Resin, resin manufacturing method, curable resin composition and cured product

Abstract

This invention provides a novel resin with excellent dielectric properties, a method for manufacturing the resin, a curable resin composition, and a cured product. This invention is a resin having the constituent units described in group (1). a, b, c, and d each independently represent the molar ratio of the constituent unit, where a is a number greater than or equal to 1, b is a number greater than or equal to 0, c is a number greater than or equal to 1, and d is a number greater than or equal to 0.

Description

Technical Field

[0001] This invention relates to novel resins, methods for manufacturing resins, curable resin compositions, and cured products. Prior Technology

[0002] Vinyl compounds and other resins containing vinyl groups are used in various materials due to their excellent heat resistance. Examples include those disclosed in Patent Document 1. On the other hand, some researchers are also exploring the use of vinyl compounds and other vinyl resins, which possess excellent heat resistance and simultaneously improve dielectric properties, as materials for electronic devices that process high-frequency signals. Such vinyl compounds and their manufacturing methods are known, for example, as disclosed in Patent Documents 2 and 3. [Previous Technical Documents] [Patent Literature]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2020-037651 [Patent Document 2] Japanese Patent Application Publication No. 2015-189925 [Patent Document 3] Japanese Patent Application Publication No. 01-108212 Summary of the Invention

[0004] Furthermore, with the technological innovations of recent years, there is a growing demand for novel vinyl resins with excellent dielectric properties and their manufacturing methods. The present invention aims to solve this problem and to provide a novel resin with excellent dielectric properties, as well as a method for manufacturing the resin, a curable resin composition, and a cured product. [Methods for solving problems]

[0005] Based on the above issues, the inventors conducted research and found that the above issues can be solved by producing resin with a predetermined structure. Specifically, the above-mentioned problem has been solved by the following method. <1> A resin having the constituent units described in group (1), Group (1): [Chemistry 1] In group (1), R1 independently represents methylene, methyleneoxy, methyleneoxymethylene, or oxymethylene; R2 represents an alkyl group having 1 to 3 carbon atoms; R3, R4, and R5 independently represent a halogen atom, an alkyl group having 1 to 10 carbon atoms, a alkyl halide having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; R6, R7, and R8 independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide having 1 to 10 carbon atoms, a hydroxyl group, a hydroxyalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; R 9 represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, a halogenated alkyl group with 1 to 10 carbon atoms, a hydroxyl group, a hydroxyalkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 12 carbon atoms; v represents 0 or 1, w represents a number from 1 to 3, and x, y, and z each independently represent a number from 0 to 3; a, b, c, and d each independently represent the molar ratio of the constituent units, where a is a number greater than 1, b is a number greater than 0, c is a number greater than 1, and d is a number greater than 0; R 1 can also bond with each other to form a cross-linked structure; * indicates the bonding position with other constituent units or end groups. <2> like <1> The resin, wherein in group (1), R6 is methyl, and R7 and R8 are hydrogen atoms. <3> like <1> or <2> The resin, wherein in group (1), R3, R4 and R5 are each independently an alkyl group having 1 to 10 carbon atoms. <4> like <1> or <2> The resin, wherein in group (1), R3, R4 and R5 are each independently an alkyl group having 1 to 5 carbon atoms. <5> like <1> to <4> The resin of any one of the above, wherein the content of phenolic hydroxyl groups in the aforementioned resin is less than 0.5 mmol / g. <6> like <1> to <5> The resin of any one of the above, wherein the content of the group (1) of the aforementioned resins, represented by the following group, is 1.0 mmol / g or more, [Chemistry 2] R6~R8 in the above base are synonyms with R6~R8 in group (1). <7> like <1> to <6> The resin of any one of the following, wherein the constituent unit described in group (1) includes at least one of the constituent units described in group (1-1), group (1-2), group (1-3), and group (1-4). Group (1-1): [Chemistry 3] In group (1-1), R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a1, b, c, and d are synonyms of R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a, b, c, and d in group (1), respectively. * indicates the bonding position with other constituent units or terminal bases; Groups (1-2): [Chemistry 4] In groups (1-2), R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a2, b, c, and d are synonyms of R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a, b, c, and d in group (1), respectively. * indicates the bonding position with other constituent units or terminal bases; Groups (1-3): [Chemistry 5] In groups (1-3), R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a3, b, c, and d are synonyms of R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a, b, c, and d in group (1), respectively. * indicates the bonding position with other constituent units or terminal bases; Groups (1-4): [Chemistry 6] In groups (1-4), R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a4, b, c and d are synonyms with R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a, b, c and d in group (1), respectively. * indicates the bond position with other constituent units or terminal bases. <8> like <7> The resin, wherein the constituent units described in group (1) include the constituent units described in group (1-1) or the constituent units described in group (1-4). <9> like <1> to <8> The resin of any one of the following, wherein the number average molecular weight Mn is 500-6,000 and the weight average molecular weight Mw is 500-15,000. <10> like <1> to <9> The resin of any one of the above, wherein the terminal group of the aforementioned resin is selected from hydrogen atom, hydroxyl and hydroxymethyl. <11> A resin is a reaction product of at least a compound represented by formula (2) and a raw material resin having the constituent units described in group (4). Equation (2): [Chemistry 7] In formula (2), R6, R7 and R8 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a alkyl halide having 1 to 10 carbon atoms, a hydroxyl group, a hydroxyalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; Group (4): [Chemistry 8] In group (4), R1 independently represents methylene, methyleneoxy, methyleneoxymethylene or oxymethylene; R2 represents alkyl with 1 to 3 carbon atoms; R3, R4 and R5 independently represent halogen atoms, alkyl with 1 to 10 carbon atoms, alkyl halide with 1 to 10 carbon atoms, hydroxyalkyl with 1 to 10 carbon atoms, or aryl with 6 to 12 carbon atoms; v represents 0 or 1, w represents 1 to 3 numbers, x, y and z independently represent 0 to 3 numbers; a, b, c and d independently represent the molar ratio of the constituent units, a is a number greater than 1, b is a number greater than 0, c is a number greater than 1, and d is a number greater than 0; R1 can also be bonded to each other to form a cross-linked structure; * indicates the bonding position with other constituent units or terminal groups. <12> A method for manufacturing a resin includes the following steps: reacting a compound represented by at least formula (2) with a raw material resin having the constituent units described in group (4) in the presence of an alkaline compound. Equation (2): [Chemistry 9] In formula (2), R6, R7 and R8 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a alkyl halide having 1 to 10 carbon atoms, a hydroxyl group, a hydroxyalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; Group (4): [Chemistry 10] In group (4), R1 independently represents methylene, methyleneoxy, methyleneoxymethylene or oxymethylene; R2 represents alkyl with 1 to 3 carbon atoms; R3, R4 and R5 independently represent halogen atoms, alkyl with 1 to 10 carbon atoms, alkyl halide with 1 to 10 carbon atoms, hydroxyalkyl with 1 to 10 carbon atoms, or aryl with 6 to 12 carbon atoms; v represents 0 or 1, w represents 1 to 3 numbers, x, y and z independently represent 0 to 3 numbers; a, b, c and d independently represent the molar ratio of the constituent units, a is a number greater than 1, b is a number greater than 0, c is a number greater than 1, and d is a number greater than 0; R1 can also be bonded to each other to form a cross-linked structure; * indicates the bonding position with other constituent units or terminal groups. <13> like <12> The method for manufacturing the resin, wherein in formula (2), R6 is methyl, and R7 and R8 are hydrogen atoms. <14> like <12> or <13> The method for manufacturing the resin, wherein in group (4), R3, R4 and R5 are each independently an alkyl group having 1 to 10 carbon atoms. <15> like <12> or <13> The method for manufacturing the resin, wherein in group (4), R3, R4 and R5 are each independently an alkyl group having 1 to 5 carbon atoms. <16> like <12> to <15> A method for manufacturing resin of any one of the above, wherein the hydroxyl value of the aforementioned raw material resin is 100~600 g / mol. <17> like <12> to <16> The method of manufacturing resin of any one of the following, wherein the constituent unit described in group (4) includes at least one of the constituent unit described in group (4-1), the constituent unit described in group (4-2), the constituent unit described in group (4-3), and the constituent unit described in group (4-4). Group (4-1): [Chemistry 11] In group (4-1), R1, R3, R4, R5, v, x, y, z, a1, b, c, and d are synonyms with R1, R3, R4, R5, v, x, y, z, a, b, c, and d in group (4), respectively. * indicates the bond position with other constituent units or terminal bases; Group (4-2): [Chemistry 12] In group (4-2), R1, R3, R4, R5, v, x, y, z, a2, b, c, and d are synonyms with R1, R3, R4, R5, v, x, y, z, a, b, c, and d in group (4), respectively. * indicates the bond position with other constituent units or terminal bases; Group (4-3): [Chemistry 13] In group (4-3), R1, R3, R4, R5, v, x, y, z, a3, b, c, and d are synonyms with R1, R3, R4, R5, v, x, y, z, a, b, c, and d in group (4), respectively. * indicates the bond position with other constituent units or terminal bases; Group (4-4): [Chemistry 14] In group (4-4), R1, R3, R4, R5, v, x, y, z, a4, b, c and d are synonyms with R1, R3, R4, R5, v, x, y, z, a, b, c and d in group (4), respectively. * indicates the bond position with other constituent units or terminal bases. <18> like <17> The method for manufacturing the resin, wherein the constituent unit described in group (4) includes the constituent unit described in group (4-1) or the constituent unit described in group (4-4). <19> like <12> to <18> The method for manufacturing resin of any one of the above, wherein the raw material resin having the constituent units described in group (4) has an average molecular weight Mn of 400 to 4,000 and a weight average molecular weight Mw of 400 to 16,000. <20> like <12> to <19> The method of manufacturing resin of any one of them, wherein the terminal group of the raw material resin having the constituent units described in group (4) is selected from hydrogen atom, hydroxyl and hydroxymethyl. <21> like <12> to <20> A method for manufacturing a resin of any one of the above, wherein the aforementioned alkaline compound comprises at least one of potassium carbonate, rubidium carbonate, and cesium carbonate. <22> like <12> to <21> The method for manufacturing the resin of any one of the above, wherein the resin manufactured is as follows: <1> to <11> The resin of any one of them. <23> A curable resin composition comprising, for example <1> to <11> The resin of any one of them. <24> like <23> The curable resin composition further includes, for example, <1> to <11> Thermosetting compounds other than resins of any of the above. <25> like <23> or <24> The thermosetting resin composition, wherein the aforementioned thermosetting compound comprises a material selected from... <1> to <11> The compound having carbon-carbon unsaturated bond groups other than any of the resins mentioned above, and at least one of epoxy resins. <26> A cured product of a curable resin composition, which is as follows <23> to <25> A hardened product of any of the following hardening resin compositions. [Effects of the Invention]

[0006] According to the present invention, novel resins with excellent dielectric properties, methods for manufacturing the resins, curable resin compositions, and cured products can be provided. Implementation

[0007] Hereinafter, a detailed description will be given of the embodiments used to implement the present invention (hereinafter referred to as "the embodiments"). Furthermore, the embodiments described below are illustrative of the present invention, and the present invention is not limited to the embodiments. Furthermore, in this specification, "~" is used to indicate the lower and upper limits of the values ​​recorded before and after it. Unless otherwise stated, all physical properties and characteristic values ​​in this specification are defined at 23°C. In this specification, the designations of groups (atomic groups) that do not specify substituted or unsubstituted groups include both unsubstituted and substituted groups (atomic groups). For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this specification, the designations that do not specify substituted or unsubstituted groups are preferred to be unsubstituted. Unless otherwise stated, the specifications shown in this specification are defined as being based on January 1, 2021, when the measurement methods and other factors differ due to the year.

[0008] The resin of this embodiment has the constituent units described in group (1). The cured resin of this type has excellent dielectric properties. In addition, a resin with excellent heat resistance can be obtained. In particular, regarding the constituent units containing vinyl groups, it is possible to manufacture it industrially at a lower cost by using the third constituent unit from the left in group (1). Furthermore, it is industrially advantageous because the refined resin can be refined with water. Group (1): [Chemistry 15] In group (1), R1 independently represents methylene, methyleneoxy, methyleneoxymethylene, or oxymethylene; R2 represents an alkyl group having 1 to 3 carbon atoms; R3, R4, and R5 independently represent a halogen atom, an alkyl group having 1 to 10 carbon atoms, a alkyl halide having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; R6, R7, and R8 independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide having 1 to 10 carbon atoms, a hydroxyl group, a hydroxyalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; R 9 represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, a halogenated alkyl group with 1 to 10 carbon atoms, a hydroxyl group, a hydroxyalkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 12 carbon atoms; v represents 0 or 1, w represents a number from 1 to 3, and x, y, and z each independently represent a number from 0 to 3; a, b, c, and d each independently represent the molar ratio of the constituent units, where a is a number greater than 1, b is a number greater than 0, c is a number greater than 1, and d is a number greater than 0; R 1 can also bond with each other to form a cross-linked structure; * indicates the bonding position with other constituent units or end groups.

[0009] In group (1), R1 independently represents methylene, methyleneoxy, methyleneoxymethylene, or oxymethylene, with methylene and methyleneoxymethylene being preferred, and methylene being even more preferred. R1 can also bond with each other to form a cross-linked structure. The following structures can be exemplified as a result of cross-linking R1. [Chemistry 16] R1 is preferred if no cross-linked structure has formed. n is a number greater than or equal to 1, usually a number between 1 and 10.

[0010] R 2 represents an alkyl group having 1 to 3 carbon atoms, preferably methyl or ethyl, with methyl being even more preferred.

[0011] R3, R4 and R5 each independently represent a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. It is preferred that each of them is an alkyl group having 1 to 10 carbon atoms, and even more preferred that each of them is an alkyl group having 1 to 5 carbon atoms. As for the halogen atom in R3~R5, fluorine or chlorine atoms are preferred. The alkyl group is 1 to 10 carbon atoms of R3 to R5, preferably alkyl group with 1 to 5 carbon atoms, preferably methyl, ethyl, isopropyl, n-propyl, n-butyl or tributyl, and even more preferably tributyl. As a halogenated alkyl group having 1 to 10 carbon atoms (R3 to R5), it is more preferably an alkyl group having 1 to 5 carbon atoms substituted with fluorine or chlorine atoms, and even more preferably a fluoromethyl, chloromethyl, fluoroethyl, or chloroethyl group. As a hydroxyalkyl group with 1 to 10 carbon atoms (R3 to R5), it is more preferably a hydroxyalkyl group with 1 to 5 carbon atoms, and even more preferably a hydroxymethyl or hydroxyethyl group. As an aryl group with 6 to 12 carbon atoms in R3 to R5, phenyl is preferred.

[0012] R6, R7, and R8 each independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, a halogenated alkyl group with 1 to 10 carbon atoms, a hydroxyl group, a hydroxyalkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 12 carbon atoms, and each independently represents a hydrogen atom, a halogen atom (preferably a chlorine or fluorine atom), or a methyl group. More ideally, R6 is a methyl group, and R7 and R8 are hydrogen atoms.

[0013] R 9 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a hydroxyl group, a hydroxyalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or a phenyl group, and even more preferably a methyl or phenyl group.

[0014] v represents 0 or 1, and may include both constituent units where v is 0 and constituent units where v is 1, but preferably includes at least constituent units where v is 0. Furthermore, states that include at least constituent units where v is 1 may also be listed. w represents a number from 1 to 3, with 2 or higher being better, and 3 or lower being more ideal. x, y, and z each independently represent the numbers 0 to 3. 1 and above are better, while 2 and below are more ideal, with 1 being the most ideal.

[0015] In group (1), the state system with R1 being methylene, R2 being methyl, R3~R5 being tributyl each independently, R6 being methyl, R7 and R8 being hydrogen atoms, R9 being methyl or phenyl, w being 2 or 3, x being 1 or 2, and y and z being 1 or 2 is more ideal.

[0016] a, b, c, and d each independently represent the molar ratio of the constituent units. a is a number greater than or equal to 1, b is a number greater than or equal to 0, c is a number greater than or equal to 1, and d is a number greater than or equal to 0. For b:a, a molar ratio of 1:0.8 or higher is preferred, and 1:3.5 or higher is even better. There is no specific upper limit for the molar ratio of b:a, but b being 0 is ideal, and it can also be less than 1:100. Furthermore, for (c+d):a, a molar ratio of 1:0.05 to 7 is preferred, and 1:0.4 to 3 is even better. Additionally, for b:(c+d): a molar ratio of 1:1.5 or higher is preferred, and 1:3 or higher is even better. There is no specific upper limit for the molar ratio of b:(c+d), but it can also be less than 1:100. For d:c: a molar ratio of 1:0.25 or higher is preferred, and 1:0.67 or higher is even better. There is no specific upper limit for the molar ratio of d:c, but d is ideal when it is 0, and it can also be below 1:100. When the sum of a, b, c and d makes all constituent units in this embodiment 100, it is better to have 90 or more in molar ratio, even better to have 95 or more, and it is even better to have 100 in all constituent units excluding the terminal bases.

[0017] The constituent units described in group (1) preferably include at least one of the constituent units described in group (1-1), group (1-2), group (1-3), and group (1-4), and more preferably include at least the constituent units described in group (1-1) or group (1-4). The resin of this embodiment, as described below, is preferably a reaction product of at least the compound represented by formula (2) and a raw material resin having the constituent units described in group (4). Alternatively, the resin of this embodiment may also be a reaction product of at least one of the compounds represented by formula (2) and formula (3) and a raw material resin having the constituent units described in group (4). The raw material resin having the constituent units described in group (4) can be exemplified by, for example, an inexpensive resin that can be synthesized from xylene and formaldehyde, namely xylene resin, and an inexpensive resin that can be synthesized from mesitylene and formaldehyde, namely mesitylene resin. When the resin of this embodiment is obtained using such raw material resins, a resin containing at least one of the constituent units described in group (1-1), group (1-2), group (1-3), and group (1-4) can be obtained. In particular, when xylene resin is used, a resin containing the constituent units described in group (1-1) can be preferentially obtained. Also, when mesitylene resin is used, a resin containing the constituent units described in group (1-4) can be preferentially obtained. The resin of this embodiment, by being made into a resin containing at least one of the constituent units described in groups (1-1) to (1-4) (for example, mesitylene resin), can increase the curing start temperature of the resin. That is, by making a resin containing at least one of the constituent units described in group (1-1), group (1-2), group (1-3), and group (1-4), the resin of this embodiment can be easily and inexpensively manufactured industrially and can be made into a resin with immediate implementability.

[0018] Group (1-1): [Chemistry 17] In group (1-1), R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a1, b, c and d are synonyms with R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a, b, c and d in group (1), respectively. * indicates the bond position with other constituent units or terminal bases. Groups (1-2): [Chemistry 18] In group (1-2), R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a2, b, c and d are synonyms with R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a, b, c and d in group (1), respectively. * indicates the bond position with other constituent units or terminal bases. Groups (1-3): [Chemistry 19] In groups (1-3), R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a3, b, c and d are synonyms of R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a, b, c and d in group (1), respectively. * indicates the bond position with other constituent units or terminal bases. Groups (1-4): [Chemistry 20] In groups (1-4), R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a4, b, c and d are synonyms with R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a, b, c and d in group (1), respectively. * indicates the bond position with other constituent units or terminal bases.

[0019] The resin of this embodiment may contain only one type of constituent unit from group (1), or it may contain two or more types of constituent units from group (1). In the case of containing two or more types, the total amount is within the range described above.

[0020] The resin of this embodiment may also include constituent units other than those shown in group (1). Furthermore, in the resin of this embodiment, each constituent unit represented by group (1) can be randomly polymerized or block polymerized.

[0021] In group (1), * indicates the bonding position with other constituent units or terminal groups. As for the terminal group, it is preferred to select hydrogen atom, hydroxyl group and hydroxymethyl group, more preferably hydrogen atom or hydroxyl group, and even more preferably hydrogen atom.

[0022] The phenolic hydroxyl content of the resin in this embodiment is preferably below 0.5 mmol / g, more preferably below 0.3 mmol / g, even more preferably below 0.2 mmol / g, even more preferably below 0.1 mmol / g, and even more preferably below 0.05 mmol / g. By setting it below the aforementioned upper limit, a resin with superior low dielectric properties can be obtained. The aforementioned lower limit of phenolic hydroxyl content is preferably 0 mmol / g, but in practice it is greater than 0 mmol / g.

[0023] Furthermore, in the group (1) of resins of this embodiment, the content of the following groups is preferably 1.0 mmol / g or more, more preferably 1.1 mmol / g or more, even more preferably 1.2 mmol / g or more, even more preferably 1.5 mmol / g or more, and even more preferably 2.0 mmol / g or more. By setting the content to the aforementioned lower limit or above, a resin with better curing properties can be obtained. Also, there is a tendency to obtain resins with better heat resistance and dielectric properties. There is no particular requirement for the upper limit, but it can be set to, for example, 5.0 mmol / g or less. [Chemistry 21] R6~R8 in the above base are synonyms with R6~R8 in group (1).

[0024] The resin of this embodiment preferably has a weight-average molecular weight (Mw) of 500 or more, more preferably 1,000 or more, more preferably 3,000 or more, more preferably 4,000 or more, and even more preferably 7,000 or more. By setting it to the aforementioned lower limit or above, the toughness and flexibility of the resin are improved, and the cracking during molding and the generation of cracks in the molded article can be more effectively suppressed. Furthermore, the resin of this embodiment preferably has a weight-average molecular weight (Mw) of 30,000 or less, more preferably 20,000 or less, more preferably 18,000 or less, more preferably 16,000 or less, and may also be 15,000 or less. By setting it to the aforementioned upper limit or below, due to the improvement of the resin's solvent solubility and the reduction of the resin's melt viscosity, there is a tendency for the resin's workability to be further improved.

[0025] The resin of this embodiment preferably has a number average molecular weight (Mn) of 500 or higher, more preferably 800 or higher, even more preferably 1,000 or higher, even more preferably 1,200 or higher, and even more preferably 1,700 or higher. By setting it to the aforementioned lower limit or higher, the toughness and flexibility of the resin are improved, and the cracking during molding and the generation of cracks in the molded product can be more effectively suppressed. Furthermore, the resin of this embodiment preferably has a number average molecular weight (Mn) of 10,000 or lower, more preferably 8,000 or lower, even more preferably 7,000 or lower, even more preferably 6,000 or lower, and may also be 4,500 or lower. By setting it to the aforementioned upper limit or lower, due to the improvement in the solvent solubility of the resin and the reduction in the melt viscosity of the resin, the workability of the resin tends to be further improved. The weight-average molecular weight and number-average molecular weight were determined according to the methods described in the examples below.

[0026] The method for manufacturing the resin according to this embodiment is characterized by comprising the following steps: reacting at least the compound represented by formula (2) with a raw material resin having the constituent units described in group (4) in the presence of an alkaline compound. By using such a method, a resin with excellent dielectric properties can be obtained. In addition, a resin with excellent heat resistance can be obtained. Furthermore, the compound represented by formula (3) can also be reacted. Equation (2): [Chemistry 22] In formula (2), R6, R7 and R8 each independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, a alkyl halide with 1 to 10 carbon atoms, a hydroxyl group, a hydroxyalkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 12 carbon atoms. Group (4): [Chemistry 23] In group (4), R1 independently represents methylene, methyleneoxy, methyleneoxymethylene or oxymethylene; R2 represents alkyl with 1 to 3 carbon atoms; R3, R4 and R5 independently represent halogen atoms, alkyl with 1 to 10 carbon atoms, alkyl halide with 1 to 10 carbon atoms, hydroxyalkyl with 1 to 10 carbon atoms, or aryl with 6 to 12 carbon atoms; v represents 0 or 1, w represents 1 to 3 numbers, x, y and z independently represent 0 to 3 numbers; a, b, c and d independently represent the molar ratio of the constituent units, a is a number greater than 1, b is a number greater than 0, c is a number greater than 1, and d is a number greater than 0; R1 can also be bonded to each other to form a cross-linked structure; * indicates the bonding position with other constituent units or terminal groups.

[0027] Equation (3): [Chemistry 24] In formula (3), R9 represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, a alkyl halide with 1 to 10 carbon atoms, a hydroxyl group, a hydroxyalkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 12 carbon atoms.

[0028] First, the details of group (4) will be explained. In group (4), R1, R2, R3, R4, R5, v, w, x, y, z, a, b, c, and d are synonyms of R1, R2, R3, v, w, x, y, z, a, b, and c in group (1), and their more ideal ranges are also the same. The terminal bases in group (4) are the same as those in group (1).

[0029] Furthermore, the constituent units described in group (4) preferably include at least one of the constituent units described in group (4-1), group (4-2), group (4-3), and group (4-4), and more preferably include the constituent units described in group (4-1) or group (4-4). By using a raw material resin that includes at least one of the constituent units described in group (4-1), group (4-2), group (4-3), and group (4-4), a resin having the constituent units described in group (1) can be manufactured more cheaply. Group (4-1): [Chemistry 25] In group (4-1), R1, R3, R4, R5, v, x, y, z, a1, b, c and d are synonyms with R1, R3, R4, R5, v, x, y, z, a, b, c and d in group (4), respectively. * indicates the bond position with other constituent units or terminal bases. Group (4-2): [Chemistry 26] In group (4-2), R1, R3, R4, R5, v, x, y, z, a2, b, c and d are synonyms with R1, R3, R4, R5, v, x, y, z, a, b, c and d in group (4), respectively. * indicates the bond position with other constituent units or terminal bases. Group (4-3): [Chemistry 27] In group (4-3), R1, R3, R4, R5, v, x, y, z, a3, b, c and d are synonyms with R1, R3, R4, R5, v, x, y, z, a, b, c and d in group (4), respectively. * indicates the bond position with other constituent units or terminal bases. Group (4-4): [Chemistry 28] In group (4-4), R1, R3, R4, R5, v, x, y, z, a4, b, c and d are synonyms with R1, R3, R4, R5, v, x, y, z, a, b, c and d in group (4), respectively. * indicates the bond position with other constituent units or terminal bases.

[0030] The raw material resin having the constituent units described in group (4) preferably has a weight average molecular weight (Mw) of 400 or more, more preferably 600 or more, more preferably 800 or more, more preferably 1,000 or more, more preferably 2,000 or more, more preferably 3,000 or more, and may also have a weight average molecular weight (Mw) of 5,000 or more. By setting it to the aforementioned lower limit value or above, the toughness and flexibility of the resin will be improved, and the cracking during molding and the generation of cracks in the molded article can be more effectively suppressed. Furthermore, the raw material resin having the constituent units described in group (4) preferably has a weight average molecular weight (Mw) of 30,000 or less, more preferably 20,000 or less, more preferably 16,000 or less, more preferably 12,000 or less, and more preferably 10,000 or less. By setting the value below the aforementioned upper limit, the resin's workability tends to be further improved due to the increased solvent solubility and decreased melt viscosity.

[0031] The raw material resin having the constituent units described in group (4) preferably has a number average molecular weight (Mn) of 400 or more, more preferably 600 or more, more preferably 800 or more, and may also have a number average molecular weight (Mn) of 1,000 or more. By setting it to the aforementioned lower limit or above, the toughness and flexibility of the resin will be improved, and the cracking during molding and the generation of cracks in the molded article can be more effectively suppressed. Furthermore, the raw material resin having the constituent units described in group (4) preferably has a number average molecular weight (Mn) of 5,000 or less, more preferably 4,000 or less, more preferably 3,500 or less, and even more preferably 2,500 or less. By setting it to the aforementioned upper limit or below, due to the improvement of the resin's solvent solubility and the reduction of the resin's melt viscosity, there is a tendency for the resin's workability to be further improved. The weight-average molecular weight and number-average molecular weight were determined according to the methods described in the examples below.

[0032] The hydroxyl value of the raw material resin having the constituent units described in group (4) is preferably 100 g / mol or higher, more preferably 130 g / mol or higher, more preferably 160 g / mol or higher, more preferably 190 g / mol or higher, and more preferably 210 g / mol or higher. By setting it to the aforementioned lower limit or higher, the amount of hydroxyl groups reacting with the compound represented by formula (2) will not exceed the required amount, and there is a tendency to further improve the dielectric properties. Furthermore, the hydroxyl value of the raw material resin having the constituent units described in group (4) is preferably 600 g / mol or lower, more preferably 550 g / mol or lower, more preferably 500 g / mol or lower, more preferably 450 g / mol or lower, more preferably 400 g / mol or lower, and may also be 360 ​​g / mol or lower. By setting it to the aforementioned upper limit or lower, there is a tendency to obtain a resin with excellent heat resistance and excellent dielectric properties. That is, by introducing the structure of the compound represented by formula (2), the resin obtained has a higher Tg but tends to have poor dielectric properties. Here, adjusting the amount of hydroxyl groups in the raw materials as described above is ideal. The hydroxyl equivalent was determined according to the description in the examples.

[0033] Next, we will explain the details of equation (2). Equation (2): [Chemistry 29] In formula (2), R6, R7 and R8 each independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, a alkyl halide with 1 to 10 carbon atoms, a hydroxyl group, a hydroxyalkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 12 carbon atoms.

[0034] In equation (2), R6, R7 and R8 are synonyms of R6, R7 and R8 in group (1) and have the same ideal range.

[0035] In the method for manufacturing resin of this embodiment, the raw material resin having the constituent unit described in group (4) and the compound represented by formula (2) may be used only one or more. In the method for manufacturing the resin of this embodiment, the molar ratio of the phenolic hydroxyl group of the raw material resin having the constituent unit described in group (4) to the compound represented by formula (2) added to the reaction system is preferably 1:1.3 to 0.4, and more preferably 1:1.2 to 0.5.

[0036] In the method for manufacturing the resin according to this embodiment, at least the compound represented by formula (2) is reacted with a raw material resin having the constituent units described in group (4) in the presence of an alkaline compound. By using an alkaline compound, the reaction between the phenolic hydroxyl groups of the raw material resin having the constituent units described in group (4) and the compound represented by formula (2) is promoted. The alkaline compound is preferably selected from at least one of potassium carbonate, rubidium carbonate, and cesium carbonate. By using such alkaline compounds as catalysts, the reaction between the raw material resin having the constituent units described in group (4) and the compound represented by formula (2) can be effectively promoted, and there is a tendency for the yield of the obtained compound to increase. In this embodiment, among potassium carbonate, rubidium carbonate, and cesium carbonate, potassium carbonate and cesium carbonate are preferred, with potassium carbonate being even better. There are no specific requirements regarding the form of potassium carbonate, rubidium carbonate, and cesium carbonate, but powder form is preferred. Furthermore, micronized powder (average particle size of approximately 10-200 μm) is preferred for potassium carbonate, rubidium carbonate, and cesium carbonate. Using powdered form increases the specific surface area, thereby improving reactivity.

[0037] In the manufacturing method of this embodiment, for each mol of the raw material resin containing the constituent unit described in group (4), it is preferable to use 1.0 mol (mol / mol-OH) or more for the basic compound, more preferably 2.5 mol or more, and ideally 10.0 mol or less, and even more preferably 7.0 mol or less. By setting the value to the aforementioned lower limit or above, there is a tendency to further enhance the reactivity of the hydroxyl groups of the raw material resin containing the constituent unit described in group (4) with the compound represented by formula (2). By setting the value to the aforementioned upper limit or below, there is a tendency to further enhance the reduction effect of manufacturing cost. In the manufacturing method of this embodiment, only one type of alkaline compound may be used, or two or more types may be used. When two or more types are used, the total amount within the above range is preferred.

[0038] In the resin manufacturing method of this embodiment, the compound represented by formula (2) and the raw material resin having the constituent units described in group (4) can also be reacted with the compound represented by formula (3). By also reacting the compound represented by formula (3), it reacts with the phenolic hydroxyl groups in the resin that has not reacted with the compound represented by formula (2), thereby reducing the hydroxyl value of the obtained resin and obtaining a resin with excellent dielectric properties. Equation (3): [Chemistry 30] In formula (3), R9 represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, a alkyl halide with 1 to 10 carbon atoms, a hydroxyl group, a hydroxyalkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 12 carbon atoms.

[0039] In equation (3), R9 is synonymous with R9 in group (1), and the more ideal range is also the same.

[0040] In the manufacturing method of this embodiment, the reaction with the raw material resin having the constituent units described in group (4) and the compound represented by formula (2) is preferably carried out at 40~110°C, and even more preferably at 50~90°C.

[0041] In the manufacturing method of this embodiment, it is more ideal to use a solvent system when reacting the raw material resin having the constituent units described in group (4) and the compound represented by formula (2). Solvents can be used without particular restrictions, but aprotic solvents are preferred, and at least one of aromatic hydrocarbon solvents and ether solvents is even better. By using aprotic solvents, there is a tendency to effectively carry out the action of O- from phenolic hydroxyl groups.

[0042] In the manufacturing method of this embodiment, it is ideal to separate and purify the resin obtained after reacting the raw material resin having the constituent units described in group (4) and the compound represented by formula (2). The separation and purification can be carried out according to conventional methods. In this embodiment, water or a solvent with water as the main component (e.g., the solvent is 70% by mass or more water) can be used for purification. In addition, after purification with water, etc., an alcohol (e.g., methanol) can be used for washing. The resin manufactured using the resin manufacturing method of this embodiment is preferably the resin of this embodiment described above. Therefore, it is preferable that the weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin manufactured using the resin manufacturing method of this embodiment are within the same range as the weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin of this embodiment described above.

[0043] <Applications> The resin of this embodiment can be used as a curable resin composition. The aforementioned curable resin composition may consist of only one or two or more resins of this embodiment, and may further include thermosetting compounds other than the resins of this embodiment. The aforementioned thermosetting compounds are preferably compounds other than the resins of this embodiment and include at least one selected from compounds having carbon-carbon unsaturated bond groups and epoxy resins. In addition, the aforementioned curable resin composition may also contain one or more additives. Examples of additives include curing initiators, flame retardants, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, dyes, pigments, tackifiers, flow modifiers, lubricants, defoamers, dispersants, leveling agents, gloss agents, and polymerization inhibitors.

[0044] Examples of hardening initiators include di-3-methoxybutyl peroxide dicarbonate, di-2-ethylhexyl peroxide dicarbonate, bis(4-tertiary butylcyclohexyl) peroxide dicarbonate, diisopropyl peroxide dicarbonate, tributyl peroxide isopropyl carbonate, dimyristyl peroxide dicarbonate, 1,1,3,3-tetramethylbutyl neodecanoate, α-isopropylphenyl peroxide neodecanoate, tributyl peroxide neodecanoate, and 1,1-bis(tertiary butyl) peroxide dicarbonate. Cyclohexane peroxide, 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane, 1,1-bis(tert-butylperoxy)cyclododecane, tert-hexyl isopropyl monocarbonate peroxide, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butyl peroxylaurate, tert-butylperoxy-2-ethylhexane, 2,5-dimethyl-2,5-di(benzoyl peroxide)hexane, tert-butyl peroxyacetic acid, 2,2-bis(di-butylperoxy)cyclohexane ... Butene (tert-butylperoxy)butene, tert-butyl peroxybenzoate, n-Butyl-4,4-bis(t-peroxy)valerate, di-t-butylperoxyisophthalate, dicumyl peroxide, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 1,3-bis(tert-butylperoxydiisopropyl)benzene, tert-butylisopropylphenyl peroxide, di-tert-butyl peroxide, p-menthane hydroperoxide, and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, etc. When the curable resin composition of this embodiment contains a curing initiator, the amount of initiator, relative to 100 parts by weight of the resin of this embodiment, is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, more preferably 1.0 parts by weight or more, and ideally, 10.0 parts by weight or less, more preferably 5.0 parts by weight or less, more preferably 3.0 parts by weight or less, and even more preferably 2.0 parts by weight or less. The curable resin composition of this embodiment may contain only one type of curing initiator or may contain two or more types of curing initiators. When two or more types are contained, the total amount within the above range is preferred.

[0045] The cured material of this embodiment is obtained by curing the aforementioned curable resin composition. Because of its excellent heat resistance and dielectric properties, this cured material is ideally suited for use as an insulating layer for printed circuit boards and as a semiconductor packaging material. [Example]

[0046] The following examples further illustrate the present invention. The materials, amounts, proportions, processing contents, and processing steps shown in the following examples can be appropriately modified without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In cases where the measuring equipment used in the embodiments is difficult to obtain due to production stoppages, other equipment with equivalent performance can be used for measurement.

[0047] <Determination of number-average molecular weight and weight-average molecular weight> The number-average molecular weight and weight-average molecular weight of the resin were determined using gel permeation chromatography (GPC). The analytical columns were connected to Showa Denko (KF-801, KF-802, KF-803, and KF-804), and the detection system used a Shimadzu RID-20A differential refractive index detector. 10 mg of the resin being analyzed was dissolved in 3 g of tetrahydrofuran in the precipitate, and the injection volume into the column was set to 20 μL. Analysis was performed at a precipitate flow rate of 1 mL / min and a column temperature of 40 °C. A molecular weight calibration curve was constructed using Tosoh's standard polystyrene PStQuick MP-N, and the converted molecular weight of polystyrene was estimated.

[0048] <Determination of Hydroxyl Value of Raw Material Resin> The hydroxyl values ​​of the raw material phenol-modified xylene resin and the raw material phenol-modified trimethylbenzene resin were determined in accordance with JIS K0070-92-7.1.

[0049] <Hydroxy content of resin> The phenolic hydroxyl content of the above resin was calculated by proton nuclear magnetic resonance (1H-NMR) analysis. Specifically, the reduction rate [%] of the proton peak area of ​​phenolic hydroxyl groups near 4.2-5.4 ppm when the proton peak area of ​​p-tert-butyl around 1.07-1.24 ppm was set to 9 was defined as the phenolic hydroxyl modification rate [%], and was calculated by the following formula. (Hydroxy content of resin [mmol / g]) = (Hydroxy content of raw resin [mmol / g]) × (100 - (Modification rate [%))) / 100 Equipment used: Bruker AVANCE III 500 (500MHz)

[0050] <Methacrylic acid content> The methacrylate content was calculated using proton nuclear magnetic resonance (1H-NMR) analysis. Specifically, the peak area of ​​the terminal proton of the methacrylate group in the 5.4-5.8 ppm range (where the proton peak area of ​​the tert-butyl group in the 1.07-1.24 ppm range is set to 9) was multiplied by 100, and the resulting value was defined as the methacrylate content [%]. The methacrylate content [mmol / g] was calculated based on the obtained methacrylate content, the modification rate of phenolic hydroxyl groups, the hydroxyl content of the raw resin, and the molecular weight of the modified substituents. Furthermore, the phenolic hydroxyl peaks of the phenol-modified xylene resin or phenol-modified trimethylbenzene resin in the 4.2-5.4 ppm range disappeared after the reaction, confirming that the reaction had been completed. Equipment used: Bruker AVANCE III 500 (500MHz)

[0051] <Synthetic Example 1: Synthesis of p-tert-butylphenol (PTBP) modified xylene resin (1)> In a 0.5 L separable flask equipped with a thermometer and a stirrer, 200.0 g of xylene-formaldehyde resin (manufactured by Fudow Corporation, "NIKANOL G"), 253.2 g (1.69 mol) of p-tert-butylphenol (manufactured by DIC Corporation), and 0.14 g (0.74 mmol) of p-toluenesulfonic acid monohydrate (manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.) were added, and the temperature was raised to 90 °C. Further, the mixture was dehydrated while the temperature was raised to 220 °C over 5 hours to allow the reaction to proceed. Then, 0.09 g (1.50 mmol) of urea (Tokyo Chemical Industries, Ltd.) was added to stop the reaction, yielding 411.4 g of p-tert-butylphenol-modified xylene resin. The number-average molecular weight, weight-average molecular weight, and hydroxyl value of the obtained resin were determined under the aforementioned conditions and are shown in Table 1.

[0052] <Synthetic Example 2: Synthesis of p-tert-butylphenol (PTBP) modified xylene resin (2)> 250.0 g of xyleneformaldehyde resin (manufactured by Fudow Corporation, "NIKANOL H"), 166.7 g (1.11 mol) of p-tert-butylphenol (manufactured by DIC Corporation), and 0.14 g (0.74 mmol) of p-toluenesulfonic acid monohydrate (manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.) were added to a 0.5 L separable flask equipped with a thermometer and a stirrer, and the mixture was heated to 115 °C. Further, the mixture was dehydrated while being heated to 180 °C for 6 hours to allow the reaction to proceed. Then, 0.14 g (2.33 mmol) of urea (Tokyo Chemical Industries, Ltd.) was added to stop the reaction, yielding 375.2 g of p-tert-butylphenol modified xylene resin. The number average molecular weight, weight average molecular weight, and hydroxyl value of the obtained resin were determined under the aforementioned conditions and are shown in Table 1.

[0053] <Synthetic Example 3: Synthesis of Tris(methylbenzene)-Formaldehyde Resin> In a 1.0L separable flask equipped with a thermometer, a Dimroth condenser, and a stirrer with a removable bottom, 621.6g of a 37% (w / w) formaldehyde aqueous solution (7.66mol of formaldehyde, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added. While stirring, 132.9g (1.33mol) of 98% (w / w) sulfuric acid (manufactured by Fujifilm and Wakamitsu Chemical Co., Ltd.) and 459.7g (3.82mol) of mesitylene (manufactured by Fujifilm and Wakamitsu Chemical Co., Ltd.) were added, and the mixture was refluxed at approximately 100°C under normal pressure for 4 hours. Next, 335g of mesitylene (manufactured by Fujifilm and Wakamitsu Chemical Co., Ltd.) was added as a diluent, and the mixture was allowed to stand. The upper oil phase was retained, and the lower aqueous phase was removed. Further, the oil phase was neutralized and washed with water, and unreacted raw materials were distilled off under reduced pressure to obtain 578.6g of mesitylene-formaldehyde resin. The number-average molecular weight and weight-average molecular weight of the obtained resins were determined according to the aforementioned conditions and are shown in Table 1.

[0054] <Synthetic Example 4: Synthesis of Trimethylbenzene Resin Modified with Tertiary Butylphenol (PTBP) (1)> In a 0.5 L separable flask equipped with a thermometer and a stirrer, 200.0 g of the trimethylbenzene-formaldehyde resin obtained in Synthesis Example 3, 163.1 g (1.09 mol) of p-tert-butylphenol (manufactured by DIC Corporation), and 0.42 g (0.22 mmol) of p-toluenesulfonic acid monohydrate (manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.) were added, and the temperature was raised to 115 °C. Further, the temperature was raised to 200 °C over 1 hour while dehydrating the resin to allow the reaction to proceed. Then, 0.05 g (0.83 mmol) of urea (Tokyo Chemical Industries, Ltd.) was added to stop the reaction, yielding 346.1 g of p-tert-butylphenol-modified trimethylbenzene resin. The number average molecular weight, weight average molecular weight, and hydroxyl value of the obtained resin were determined under the aforementioned conditions and are shown in Table 1.

[0055] <Synthetic Example 5: Synthesis of Trimethylbenzene Resin Modified with Tertiary Butylphenol (PTBP) (2)> In a 0.5-liter separable flask equipped with a thermometer and a stirrer, 100.3 g of the trimethylbenzeneformaldehyde resin obtained in Synthesis Example 3, 134.1 g (0.89 mol) of p-tert-butylphenol (manufactured by DIC Corporation), 9.32 g of 92% paraformaldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and 0.28 g (0.15 mmol) of p-toluenesulfonic acid monohydrate (manufactured by Fujifilm and Wako Pure Chemical Co., Ltd.) were added, and the temperature was raised to 90°C. Further, the mixture was dehydrated while the temperature was raised to 220°C for 5 hours to allow the reaction to proceed. Then, 0.04 g (0.67 mmol) of urea (Tokyo Chemical Industry Co., Ltd.) was added to stop the reaction, yielding 251.6 g of p-tert-butylphenol-modified trimethylbenzeneformaldehyde resin. The number-average molecular weight, weight-average molecular weight, and hydroxyl value of the obtained resin were determined under the aforementioned conditions and are shown in Table 1.

[0056] [Table 1] Synthesis example 1 Synthesis example 2 Synthesis example 3 Synthesis example 4 Synthesis example 5 Types of raw material resins xylene resin xylene resin Trimethylbenzene resin Trimethylbenzene resin Number average molecular weight (Mn) 1,922 1,264 486 1,651 1,648 Weight average molecular weight (Mw) 8,126 7,109 686 4,975 3,745 Hydroxyl value [g / OH-mol] 229 340 315 252 Hydroxyl content [mmol / g] 4.37 2.94 3.17 3.97

[0057] Example 1 Under nitrogen atmosphere, 22.0 g (96.2 mmol in hydroxyl molar conversion) of the p-tert-butylphenol modified xylene resin obtained in Synthesis Example 1, 190 g of tetrahydrofuran (manufactured by Fujifilm and Kakuzo Chemical Co., Ltd.), 66.5 g (481 mmol) of potassium carbonate (manufactured by Fujifilm and Kakuzo Chemical Co., Ltd., with an average particle size of less than 150 μm) and 11.2 g (72.7 mmol) of methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 300 mL four-necked flask equipped with a stirrer, thermometer, and reflux tube. The mixture was reacted at 70 °C for 24 hours. Further, 18.1 g (177 mmol) of acetic anhydride (manufactured by Fujifilm and Kakuzo Chemical Co., Ltd.) was added, and the mixture was reacted at 70 °C for another 24 hours. After cooling the reaction solution with air, it was filtered through a 0.45 μm filter, and the resulting solution was added dropwise to purified water to solidify it. The solid was recovered and washed with purified water, followed by washing with methanol. The resulting solid was then washed again with purified water and methanol, and dried under reduced pressure to obtain 23.1 g of the target methacrylic acid compound. The number-average molecular weight, weight-average molecular weight, and methacrylic acid group content of the obtained methacrylic acid compound were determined under the aforementioned conditions and are shown in Table 2. The cured material was prepared according to the following method. Furthermore, the dielectric properties, glass transition temperature, and 5% weight loss temperature of the obtained cured material were measured and are shown in Table 2.

[0058] <Making of Hardened Materials> The hardened material is produced by placing a mixture obtained by adding 1.5 parts by weight of PERBUTYL (registered trademark) P (manufactured by Nippon Oil Company) to the methacrylic acid compound obtained above into a mold with a length of 100 mm and a width of 30 mm, and then subjecting it to vacuum hot pressing at a pressure of 1.92 MPa and a temperature of 200°C for 1.5 hours. Equipment used: 5-segment pressing machine VH2-1630 manufactured by Beichuan Precision Machinery Co., Ltd.

[0059] <Determination of Dielectric Properties of Hardened Materials> The dielectric constant and dielectric loss tangent of the hardened material were determined at 10 GHz by cutting the obtained hardened material into pieces with a thickness of 1 mm, a width of 0.8 mm, and a length of 100 mm, drying them at 120 °C for 1 hour, and then using the cavity resonance perturbation method. Equipment used: Agilent 8722ES Network Analyzer

[0060] <Determination of Glass Transfer Temperature of Hardened Materials> The glass transition temperature of a hardened material is defined as the peak temperature at which the dynamic elastic modulus is obtained by dynamic viscoelasticity measurement of a cut piece of the hardened material measuring 5 mm wide and 40 mm long. The unit is expressed in °C. Equipment used: Hitachi High-Tech Science DMA7100 Heating rate: 5℃ / min Frequency: Sine wave, 10Hz

[0061] <Determination of 5% weight loss temperature of hardened material> The 5% weight reduction temperature of the hardened material is defined as the temperature at which the weight of a 5% decrease is achieved when the hardened material is cut into approximately 10 mg portions and subjected to simultaneous thermogravimetric and differential thermal analysis. The unit is expressed in °C. Equipment used: Hitachi High-Tech Science STA7200 Heating rate: 10℃ / min

[0062] Example 2 In Example 1, the amount of potassium carbonate (manufactured by Fujifilm and Hikari Pure Chemical Industries, with an average particle size of less than 150 μm) added was changed to 66.4 g (480 mmol), the amount of methacrylic anhydride (manufactured by Tokyo Chemical Industries, Ltd.) added was changed to 12.4 g (80.5 mmol), and the amount of acetic anhydride (manufactured by Fujifilm and Hikari Pure Chemical Industries, Ltd.) added was changed to 14.9 g (146 mmol). Otherwise, the reaction and purification were carried out in the same manner as in Example 1, yielding 21.6 g of the target methacrylic acid compound. The number-average molecular weight, weight-average molecular weight, and methacrylation rate of the obtained methacrylic acid compound were determined under the aforementioned conditions and are shown in Table 2. The dielectric properties, glass transition temperature, and 5% weight reduction temperature of the prepared hardened material were measured in the same manner as in Example 1, and are shown in Table 2.

[0063] Example 3 The amounts of p-tert-butylphenol-modified xylene resin added in Example 1 were changed to 22.1 g (equivalent to 96.3 mmol in hydroxyl moles), tetrahydrofuran (manufactured by Fujifilm and Hikari Pure Chemical Industries Co., Ltd.) to 191 g, potassium carbonate (manufactured by Fujifilm and Hikari Pure Chemical Industries Co., Ltd., with an average particle size of less than 150 μm) to 66.6 g (482 mmol), methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) to 12.3 g (79.7 mmol), and acetic anhydride (manufactured by Fujifilm and Hikari Pure Chemical Industries Co., Ltd.) to 15.3 g (150 mmol). Otherwise, the reaction and purification were carried out in the same manner as in Example 1, yielding 23.8 g of the target methacrylic acid compound. The number-average molecular weight, weight-average molecular weight, and methacrylation rate of the obtained methacrylic acid compound were determined under the aforementioned conditions and are shown in Table 2. The dielectric properties, glass transition temperature, and 5% weight reduction temperature of the prepared hardened material were measured in the same manner as in Example 1, and are shown in Table 2.

[0064] Example 4 The amounts of potassium carbonate (manufactured by Fujifilm and Hikari Pure Chemical Industries, with an average particle size of less than 150 μm) added in Example 1 were changed to 66.5 g (481 mmol), methacrylic anhydride (manufactured by Tokyo Chemical Industries, Ltd.) added to 13.7 g (88.8 mmol), and acetic anhydride (manufactured by Fujifilm and Hikari Pure Chemical Industries, Ltd.) added to 11.8 g (115 mmol). Otherwise, the reaction and purification were carried out in the same manner as in Example 1, yielding 23.9 g of the target methacrylic acid compound. The number-average molecular weight, weight-average molecular weight, and methacrylation rate of the obtained methacrylic acid compound were determined under the aforementioned conditions and are shown in Table 2. The dielectric properties, glass transition temperature, and 5% weight reduction temperature of the prepared hardened material were measured in the same manner as in Example 1, and are shown in Table 2.

[0065] Example 5 The p-tert-butylphenol modified xylene resin obtained in Synthesis Example 1 was replaced with 22.6 g (66.4 mmol in hydroxyl molars) of the p-tert-butylphenol modified xylene resin obtained in Synthesis Example 2. The amount of tetrahydrofuran (manufactured by Fujifilm and Hikari Pure Chemical Industries Co., Ltd.) was changed to 200 g, the amount of potassium carbonate (manufactured by Fujifilm and Hikari Pure Chemical Industries Co., Ltd., with an average particle size of 150 μm or less) was changed to 45.9 g (332 mmol), the amount of methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to 12.6 g (81.7 mmol), and the amount of acetic anhydride (manufactured by Fujifilm and Hikari Pure Chemical Industries Co., Ltd.) was changed to 8.1 g (79.5 mmol). Otherwise, the reaction and purification were carried out in the same manner as in Example 1 to obtain 20.7 g of the methacrylic acid compound as the target product. The number-average molecular weight, weight-average molecular weight, and methacrylation rate of the obtained methacrylic acid compounds were determined under the aforementioned conditions and are shown in Table 2. The dielectric properties and 5% weight reduction temperature of the hardened material were measured in the same manner as in Example 1, and are shown in Table 2.

[0066] Example 6 In Example 1, the amount of tert-butylphenol-modified xylene resin added was changed to 17.1 g (equivalent to 74.5 mmol in hydroxyl moles), the amount of tetrahydrofuran (manufactured by Fujifilm and Hikari Pure Chemical Industries Co., Ltd.) was changed to 223 g, the amount of potassium carbonate (manufactured by Fujifilm and Hikari Pure Chemical Industries Co., Ltd., with an average particle size of less than 150 μm) was changed to 60.4 g (437 mmol), the amount of methacrylic anhydride (manufactured by Tokyo Chemical Industries Co., Ltd.) was changed to 10.4 g (67.3 mmol), and benzoic anhydride (manufactured by Tokyo Chemical Industries Co., Ltd.) was used instead of acetic anhydride (manufactured by Fujifilm and Hikari Pure Chemical Industries Co., Ltd.). Otherwise, the reaction and purification were carried out in the same manner as in Example 1, yielding 21.4 g of the target methacrylic acid compound. The number-average molecular weight, weight-average molecular weight, and methacrylation rate of the obtained methacrylic acid compound were determined under the aforementioned conditions and are shown in Table 3. The dielectric properties, glass transition temperature, and 5% weight reduction temperature of the prepared hardened material were measured in the same manner as in Example 1, and are shown in Table 3.

[0067] Example 7 The p-tert-butylphenol modified xylene resin obtained in Synthesis Example 1 of Example 1 was replaced with 22.2 g (70.5 mmol in terms of hydroxyl moles) of p-tert-butylphenol modified mesitylene resin obtained in Synthesis Example 4. The amount of tetrahydrofuran (manufactured by Fujifilm and Hikari Pure Chemical Industries Co., Ltd.) was changed to 200 g, the amount of potassium carbonate (manufactured by Fujifilm and Hikari Pure Chemical Industries Co., Ltd., with an average particle size of less than 150 μm) was changed to 38.8 g (281 mmol), the amount of methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to 13.3 g (86.4 mmol), and the amount of acetic anhydride (manufactured by Fujifilm and Hikari Pure Chemical Industries Co., Ltd.) was changed to 5.77 g (56.5 mmol). Otherwise, the reaction and purification were carried out in the same manner as in Example 1 to obtain 24.4 g of the methacrylic acid compound as the target product. The number-average molecular weight, weight-average molecular weight, and methacrylation rate of the obtained methacrylic acid compounds were determined under the aforementioned conditions and are shown in Table 3. The dielectric properties, glass transition temperature, and 5% weight reduction temperature of the prepared hardened material were measured in the same manner as in Example 1, and are shown in Table 3.

[0068] Example 8 The p-tert-butylphenol modified xylene resin obtained in Synthesis Example 1 of Example 1 was replaced with 15.0 g (59.8 mmol in terms of hydroxyl moles) of p-tert-butylphenol modified mesitylene resin obtained in Synthesis Example 5. The amount of tetrahydrofuran (manufactured by Fujifilm and Hikari Pure Chemical Industries Co., Ltd.) was changed to 136 g, the amount of potassium carbonate (manufactured by Fujifilm and Hikari Pure Chemical Industries Co., Ltd., with an average particle size of less than 150 μm) was changed to 33.4 g (242 mmol), the amount of methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to 11.3 g (73.3 mmol), and the amount of acetic anhydride (manufactured by Fujifilm and Hikari Pure Chemical Industries Co., Ltd.) was changed to 4.88 g (47.8 mmol). Otherwise, the reaction and purification were carried out in the same manner as in Example 1 to obtain 16.6 g of the methacrylic acid compound as the target product. The number-average molecular weight, weight-average molecular weight, and methacrylation rate of the obtained methacrylic acid compounds were determined under the aforementioned conditions and are shown in Table 3. The dielectric properties, glass transition temperature, and 5% weight reduction temperature of the prepared hardened material were measured in the same manner as in Example 1, and are shown in Table 3.

[0069] Reference Example 1 A mixture obtained by adding 1.5 parts by weight of PERBUTYL (registered trademark) P (manufactured by Nippon Oil Co., Ltd.) to SA9000 (manufactured by SABIC), a polyphenylene ether with methacrylic groups at both ends, was used to prepare a cured product in the same manner as in Example 1. The dielectric properties, glass transition temperature, and 5% weight reduction temperature of the obtained cured product were measured and are shown in Table 3.

[0070] [Table 2] Example 1 Example 2 Example 3 Example 4 Example 5 raw material resin Synthesis example 1 Synthesis example 1 Synthesis example 1 Synthesis example 1 Synthesis example 2 Number average molecular weight (Mn) 2,590 2,883 3,005 4,568 1,618 Weight average molecular weight (Mw) 9,925 10,164 10,475 13,120 8,031 Hydroxyl content after modification [mmol / g] 0.095 - - - - Unmodified rate [%] 2.17 0 0 0 0 methacrylic acid group content [mmol / g] 2.48 2.71 2.74 2.80 2.15 Dielectric constant (10GHz) 2.42 2.39 2.41 2.40 2.39 Dielectric loss tangent (10GHz) 0.0046 0.0044 0.0044 0.0040 0.0044 Glass transition temperature [℃] 167 173 179 193 5% weight reduction in temperature [℃] 357 351 375 378 379

[0071] [Table 3] Example 6 Example 7 Example 8 Reference Example 1 raw material resin Synthesis example 1 Synthesis example 4 Synthesis example 5 - Number average molecular weight (Mn) 3,374 2,086 2,037 Weight average molecular weight (Mw) 11,025 6,084 5,203 Hydroxyl content after modification [mmol / g] - - - Unmodified rate [%] 0 0 0 methacrylic acid group content [mmol / g] 1.73 2.19 2.84 0.77 Dielectric constant (10GHz) 2.43 2.39 2.37 2.43 Dielectric loss tangent (10GHz) 0.0048 0.0046 0.0045 0.0049 Glass transition temperature [℃] 193 189 182 157 5% weight reduction in temperature [℃] 378 345 371 307

Claims

1. A resin having the constituent units described in group (1), wherein the phenolic hydroxyl content of the resin is 0.5 mmol / g or less, group (1): In group (1), R1 independently represents methylene, methyleneoxy, methyleneoxymethylene or oxymethylene; R2 represents an alkyl group having 1 to 3 carbon atoms; R3, R4 and R5 independently represent a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; R6, R7 and R8 independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a hydroxyl group, a hydroxyalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; R 9 represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, a alkyl halide with 1 to 10 carbon atoms, a hydroxyl group, a hydroxyalkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 12 carbon atoms; v represents 0 or 1, w represents a number from 1 to 3, and x, y, and z each independently represent a number from 0 to 3; a, b, c, and d each independently represent the molar ratio of the constituent units, where a is a number greater than 1, b is a number greater than 0, c is a number greater than 1, and d is a number greater than 0; R1 can also bond to each other to form a cross-linked structure; * indicates the bonding position with other constituent units or end groups.

2. The resin as requested in item 1, wherein, In group (1), R6 is a methyl group, and R7 and R8 are hydrogen atoms.

3. The resin as requested in item 1 or 2, wherein, In group (1), R3, R4 and R5 are each independently an alkyl group having 1 to 10 carbon atoms.

4. The resin as requested in item 1 or 2, wherein, In group (1), R3, R4 and R5 are each independently an alkyl group having 1 to 5 carbon atoms.

5. The resin as requested in item 1 or 2, wherein, The content of the groups (1) of the resin is 1.0 mmol / g or more, and R6 to R8 in the above groups are synonyms with R6 to R8 in group (1).

6. The resin as requested in item 1 or 2, wherein, The constituent units described in group (1) include at least one of the constituent units described in group (1-1), group (1-2), group (1-3), and group (1-4). Group (1-1): In group (1-1), R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a1, b, c, and d are synonyms with R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a, b, c, and d in group (1), respectively. * indicates the bonding position with other constituent units or end bases. Group (1-2): In group (1-2), R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a2, b, c, and d are synonyms of R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a, b, c, and d in group (1), respectively. * indicates the bond position with other constituent units or end bases; Group (1-3): In group (1-3), R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a3, b, c, and d are synonyms of R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a, b, c, and d in group (1), respectively. * indicates the bond position with other constituent units or end bases; Group (1-4): In groups (1-4), R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a4, b, c, and d are synonyms with R1, R3, R4, R5, R6, R7, R8, R9, v, x, y, z, a, b, c, and d in group (1), respectively. * indicates the bond position with other constituent units or end bases.

7. The resin as claimed in claim 6, wherein, The constituent units described in group (1) include the constituent units described in group (1-1) or group (1-4).

8. The resin as requested in item 1 or 2, wherein, The number average molecular weight Mn is 500~6,000, and the weight average molecular weight Mw is 500~15,000.

9. The resin as requested in item 1 or 2, wherein, The terminal groups of the resin are selected from hydrogen atoms, hydroxyl groups, and hydroxymethyl groups.

10. A resin is a reaction product of a compound represented by at least formula (2) and a raw material resin having the constituent units described in group (4), formula (2): In formula (2), R6, R7 and R8 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxyl group, a hydroxyalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; Group (4): In group (4), R1 independently represents methylene, methyleneoxy, methyleneoxymethylene or oxymethylene; R2 represents alkyl with 1 to 3 carbon atoms; R3, R4 and R5 independently represent halogen atoms, alkyl with 1 to 10 carbon atoms, alkyl halide with 1 to 10 carbon atoms, hydroxyalkyl with 1 to 10 carbon atoms, or aryl with 6 to 12 carbon atoms; v represents 0 or 1, w represents 1 to 3 numbers, x, y and z independently represent 0 to 3 numbers; a, b, c and d independently represent the molar ratio of the constituent units, a is a number greater than 1, b is a number greater than 0, c is a number greater than 1, and d is a number greater than 0; R1 can also be bonded to each other to form a cross-linked structure; * indicates the bonding position with other constituent units or end groups.

11. A method for manufacturing a resin, comprising the following steps: reacting a compound represented by at least formula (2) with a raw material resin having the constituent units described in group (4) in the presence of an alkaline compound, formula (2): In formula (2), R6, R7 and R8 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a hydroxyl group, a hydroxyalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; Group (4): In group (4), R1 independently represents methylene, methyleneoxy, methyleneoxymethylene or oxymethylene; R2 represents alkyl with 1 to 3 carbon atoms; R3, R4 and R5 independently represent halogen atoms, alkyl with 1 to 10 carbon atoms, alkyl halide with 1 to 10 carbon atoms, hydroxyalkyl with 1 to 10 carbon atoms, or aryl with 6 to 12 carbon atoms; v represents 0 or 1, w represents 1 to 3 numbers, x, y and z independently represent 0 to 3 numbers; a, b, c and d independently represent the molar ratio of the constituent units, a is a number greater than 1, b is a number greater than 0, c is a number greater than 1, and d is a number greater than 0; R1 can also be bonded to each other to form a cross-linked structure; * indicates the bonding position with other constituent units or end groups.

12. A method for manufacturing the resin as described in claim 11, wherein, In formula (2), R6 is a methyl group, and R7 and R8 are hydrogen atoms.

13. A method for manufacturing the resin as described in claim 11 or 12, wherein, In group (4), R3, R4 and R5 are each independently an alkyl group having 1 to 10 carbon atoms.

14. A method for manufacturing the resin as described in claim 11 or 12, wherein, In group (4), R3, R4 and R5 are each independently an alkyl group having 1 to 5 carbon atoms.

15. A method for manufacturing the resin as described in claim 11 or 12, wherein, The hydroxyl value of the raw material resin is 100~600g / mol.

16. A method for manufacturing the resin as described in claim 11 or 12, wherein, The constituent units described in group (4) include at least one of the constituent units described in group (4-1), group (4-2), group (4-3), and group (4-4). Group (4-1): In group (4-1), R1, R3, R4, R5, v, x, y, z, a1, b, c, and d are synonyms of R1, R3, R4, R5, v, x, y, z, a, b, c, and d in group (4), respectively. * indicates the bonding position with other constituent units or end bases. Group (4-2): In group (4-2), R1, R3, R4, R5, v, x, y, z, a2, b, c, and d are synonyms of R1, R3, R4, R5, v, x, y, z, a, b, c, and d in group (4), respectively. * indicates the bond position with other constituent units or end bases; Group (4-3): In group (4-3), R1, R3, R4, R5, v, x, y, z, a3, b, c, and d are synonyms of R1, R3, R4, R5, v, x, y, z, a, b, c, and d in group (4), respectively. * indicates the bond position with other constituent units or end bases; Group (4-4): In group (4-4), R1, R3, R4, R5, v, x, y, z, a4, b, c and d are synonyms with R1, R3, R4, R5, v, x, y, z, a, b, c and d in group (4), respectively. * indicates the bond position with other constituent units or end bases.

17. The method for manufacturing the resin as described in claim 16, wherein, The constituent units described in group (4) include the constituent units described in group (4-1) or group (4-4).

18. A method for manufacturing the resin as described in claim 11 or 12, wherein, The raw material resin having the constituent units described in group (4) has a number average molecular weight Mn of 400 to 4,000 and a weight average molecular weight Mw of 400 to 16,000.

19. A method for manufacturing the resin as described in claim 11 or 12, wherein, The terminal groups of the raw material resin having the constituent units described in group (4) are selected from hydrogen atoms, hydroxyl groups and hydroxymethyl groups.

20. A method for manufacturing the resin as described in claim 11 or 12, wherein, The alkaline compound contains at least one of potassium carbonate, rubidium carbonate, and cesium carbonate.

21. A method for manufacturing the resin as described in claim 11 or 12, wherein, The resin manufactured is a resin having the constituent units described in group (1), group (1): In group (1), R1 independently represents methylene, methyleneoxy, methyleneoxymethylene or oxymethylene; R2 represents an alkyl group having 1 to 3 carbon atoms; R3, R4 and R5 independently represent a halogen atom, an alkyl group having 1 to 10 carbon atoms, a alkyl halide having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; R6, R7 and R8 independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide having 1 to 10 carbon atoms, a hydroxyl group, a hydroxyalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; R 9 represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, a alkyl halide with 1 to 10 carbon atoms, a hydroxyl group, a hydroxyalkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 12 carbon atoms; v represents 0 or 1, w represents a number from 1 to 3, and x, y, and z each independently represent a number from 0 to 3; a, b, c, and d each independently represent the molar ratio of the constituent units, where a is a number greater than 1, b is a number greater than 0, c is a number greater than 1, and d is a number greater than 0; R1 can also bond to each other to form a cross-linked structure; * indicates the bonding position with other constituent units or end groups.

22. A curable resin composition comprising the resin of any one of claims 1 to 10.

23. The curable resin composition of claim 22 further includes thermosetting compounds other than the resin.

24. The curable resin composition as claimed in claim 23, wherein, The thermosetting compound includes at least one of compounds with carbon-carbon unsaturated bond groups other than the resin and epoxy resin.

25. A cured product of a curable resin composition, which is a cured product of a curable resin composition as claimed in any one of claims 22 to 24.

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