered crystals are preferably washed with water or an organic solvent. As the organic solvent used, a chain aliphatic carboxylic acid ester solvent with a total carbon number of 6 to 8, which is used in the crystallization process, is preferred. The amount of this chain aliphatic carboxylic acid ester solvent with a total carbon number of 6 to 8 used for washing is preferably 0.5 to 10.0 times the weight of the crystals of compound (1B-4), more preferably 0.5 to 5.0 times the weight, even more preferably 1.0 to 5.0 times the weight, and particularly preferably 1.0 to 3.0 times the weight.

[0221] (Post-isolation treatment of crystals of compound (1B-4)) The crystals of the filtered and separated compound (1B-4) can be dried to remove the solvent adhering to the crystals by performing a drying process under specified conditions.

[0222] The drying temperature is preferably in the range of 20~100℃, and more preferably in the range of 30~80℃.

[0223] Drying can be carried out under normal pressure or under reduced pressure. When carried out industrially, since the solvent used can be removed, it is preferred to be carried out under reduced pressure of 20 kPa or less, more preferably under reduced pressure of 10 kPa or less, even more preferably under reduced pressure of 5 kPa or less, and particularly preferably under reduced pressure of 2 kPa or less.

[0224] <Curing Resin Composition> The triphenylalkane compound represented by general formula (1B) of the present invention can be used in a curable resin composition containing polyphenylene ether resin as component A and the triphenylalkane compound represented by general formula (1B) as component B. The triphenylalkane compound represented by general formula (1B) as component B in the curable resin composition of the present invention preferably functions as a curing agent.

[0225] The curable resin composition preferably contains components A and B, and may further contain components C and / or D as described below, if necessary.

[0226] <Component A> Regarding the polyphenylene ether resin used as component A, there are no particular limitations on the polyphenylene ether resin that can be used, but it is preferable to have a polyphenylene ether resin having a repeating unit represented by general formula (5), and more preferably a polyphenylene ether resin having a repeating unit represented by general formula (5-1). As the terminal structure of such a polyphenylene ether resin, hydrogen atoms or substituents having unsaturated bonds can be listed. As the terminal structure on the oxygen atom side of the repeating unit, substituents having unsaturated bonds are preferred.

[0227] Substituents with unsaturated bonds include acrylate groups, methacrylate groups, alkenyl ether groups with 2 to 4 carbon atoms, or styryl ether groups (CH2=CHC6H4O-), which are preferred, with acrylate groups or methacrylate groups being particularly preferred.

[0228] [Chemistry 31]

[0229] (In the formula, R5 independently represents a chain alkyl group with 1 to 6 carbon atoms, a branched alkyl group with 3 to 6 carbon atoms, a cyclic alkyl group with 5 or 6 carbon atoms, a phenyl group, or a halogen atom; p independently represents 0, 1, 2, or 3; and q independently represents an integer greater than 1.) [Chemistry 32]

[0230] (In the formula, the definition of q is the same as in general formula (5).) Specific examples of polyphenylene ether resin as component A include, for example, copolymers of poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), 2,6-dimethylphenol and other phenols (e.g., 2,3,6-trimethylphenol, 2-methyl-6-butylphenol, etc.), polyphenylene ether copolymers obtained by coupling 2,6-dimethylphenol with biphenols, bisphenols or triphenols, and polyphenylene ether copolymers obtained by coupling 2,6-dimethylphenol and other phenols (e.g., 2,3,6-trimethylphenol, 2-methyl-6-butylphenol, etc.) with biphenols, bisphenols or triphenols, etc.

[0231] Furthermore, examples of polyphenylene ether resins with terminal substituents having unsaturated bonds such as acrylate groups, methacrylate groups, alkenyl ether groups with 2 to 4 carbon atoms, or styryl ether groups (CH2=CHC6H4O-) can also be cited. For example, a polyphenylene ether resin can be obtained by terminal (meth)acrylate esterification of a copolymer of 2,6-dimethylphenol and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane.

[0232] Polyphenylene ether resins that can be used as component A are preferably polyphenylene ether resins modified with functional groups having unsaturated double bonds.

[0233] The functional group with unsaturated double bonds used for modification is preferably acrylate group, methacrylate group, alkenyl ether group or styryl ether group with 2 to 4 carbon atoms, and acrylate group or methacrylate group is particularly preferred.

[0234] Among polyphenylene ether resins modified with functional groups having unsaturated double bonds, polyphenylene ether resins modified with functional groups having unsaturated double bonds are more preferably polyphenylene ether copolymers obtained by coupling 2,6-dimethylphenol with biphenols, bisphenols, or triphenols; or polyphenylene ether resins modified with functional groups having unsaturated double bonds are polyphenylene ether copolymers obtained by coupling 2,6-dimethylphenol and other phenols (e.g., 2,3,6-trimethylphenol, 2-methyl-6-butylphenol, etc.) with biphenols, bisphenols, or triphenols. 2,6-dimethylphenol and biphenols are even more preferred. Polyphenylene ether resin obtained by esterification of the end (meth)acrylate of polyphenylene ether copolymers obtained by coupling with bisphenols or triphenols, or polyphenylene ether resin obtained by esterification of the end (meth)acrylate of polyphenylene ether copolymers obtained by coupling with biphenols, bisphenols or triphenols, particularly preferred is polyphenylene ether resin obtained by esterification of the end (meth)acrylate of copolymers of 2,6-dimethylphenol and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane.

[0235] <Ingredient B> The curable resin composition of the present invention contains component B in the range of 1.0 to 10.0 parts by weight relative to 100 parts by weight of component A, preferably in which component B functions as a curing agent.

[0236] The content of component B is more preferably in the range of 1.0 to 8.0 parts by weight relative to 100 parts by weight of component A, and particularly preferably in the range of 1.0 to 5.5 parts by weight.

[0237] The amount of component B used in the curable resin composition of the present invention is extremely small compared to the amount of curing agent used in the past, and a cured product with excellent physical properties can be obtained even with a reduced amount used, which is therefore useful. Furthermore, compared to conventional curable resin compositions, since the proportion of polyphenylene ether resin with a low relative permittivity and dielectric loss tangent can be increased, it is expected that printed circuit boards with excellent electrical properties can be obtained, for example, when used as substrate materials for printed circuit boards.

[0238] The curable resin composition of the present invention preferably contains only a triphenylalkane compound represented by general formula (1B) as a curing agent. However, it may also contain other known curing agents other than the triphenylalkane compound represented by general formula (1B) without impairing the effects of the present invention.

[0239] Other known curing agents include, for example, triallyl isocyanurate compounds, allyl-containing compounds other than triphenylalkanes represented by general formula (1B), polyfunctional allyl ether compounds having two or more allyl ether groups in the molecule, polyfunctional (meth)acrylate compounds having two or more (meth)acryloyl groups in the molecule, and polyfunctional ethylene compounds.

[0240] When other known curing agents are included, the curing agent contained in the curable resin composition of the present invention preferably contains 50% to 99% by weight of a triphenylalkane compound represented by general formula (1B), more preferably 60% to 99% by weight, even more preferably 70% to 99% by weight, and particularly preferably 80% to 99% by weight.

[0241] <Ingredient C> The curable resin composition of the present invention preferably contains a curing reaction initiator as component C, in addition to components A and B. Component C is added to promote the crosslinking reaction of the curable resin composition containing components A and B.

[0242] As for component C, there are no particular restrictions as long as it can promote the cross-linking reaction. Examples include imidazoles, tertiary amines, quaternary ammonium salts, boron trifluoride amine complexes, organophosphorus compounds, organophosphorus salt plasma catalysts, organic peroxides, hydroperoxides, azobisisobutyronitrile and other free radical polymerization initiators, among which organic peroxides are preferred.

[0243] Examples of organic peroxides include di-tert-butyl peroxide, dilauroyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)octane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne, di-n-propyl peroxydicarbonate, and other aliphatic organic peroxides, as well as benzoyl peroxide, dicumyl peroxide, and other peroxides. Aromatic organic peroxides containing aromatic rings include tert-butyl benzoate, tert-amyl peroxide, tert-butylcumyl peroxide, bis(1-tert-butylperoxy-1-methylethyl)benzene, 2-phenyl-2-[(2-phenylpropan-2-yl)peroxy]propane, α,α'-di(tert-butylperoxy)diisopropylbenzene, α,α'-bis(tert-butylperoxy-m-isopropyl)benzene, and di-tert-butylperoxyisophthalate. Aromatic organic peroxides are preferred among these.

[0244] As aromatic organic peroxides, dicumyl peroxide, tert-butylcumyl peroxide, bis(1-tert-butylperoxy-1-methylethyl)benzene, and 2-phenyl-2-[(2-phenylpropan-2-yl)peroxy]propane are more preferred, and 2-phenyl-2-[(2-phenylpropan-2-yl)peroxy]propane is particularly preferred.

[0245] Component C can be used alone or in combination with two or more components.

[0246] The content of component C, relative to 100 parts by weight of component A, is preferably in the range of 0.05 to 1.0 parts by weight, more preferably in the range of 0.05 to 0.9 parts by weight, even more preferably in the range of 0.15 to 0.8 parts by weight, and particularly preferably in the range of 0.3 to 0.7 parts by weight.

[0247] <Ingredient D> The curable resin composition of the present invention preferably contains a filler as component D, in addition to components A, B and, if necessary, component C.

[0248] As for component D, there are generally no special restrictions, as long as it is a known filler that can be used in curable resin compositions. For example, inorganic fillers such as silica, alumina, magnesium oxide, boron nitride, aluminum nitride, silicon nitride, silicon carbide, and hexagonal boron nitride can be mixed and used.

[0249] Regarding the content of component D, it is preferable to contain 10 to 150 parts by weight of component D relative to 100 parts by weight of the total amount of component A and component B or component A, component B and component C, and more preferably 10 to 100 parts by weight.

[0250] The method for preparing the curable resin composition of the present invention is not particularly limited. For example, in addition to mixing the above-mentioned components and mixing or dispersing them by a mixer, methods such as uniformly dissolving and dispersing each component in a solvent and evaporating the solvent can be listed.

[0251] <Component E> The cured product of the curable resin composition of the present invention refers to the cured product (prepreg) obtained by mixing the above-mentioned curable resin composition with reinforcing fibers that are commonly used as component E in prepregs as needed, and then semi-curing (stage B) the mixture, or by further curing (stage C) the mixture (cured product of prepreg).

[0252] As the reinforcing fiber for component E, various inorganic or organic fibers such as carbon fiber, aramid fiber, nylon fiber, high-strength polyester fiber, glass fiber, boron fiber, alumina fiber, and silicon nitride fiber can be used. Among these, carbon fiber, aramid fiber, glass fiber, boron fiber, alumina fiber, and silicon nitride fiber are examples of fibers that can be used from the viewpoint of specific strength and specific modulus. From the viewpoint of insulation, glass fiber is preferred.

[0253] The thickness of the reinforcing fiber is preferably 0.3 mm or less, more preferably 0.15 mm or less, and even more preferably 0.1 mm or less.

[0254] Component E can be used alone or in combination with two or more.

[0255] <Prepreg> There are no particular limitations on the manufacturing method of the prepreg. Known methods for manufacturing prepregs can be used. For example, a varnish containing a varnish solvent as component F can be mixed into the curable resin composition involved in the present invention described above. Further reinforcing fibers as component E can be mixed in as needed. The varnish can be stretched onto a support such as a polyimide or polyester film or a glass substrate. It can be semi-cured (stage B) by heating and drying as needed.

[0256] Regarding the method of mixing the varnish and the reinforcing fiber as component E, examples include methods such as coating the reinforcing fiber as component E with varnish or impregnation.

[0257] Other methods for manufacturing prepregs include adding the aforementioned curable resin composition to a metal mold or similar material without producing a varnish, or heating and melting the composition and then injecting it into a metal mold or similar material, followed by heating it to a specified temperature to cure it.

[0258] Regarding the heating temperature (semi-curing temperature) during semi-curing (B-stage), since the solvent removal process is carried out simultaneously during drying, a temperature above the boiling point of a solvent with good solvent removal efficiency is preferred.

[0259] Specifically, the preferred temperature range is 80~200℃, and the more preferred temperature range is 140~180℃.

[0260] <Component F> As a varnish solvent that can be used in the preparation of the varnish of the curable resin composition of the present invention, the component F can be used as long as it can dissolve or disperse the curable resin composition, and there are no particular limitations. Examples include aromatic compounds such as toluene and xylene, ketone compounds such as methyl ethyl ketone, cyclopentanone, and cyclohexanone, and chlorine organic solvents such as chloroform.

[0261] Among them, aromatic compounds such as toluene and xylene, ketone compounds such as methyl ethyl ketone, cyclopentanone, and cyclohexanone are preferred, aromatic compounds such as toluene and xylene are more preferred, and toluene is particularly preferred.

[0262] The curable resin composition preferably contains 50 to 200 parts by weight of component F relative to 100 parts by weight, and more preferably 70 to 150 parts by weight of component F.

[0263] <Cured product> The prepreg is heated to a specified temperature to further cure it (C-stage curing) to produce a cured product (cured prepreg). The curing temperature can be appropriately determined in the range of 105 to 270°C.

[0264] The curable resin compositions of the present invention, or prepregs, varnishes, and cured products thereof, can be used, for example, as materials for electronic devices such as printed circuit boards.

[0265] Example The present invention will be specifically described below through embodiments, but the present invention is not limited to these embodiments.

[0266] <Analytical Methods for Triphenylalkanes> 1. Purity analysis (High-performance liquid chromatography (HPLC) analysis) (Apparatus and conditions) High-performance liquid chromatography (HPLC) system: Prominence UFLC / manufactured by Shimadzu Corporation Column oven: CTO-20A Detector: SPD-20A Column: HALO C18 column (3mm inner diameter, 75mm length) Incubator temperature: 50℃ Flow rate: 0.7 mL / min Mobile phase: (A) 0.2 vol% aqueous acetic acid solution, (B) methanol Gradient condition: (B) Volume % (time after analysis begins) 0~3min, 20% 3~18min, 20%→100% 18~21min, 100% Injection volume: 5 μL Detection wavelength: 280nm 2. Determination of melting point and glass transition temperature (Tg) (differential scanning calorimetry (DSC) analysis) (Analysis Methods) Take 5 mg of the analytical sample into an aluminum sample container, cap and press firmly to prepare the sample. Analyze the obtained sample using the following apparatus and conditions. The melting point is defined as the onset temperature of the endothermic peak corresponding to the melting of the crystal.

[0267] The measured samples were reanalyzed under the same conditions, and the midpoint of the newly appearing step-like peak change was taken as the glass transition temperature (Tg).

[0268] (Apparatus and conditions) Device: DSC7020 / manufactured by Hitachi High Tech Science Co., Ltd. Heating rate: 10℃ / min. Measurement temperature range: 30~300℃ Measurement atmosphere: Nitrogen 50 mL / min. 3. Determination of thermogravimetric (TG) loss and 5% temperature of weight loss (Td5) (thermogravimetric (TG) analysis) The compounds were evaluated by measuring their thermal weight loss and 5% temperature of weight loss using the following apparatus and conditions.

[0269] (Apparatus and conditions) Device: DTG-60A / Shimadzu Corporation Temperature: 30→400℃ (heating rate 10℃ / min) Measurement atmosphere: Open, nitrogen 50 mL / min. Sample weight: 8~12mg Sample container material: Aluminum 4. Determination of refractive index N-methylpyrrolidone and each sample were mixed in any weight ratio, and the refractive index of each sample solution was measured at 20°C.

[0270] Apparatus: RA-500 refractometer / manufactured by Kyoto Electronics Industry Co., Ltd. The obtained refractive index values ​​were plotted against the solution concentration to form a linear function. The value of the function when the sample concentration reached 100% was obtained by extrapolation and used as the refractive index of each sample monomer.

[0271] <Analytical Methods for Cured Products of Curable Resin Compositions> 5. Determination of dielectric constant and dielectric loss tangent The relative permittivity and dielectric loss tangent of a resin film obtained by curing a curable resin composition were determined using the following apparatus and conditions.

[0272] (Apparatus and conditions) Device: Cavity resonator manufactured by AET Corporation Sample size: 500mm × 500mm Frequency: 10GHz Mode: TE Measurement temperature: 25℃ 6. Determination of storage modulus (Dynamic viscoelasticity determination (DMA)) Using the apparatus described below and under the conditions described below, the resin film obtained by curing a curable resin composition was measured, and the measured values ​​at 30°C and 40°C were taken as the storage modulus.

[0273] (Apparatus and conditions) Device: DMA850 / TA Instrument Co., Ltd. Sample dimensions: 3mm wide, 15mm long Conditions: Frequency 1.0 Hz, Amplitude (displacement) 15.0 μm, Temperature range 25~200℃, Heating rate 2℃ / min Measurement mode: Tension <Preparation of Triphenylalkanes> <Example 1> <Synthesis of Compound (1A-3)> Add 119.8 g of 2,6-xylenol, 12.1 g of toluene, and 6.5 g of 1-dodecyl mercaptan to a 500 mL four-necked flask equipped with a thermometer, stirrer, dropping funnel, and condenser, and then add 20.5 g of 35% hydrochloric acid dropwise. Add a mixed solution of 65.1 g of 4-(2-hydroxyethoxy)benzaldehyde and 16.2 g of toluene dropwise over 2 hours while maintaining the temperature at 40 °C. After the addition is complete, allow the mixture to react for another 5 hours.

[0274] After the reaction was complete, sodium hydroxide aqueous solution was added to the reaction solution for neutralization, followed by the addition of 240.4 g of toluene. The solution temperature was raised to 80°C, stirred, and allowed to stand before removing the aqueous layer. Then, 153.8 g of water was added, stirred, allowed to stand, and the aqueous layer was removed. This process was repeated, followed by the addition of 200 g of toluene. The solution was cooled to 30°C, and the precipitated solid was separated by filtration.

[0275] 172.1 g of the obtained solid and 516.6 g of toluene were added to a 1 L four-necked flask equipped with a thermometer, stirrer, and condenser, and the mixture was heated to 85 °C to dissolve it. The solution was cooled to 30 °C, and the precipitated solid was separated by filtration and dried to obtain 94.1 g of orange powder. The yield of 4-(2-hydroxyethoxy)benzaldehyde relative to the starting material was 61%.

[0276] Through the obtained solid 1 H-NMR and LC-MS analyses confirmed the compound as the target compound (1A-3).

[0277] 1 H-NMR (400MHz, DMSO-d6 / TMS): δ2.08 (s, 12H), 3.70 (dd, J=4.8Hz, 5.2Hz, 2H), 3.92 (t, J=4.8Hz, 2H), 4.8 7 (t, J=5.2Hz, 1H), 5.15 (s, 1H), 6.60 (s, 4H), 6.82 (d, J=8.8Hz, 2H), 6.95 (d, J=8.8Hz, 2H), 8.03 (s, 2H). LC-MS (mass analysis / electrospray ionization): 391.2 (MH) - The purity of the obtained compound (1A-3) crystals was 97.7%.

[0278] The crystals obtained using the above method underwent DSC and PXRD analysis. The analytical charts are shown below. Figure 1 and 2 .

[0279] Based on the DSC analysis of the crystals of the obtained compound (1A-3), the onset temperature (melting point) of the endothermic peak is 144.0 °C. This endothermic peak is considered to correspond to the melting of the crystal. Furthermore, the glass transition temperature is 97.7 °C.

[0280] Based on the thermogravimetric (TG) analysis of the crystals of the obtained compound (1A-3), the 5% weight loss temperature was 324.8 °C.

[0281] The diffraction pattern was also observed in PXRD analysis, thus confirming it as a crystal. The diffraction angles 2θ (°) of the observed diffraction peaks and the peaks with a relative intensity of 15 or higher relative to the peak with the maximum intensity are shown in Table 1.

[0282] [Table 1]

[0283] The resulting compound (1A-3) has a refractive index of 1.620.

[0284] <Example 2> <Synthesis of Compound (1A-4)> Add 27.6 g of 2,5-xylenol, 27.8 g of toluene, and 0.75 g of 1-dodecyl mercaptan to a 500 mL four-necked flask equipped with a thermometer, stirrer, dropping funnel, and condenser, and then add 2.4 g of 35% hydrochloric acid dropwise. Add a mixed solution of 7.5 g of 4-(2-hydroxyethoxy)benzaldehyde and 3.9 g of toluene dropwise to the flask over 1 hour while maintaining the temperature at 40 °C. After the addition is complete, allow the mixture to react for another 2 hours.

[0285] After the reaction was complete, sodium hydroxide aqueous solution was added to the slurry-like reaction solution for neutralization, followed by the addition of 52.8 g of toluene and 17.7 g of water. The solution was heated to 80°C and stirred. After standing, the water layer was removed. The slurry solution was then cooled to 30°C and filtered to separate the solids.

[0286] Add 20.1 g of the obtained solid (14.6 g of which is solid content) and 61.5 g of methyl isobutyl ketone (MIBK) to a 500 mL four-necked flask equipped with a thermometer, stirrer, and condenser. Heat to 85 °C to dissolve the solid. Add 20.3 g of water to the solution, stir, let stand, remove the water layer, and repeat the same water washing operation twice.

[0287] The solvent is recovered from the liquid by distillation, and after drying and solidification, an equal amount of MIBK is returned to the system. The solution is then cooled to 25°C. The pink solid precipitated when the solution temperature is between 30 and 40°C is separated by filtration and dried at 80°C under reduced pressure to obtain a pink powder.

[0288] Through the obtained solid 1 H-NMR and LC-MS analyses confirmed the compound as the target compound (1A-4).

[0289] 1 H-NMR (400MHz, DMSO-d6 / TMS): δ1.95 (s, 6H), 1.98 (s, 6H), 3.71 (dd, J=5.2Hz, 5.6Hz, 2H), 3.94 (t, J=5.2Hz, 2H), 4.8 7 (t, J=5.6Hz, 1H), 5.36 (s, 1H), 6.32 (s, 2H), 6.57 (s, 2H), 6.83 (d, J=8.8Hz, 2H), 6.88 (d, J=8.8Hz, 2H), 8.96 (s, 2H). LC-MS (mass analysis / electrospray ionization): 391.2 (MH) - The purity of the obtained compound (1A-4) crystals was 99.7%.

[0290] The obtained crystal (α crystal) was subjected to DSC and PXRD analysis using the above method. The analytical charts are shown below. Figure 3 and 4 .

[0291] Regarding the DSC analysis results of the obtained compound (1A-4) crystals, the onset temperatures of the endothermic peaks were 124.7 °C and 205.2 °C. Furthermore, the glass transition temperature was 87.2 °C.

[0292] Thermogravimetric (TG) analysis of the obtained compound (1A-4) crystals (α crystals) showed a 6.1% weight loss in the range of approximately 115°C to 140°C, with a sharp weight loss observed at temperatures above approximately 260°C. This analysis is illustrated in the following graph. Figure 5 The 5% weight loss temperature is 136.0℃.

[0293] Based on the results of DSC and TG analyses, the endothermic peak at an initial temperature of 124.7℃ in the DSC analysis is considered to correspond to the detachment of the solvent surrounding the crystal, while the endothermic peak at an initial temperature of 205.2℃ corresponds to the melting of the crystal. That is, the crystal is a crystal surrounded by the solvent used during crystallization, namely MIBK. The melting point of this crystal is 205.2℃.

[0294] The diffraction pattern was also observed in PXRD analysis, thus confirming it as a crystal. The diffraction angles 2θ (°) of the observed diffraction peaks and the peaks with a relative intensity of 15 or higher relative to the peak with the maximum intensity are shown in Table 2.

[0295] [Table 2]

[0296] <Example 3> The crystals (α crystals) obtained in Example 2 were further heated at 140°C under reduced pressure to obtain 11.0 g of orange powder. The yield of crystals (β crystals) of the compound (1A-4) of 4-(2-hydroxyethoxy)benzaldehyde, relative to the starting material used in Example 2, was 62%.

[0297] The purity of the obtained compound (1A-4) crystals (β crystals) was 99.8%.

[0298] The obtained crystal (β crystal) was subjected to DSC and PXRD analysis using the above method. The analytical charts are shown below. Figure 6 and 7 .

[0299] Based on the DSC analysis of the crystals (β crystals) of the obtained compound (1A-4), the onset temperature (melting point) was 206.4 °C. Furthermore, the glass transition temperature was 87.3 °C.

[0300] Based on the thermogravimetric (TG) analysis of the obtained compound (1A-4) crystals (β crystals), the 5% weight loss temperature was 312.1 °C. This analysis suggests that the obtained crystals (β crystals) are non-solvent-bound crystals, and the MIBK of the crystallization solvent bound in the α crystals detaches upon heating.

[0301] The diffraction pattern was also observed in PXRD analysis, thus confirming it as a crystal. Furthermore, the change in the diffraction pattern before and after further heating confirmed a change in the crystal phase. The diffraction angles 2θ (°) of the observed diffraction peaks and the peaks with a relative intensity of 15 or higher relative to the peak with the maximum intensity are shown in Table 3.

[0302] [Table 3]

[0303] The resulting compound (1A-4) has a refractive index of 1.620.

[0304] <Example 4> Add 367.6 g of 2,5-xylenol, 551.7 g of toluene, and 10.1 g of 1-dodecyl mercaptan to a 2 L four-necked flask equipped with a thermometer, stirrer, dropping funnel, and condenser, and then add 30.7 g of 35% hydrochloric acid dropwise. Add a mixed solution of 99.1 g of 4-(2-hydroxyethoxy)benzaldehyde and 50.1 g of toluene dropwise over 2 hours while maintaining the temperature at 40 °C. After the addition is complete, allow the mixture to react for an additional 18 hours.

[0305] After the reaction was complete, sodium hydroxide aqueous solution was added to the slurry-like reaction solution for neutralization, followed by the addition of 84.9 g of water. The solution temperature was raised to 80°C and stirred. After standing, the water layer was removed. The slurry solution was then cooled to 30°C and filtered to separate the solids.

[0306] Add 372.7 g of the obtained solid and 1141.4 g of methyl isobutyl ketone (MIBK) to a 3 L four-necked flask equipped with a thermometer, stirrer, and condenser, and heat to 85 °C to dissolve them. Add 372.1 g of water to the solution, stir, let stand, remove the water layer, and perform the same water washing operation twice.

[0307] After recovering 393.9 g of MIBK by distillation, the solution was cooled from 85°C to 40°C at a rate of 10°C / hour, and then further cooled to 25°C. The solid that precipitated at 70°C and whose precipitation increased at 65°C was separated by filtration, yielding 176.5 g of powder. The filtrate from this filtration process was collected in a flask and used in Example 5 described later. The filtered powder was dried to obtain 134.9 g of orange powder.

[0308] The purity, determined by high performance liquid chromatography, was 99.7%. The yield of 4-(2-hydroxyethoxy)benzaldehyde relative to the starting material was 58%.

[0309] The obtained crystal (γ crystal) was subjected to DSC and PXRD analysis using the above method. The analytical charts are shown below. Figure 8 and 9 .

[0310] Regarding the DSC analysis results of the obtained compound (1A-4) crystals, the onset temperatures of the endothermic peaks were 197.6 °C and 206.2 °C. Furthermore, the glass transition temperature was 80.8 °C.

[0311] Based on the thermogravimetric (TG) analysis of the crystals (γ crystals) of the obtained compound (1A-4), the 5% weight loss temperature was 310.8 °C.

[0312] The results of DSC and TG analysis show that it has a crystalline melting point at 197.6℃ and 206.2℃, respectively.

[0313] The diffraction pattern was also observed in PXRD analysis, thus confirming that it was a crystal. Furthermore, since the diffraction pattern differed from that of the crystal of compound (1A-4) obtained in Example 2, it was confirmed that a different crystal was obtained. The diffraction angles 2θ (°) of the observed diffraction peaks and the peaks with a relative intensity of 15 or higher relative to the peak with the maximum intensity are shown in Table 4.

[0314] [Table 4]

[0315] <Example 5> Pink crystals precipitated from the filtrate (MIBK solution of compound (1A-4)) obtained during the filtration and separation of crystals in the flask in Example 4 when it was left to stand at room temperature (20°C).

[0316] The precipitated crystals are filtered and dried by heating at 60°C under reduced pressure.

[0317] The obtained crystal (α crystal) was subjected to DSC analysis using the above method. The analysis results are shown in the figure. Figure 10 .

[0318] Regarding the DSC analysis results of the crystals of the obtained compound (1A-4), the onset temperatures of the endothermic peaks were 124.0 °C and 204.7 °C. Furthermore, the glass transition temperature was 79.1 °C.

[0319] Thermogravimetric (TG) analysis of the crystals (α-crystals) of the obtained compound (1A-4) showed a 10.2% weight loss in the range of approximately 115°C to 140°C, and a sharp weight loss at higher temperatures above approximately 260°C. The analytical plot is shown in [the graph]. Figure 11 The 5% weight loss temperature is 84.7℃.

[0320] Based on the results of DSC and TG analyses, the endothermic peak at an initial temperature of 124.0℃ in the DSC analysis is considered to correspond to the detachment of the solvent surrounding the crystal, and the endothermic peak at an initial temperature of 204.7℃ corresponds to the melting of the crystal. Therefore, the crystal is considered to be surrounded by the solvent used during crystallization, namely MIBK. The melting point of this crystal is 204.7℃.

[0321] <Comparative Synthesis of Examples 1 and 2> The compounds represented by chemical formulas (A-1) and (A-2) are synthesized in accordance with the matters described in Patent Document 1 above. They are respectively named compound (A-1) and compound (A-2).

[0322] [Chemistry 33]

[0323] The analytical results of each compound in Examples 1-5 and Comparative Example 1 based on the above analytical methods are summarized in Table 5.

[0324] [Table 5]

[0325] A comparison of the chemical structures of the triphenylalkane compounds (1A-3) and (1A-4) of the present invention with those of the previously known compound (A-1) reveals that they differ in the presence of hydroxyethoxy groups.

[0326] It is clear that compounds (1A-3) and (1A-4) have lower refractive indices compared to compound (A-1).

[0327] According to Maxwell's equations, there is a relationship between the dielectric constant (ε) and the refractive index (n) of a material: ε = n² (this relationship is described, for example, in Shogo Saito, Electron Photography, Vol. 11, No. 1, pp. 26-32, 1972). In other words, the smaller the refractive index of a material, the lower its dielectric constant.

[0328] That is, it is clear that the triphenylalkane compound of the present invention has a lower dielectric constant and improved dielectric properties due to the presence of a hydroxyethoxy group.

[0329] It was determined that compounds (1A-3) and (1A-4) have higher 5% weight loss temperatures than compound (A-1) and exhibit excellent thermal stability under high-temperature conditions.

[0330] <Example 6> <Synthesis of Compound (1B-3)> 14.8 g of compound (1A-3) obtained in Example 1, 13.4 g of potassium carbonate, and 75.1 g of acetone were added to a 500 mL four-necked flask equipped with a thermometer, stirrer, dropping funnel, and condenser. While maintaining the temperature at 40 °C, 11.7 g of allyl bromide was added dropwise. After the addition was complete, the mixture was refluxed at 60 °C for 24 hours. Then, 0.5 g of potassium carbonate and 0.5 g of allyl bromide were added, and the reaction was allowed to proceed for another 4 hours.

[0331] After the reaction was complete, the reaction solution was filtered through filter paper to remove insoluble matter. The solvent in the filtrate was removed by vacuum distillation, followed by the addition of 17.8 g of butyl acetate and 17.8 g of water. The mixture was heated to 40°C and stirred. The aqueous layer was removed from the separated organic and aqueous layers after settling. After two water washes of the organic layer, the solvent in the resulting oil layer was removed by vacuum distillation to obtain 17.1 g of an orange oil.

[0332] The resulting oily substance 1 H-NMR and LC-MS analyses confirmed the compound as the target compound (1B-3).

[0333] 1 H-NMR (400MHz, DMSO-d6 / TMS): δ2.14 (s, 12H), 3.70 (dd, J=4.8Hz, 5.6Hz, 2H), 3.93 (t, J=4.8Hz, 2H), 4.26 (d, J=5.2Hz, 4H), 4.87 (t, J=5.6Hz, 1H), 5.22 (dd, J=1.6Hz, 10.4Hz, 2H), 5.27 (s, 1H), 5.41 (dd, J=2.0Hz, 17.2Hz, 2H), 6. 02-6.12 (m, 2H), 6.74 (s, 4H), 6.84 (d, J = 8.8Hz, 2H), 6.98 (d, J = 8.8Hz, 2H). LC-MS (mass analysis / electrospray ionization): 495.3 (M + Na) ＋ The purity, determined by high performance liquid chromatography, was 95.0%. The 5% weight loss temperature was 222.6℃.

[0334] The resulting compound (1B-3) has a refractive index of 1.581.

[0335] <Example 7> <Synthesis of Compound (1B-4)> 5.1 g of compound (1A-4) obtained in Example 3, 5.5 g of potassium carbonate, and 25.1 g of acetone were added to a 500 mL four-necked flask equipped with a thermometer, stirrer, dropping funnel, and condenser. While maintaining the temperature at 40 °C, 4.7 g of allyl bromide was added dropwise. After the addition was complete, the mixture was refluxed at 60 °C for 24 hours. Then, 0.9 g of potassium carbonate and 1.5 g of allyl bromide were added, and the reaction was allowed to continue for another 30 hours.

[0336] After the reaction was complete, the reaction solution was filtered through filter paper to remove insoluble matter. The solvent in the filtrate was removed by vacuum distillation, followed by the addition of 12.3 g of butyl acetate and 12.3 g of water. The mixture was heated to 40°C and stirred. The aqueous layer was removed from the separated organic and aqueous layers after settling. After two washes of the organic layer with water, a yellow solid precipitated when the solvent in the resulting oil layer was removed by vacuum distillation. The solid was separated by filtration, washed with 6.0 g of methanol, and dried to obtain a yellow powder.

[0337] Through the obtained crystal 1 H-NMR and LC-MS analyses confirmed the compound as the target compound (1B-4).

[0338] 1 H-NMR (400MHz, DMSO-d6 / TMS): δ2.00 (s, 6H), 2.07 (s, 6H), 3.71 (t, J=4.8Hz, 2H), 3.94 (t, J=4.8Hz, 2H), 4.52 (d, J=5.2Hz, 4H), 4.87 (s, 1H), 5.24 (dd, J=1. 6Hz, 10.6Hz, 2H), 5.40 (dd, J=2.0Hz, 17.4Hz, 2H), 5.45 (s, 1H), 6.01-6.10 (m , 2H), 6.42 (s, 2H), 6.75 (s, 2H), 6.85 (d, J = 8.8Hz, 2H), 6.89 (d, J = 8.8Hz, 2H). LC-MS (mass analysis / electrospray ionization): 495.3 (M + Na) ＋ The purity, determined by high performance liquid chromatography, was 96.1%.

[0339] The crystals obtained using the above method underwent DSC and PXRD analysis. The analytical charts are shown below. Figure 12 and 13 .

[0340] Based on the DSC analysis of the crystals of the obtained compound (1B-4), the onset temperature of the endothermic peak is 119.7℃ (melting point). This endothermic peak is considered to correspond to the melting of the crystals.

[0341] The results of thermogravimetric (TG) analysis of the crystals of the obtained compound (1B-4) showed a 5% weight loss temperature of 296.8 °C.

[0342] The resulting compound (1B-4) has a refractive index of 1.591.

[0343] The diffraction pattern was also observed in PXRD analysis, thus confirming it as a crystal. The diffraction angles 2θ (°) of the observed diffraction peaks and the peaks with a relative intensity of 15 or higher relative to the peak with the maximum intensity are shown in Table 6.

[0344] [Table 6]

[0345] The analytical results based on the above-described analytical methods for the compounds of Examples 6 and 7 and Comparative Example 2 are summarized in Table 7.

[0346] [Table 7]

[0347] <Preparation and Evaluation of Curable Resin Compositions and Cured Products> The components used in the manufacture of the curable resin composition and its cured product are shown below.

[0348] [Polyphenylene ether resin] (ingredient A) Terminally (meth)acrylated polyether resin of a copolymer of 2,6-dimethylphenol and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane [Curing agent] (Ingredient B) Compound (1B-3) prepared in Example 6 Compound (1B-4) prepared in Example 7 (Comparative compounds) Compound (A-2) prepared in Comparative Example 2 [Reaction initiator] (Ingredient C) Dicumyl peroxide (manufactured by Nippon Yushi Co., Ltd.: trade name "PERCUMYL D") [Varnish Solvent] (Component F) Toluene <Preparation of Curable Resin Compositions and Prepregs> Take 100 parts by weight of a copolymer of 2,6-dimethylphenol and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, an end-terminated polyether resin esterified with (meth)acrylate, 100 parts by weight of toluene, any one of the above-mentioned curing agents, and 0.63 parts by weight of dicumyl peroxide, and stir with a magnetic stirrer at room temperature to prepare a varnish of a curable resin composition.

[0349] The varnish was applied to a 20cm square polyimide film (manufactured by Ube Industries, Ltd., trade name "UPILEX") with a thickness of 0.2mm. Subsequently, the varnish, which had been dried at room temperature, was treated in a vacuum dryer at 105°C for 1 hour to remove the solvent, thereby obtaining a prepreg of the semi-cured material.

[0350] <Preparation of cured products (resin films) of curable resin compositions> The aforementioned prepreg was used to sandwich the two sides of an aluminum foil (thickness: 0.12mm) with 9cm × 4cm holes. Two additional polyimide films were then used to sandwich the film from both sides, followed by a 25cm × 25cm metal plate. Subsequently, the film was pressure-cured using a vacuum hot press (manufactured by Toyo Seiki Co., Ltd.) under the following temperature, pressure, and time conditions: heating temperature 105°C, pressure 10MPa, 30 minutes → heating temperature 150°C, pressure 10MPa, 1 hour → heating temperature 200°C, pressure 10MPa, 1 hour → heating temperature 250°C, pressure 10MPa, 1 hour → heating temperature 270°C, pressure 10MPa, 1 hour. The polyimide film adhering to the surface of the cured body was removed to obtain a resin film.

[0351] As shown in Table 8, cured products of the above-described curable resin compositions were manufactured by changing the curing agent used. The results of the physical property evaluation of Examples 8 and 9 and Comparative Example 3 are shown in Table 8 below.

[0352] [Table 8]

[0353] It was found that the cured resin compositions of Examples 8 and 9, which used the triphenylalkane compound of the present invention as a curing agent, had a lower dielectric constant and a smaller storage modulus compared with Comparative Example 3, which used a conventionally known compound (A-2) as a curing agent.

[0354] That is, it is clear that the cured product of the present invention has excellent dielectric properties and excellent flexibility.

Claims

1. A triphenylalkane compound, characterized in that, Represented by general formula (1), [Chemistry 1] In the formula, R1 independently represents a hydrogen atom or an alkenyl group having 2 to 4 carbon atoms, R2 represents an alkylene group having 1 to 4 carbon atoms, R3 independently represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom, R4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m and n independently represent 0, 1, 2, or 3.

2. The compound according to claim 1, characterized in that, In the general formula (1), R4 is a hydrogen atom or a methyl group.

3. The compound according to claim 1, characterized in that, In the general formula (1), R1 is each independently a hydrogen atom, vinyl, allyl or 1-propenyl, and R2 is 1,2-ethylene.

4. The compound according to claim 1, characterized in that, The triphenylalkane compound represented by the general formula (1) is a compound represented by any one of the chemical formulas (1A-1) to (1A-24) and (1B-1) to (1B-24). [Chemistry 2] [Chemistry 3] [Chemistry 4] [Chemistry 5] [Chemistry 6] [Chemistry 7] [Chemistry 8] [Chemistry 9] 。 5. A curable resin composition, characterized in that, Component A contains polyphenylene ether resin, and component B contains a compound represented by general formula (1B). [Chemistry 10] In the formula, R 1a Each of the alkenyl groups with 2 to 4 carbon atoms is represented independently, and R2 to R4, m and n are defined in the same way as in general formula (1).

6. The curable resin composition according to claim 5, characterized in that, It contains 100 parts by weight of component A and 1.0 to 10.0 parts by weight of component B.

7. The curable resin composition according to claim 6, characterized in that, The curable resin composition further contains a curing reaction initiator as component C.

8. The curable resin composition according to claim 7, characterized in that, The curable resin composition further contains a filler as component D.

9. A prepreg, characterized in that, The curable resin composition of claim 5 is obtained by semi-curing.

10. A cured product of a fiber-reinforced curable resin composition, characterized in that, The curable resin composition of claim 5 is obtained by mixing it with reinforcing fibers as component E and then curing it.

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