Resin, method for producing resin, curable resin composition, and cured object

Abstract

Provided are a novel resin having excellent dielectric characteristics, a method for producing the resin, a curable resin composition, and a cured object. The resin has constituent units given in group (1) (wherein a, b, c, and d independently indicate the molar proportions of the respective constituent units, and a is a number of 1 or larger, b is a number of 0 or larger, c is a number of 1 or larger, and d is a number of 0 or larger).

Description

Resin, method for producing resin, curable resin composition and cured product

[0001] The present invention relates to a novel resin, a method for producing the resin, a curable resin composition, and a cured product.

[0002] Resins having vinyl groups, such as vinyl compounds, have excellent heat resistance and are therefore used in various materials. For example, the one disclosed in Patent Document 1 is known. Meanwhile, studies are also underway to utilize the excellent heat resistance of resins having vinyl groups, such as vinyl compounds, while improving their dielectric properties, to use them as materials for electronic devices that handle high-frequency signals. Such vinyl compounds and methods for producing them are known, for example, from Patent Documents 2 and 3.

[0003] Japanese Patent Application Laid-Open No. 2020-037651 Japanese Patent Application Laid-Open No. 2015-189925 Japanese Patent Application Laid-Open No. 01-108212

[0004] With recent technological innovations, there is a demand for novel resins having vinyl groups with excellent dielectric properties, and methods for producing the same. The present invention aims to solve such problems, and provides a novel resin with excellent dielectric properties, a method for producing the resin, a curable resin composition, and a cured product.

[0005] As a result of investigations conducted by the present inventors in light of the above-mentioned problems, it was found that the above-mentioned problems can be solved by using a resin having a predetermined structure. Specifically, the above-mentioned problems were solved by the following means. <1> Resins having structural units described in Group (1). Group (1) (In group (1), R １ R each independently represents a methylene group, a methyleneoxy group, a methyleneoxymethylene group, or an oxymethylene group. ２ represents an alkyl group having 1 to 3 carbon atoms. ３ , R ４ and R ５ R each independently represents 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. ６ , R ７and R ８ R each independently 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. 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. 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 structural unit, a is a number of 1 or more, b is a number of 0 or more, c is a number of 1 or more, and d is a number of 0 or more. R １ may be bonded to each other to form a crosslinked structure. * indicates the bonding position with another structural unit or a terminal group.) <2> In group (1), R ６ is a methyl group, and R ７ and R ８ <3> The resin according to <1>, wherein R is a hydrogen atom. ３ , R ４ and R ５ are each independently an alkyl group having 1 to 10 carbon atoms. ３ , R ４ and R ５ are each independently an alkyl group having 1 to 5 carbon atoms. <5> The resin according to any one of <1> to <4>, wherein the resin has a phenolic hydroxyl group content of 0.5 mmol / g or less. <6> The resin according to any one of <1> to <5>, wherein the content of the group represented by the following in group (1) of the resin is 1.0 mmol / g or more. (R in the above group ６ ~R ８ is R in group (1). ６ ~R ８<7> The resin according to any one of <1> to <6>, wherein the structural unit described in group (1) includes at least one of the structural units described in group (1-1), the structural units described in group (1-2), the structural units described in group (1-3), and the structural units described in group (1-4). Group (1-1) (In group (1-1), R １ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , v, x, y, z, a1, b, c and d are R in group (1), respectively. １ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , v, x, y, z, a, b, c and d. * indicates the bonding position with other structural units or terminal groups.) Group (1-2) (In group (1-2), R １ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , v, x, y, z, a2, b, c and d are R in group (1), respectively. １ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , v, x, y, z, a, b, c and d. * indicates the bonding position with other structural units or terminal groups.) Group (1-3) (In group (1-3), R １ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９, v, x, y, z, a3, b, c and d are R in group (1), respectively. １ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , v, x, y, z, a, b, c and d. * indicates the bonding position with other structural units or terminal groups.) Group (1-4) (In group (1-4), R １ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , v, x, y, z, a4, b, c and d are R in group (1), respectively. １ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , v, x, y, z, a, b, c, and d are synonymous. * indicates the bonding position with another structural unit or terminal group.) <8> The resin according to <7>, in which the structural unit described in group (1) includes a structural unit described in group (1-1) or a structural unit described in group (1-4). <9> The resin according to any one of <1> to <8>, in which the number average molecular weight (Mn) is 500 to 6,000 and the weight average molecular weight (Mw) is 500 to 15,000. <10> The resin according to any one of <1> to <9>, in which the terminal groups of the resin are selected from hydrogen atoms, hydroxyl groups, and hydroxymethyl groups. <11> A resin that is a reaction product of at least a compound represented by formula (2) and a raw material resin having a structural unit described in group (4). Formula (2) (In formula (2), R ６ , R ７ and R ８ each independently 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.) Group (4) (In group (4), R １ R each independently represents a methylene group, a methyleneoxy group, a methyleneoxymethylene group, or an oxymethylene group. ２ represents an alkyl group having 1 to 3 carbon atoms. ３ , R ４ and R ５ each independently represents 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. 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 structural units, where a is a number of 1 or more, b is a number of 0 or more, c is a number of 1 or more, and d is a number of 0 or more. R １ may be bonded to each other to form a crosslinked structure. * indicates the bonding position with another structural unit or a terminal group.) <12> A method for producing a resin, comprising reacting at least a compound represented by formula (2) with a raw material resin having a structural unit described in group (4) in the presence of a basic compound. Formula (2) (In formula (2), R ６ , R ７ and R ８ each independently 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.) Group (4) (In group (4), R １ R each independently represents a methylene group, a methyleneoxy group, a methyleneoxymethylene group, or an oxymethylene group. ２ represents an alkyl group having 1 to 3 carbon atoms. ３ , R ４ and R ５each independently represents 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. 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 structural units, where a is a number of 1 or more, b is a number of 0 or more, c is a number of 1 or more, and d is a number of 0 or more. R １ may be bonded to each other to form a crosslinked structure. * indicates the bonding position with another structural unit or a terminal group.) <13> In formula (2), R ６ is a methyl group, and R ７ and R ８ <14> The method for producing a resin according to <12>, wherein R is a hydrogen atom. ３ , R ４ and R ５ <15> The method for producing a resin according to <12> or <13>, wherein R ３ , R ４ and R ５ are each independently an alkyl group having 1 to 5 carbon atoms. <16> A method for producing a resin according to any one of <12> to <15>, wherein the hydroxyl value of the raw material resin is 100 to 600 g / mol. <17> A method for producing a resin according to any one of <12> to <16>, wherein the structural unit according to group (4) includes at least one of a structural unit according to group (4-1), a structural unit according to group (4-2), a structural unit according to group (4-3), and a structural unit according to group (4-4). Group (4-1) (In group (4-1), R １ , R ３ , R ４ , R ５ , v, x, y, z, a1, b, c and d are R in group (4), respectively. １ , R ３ , R ４ , R ５, v, x, y, z, a, b, c and d. * indicates the bonding position with other structural units or terminal groups.) Group (4-2) (In group (4-2), R １ , R ３ , R ４ , R ５ , v, x, y, z, a2, b, c and d are R in group (4), respectively. １ , R ３ , R ４ , R ５ , v, x, y, z, a, b, c and d. * indicates the bonding position with other structural units or terminal groups.) Group (4-3) (In group (4-3), R １ , R ３ , R ４ , R ５ , v, x, y, z, a3, b, c and d are R in group (4), respectively. １ , R ３ , R ４ , R ５ , v, x, y, z, a, b, c and d. * indicates the bonding position with other structural units or terminal groups.) Group (4-4) (In group (4-4), R １ , R ３ , R ４ , R ５ , v, x, y, z, a4, b, c and d are R in group (4), respectively. １ , R ３ , R ４ , R ５, v, x, y, z, a, b, c, and d are synonymous. * indicates the bonding position to another structural unit or terminal group.) <18> A method for producing the resin according to <17>, in which the structural unit described in group (4) includes a structural unit described in group (4-1) or a structural unit described in group (4-4). <19> A method for producing the resin according to any one of <12> to <18>, in which the raw material resin having the structural unit 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. <20> A method for producing the resin according to any one of <12> to <19>, in which the end group of the raw material resin having the structural unit described in group (4) is selected from a hydrogen atom, a hydroxyl group, and a hydroxymethyl group. <21> A method for producing the resin according to any one of <12> to <20>, in which the basic compound includes at least one of potassium carbonate, rubidium carbonate, and cesium carbonate. <22> The method for producing a resin according to any one of <12> to <21>, wherein the produced resin is a resin according to any one of <1> to <11>. <23> A curable resin composition comprising the resin according to any one of <1> to <11>. <24> The curable resin composition according to <23>, further comprising a thermosetting compound other than the resin according to any one of <1> to <11>. <25> The curable resin composition according to <23> or <24>, wherein the thermosetting compound comprises at least one selected from a compound having a carbon-carbon unsaturated bond group other than the resin according to any one of <1> to <11> and an epoxy resin. <26> A cured product of the curable resin composition according to any one of <23> to <25>.

[0006] The present invention makes it possible to provide a novel resin having excellent dielectric properties, a method for producing the resin, a curable resin composition, and a cured product.

[0007] Hereinafter, a detailed description of an embodiment of the present invention (hereinafter simply referred to as "the present embodiment") will be given. Note that the following present embodiment is an example for explaining the present invention, and the present invention is not limited to this embodiment. In this specification, the term "to" is used to mean that the numerical values ​​before and after it are included as lower and upper limits. In this specification, various physical property values ​​and characteristic values ​​are those at 23°C unless otherwise specified. In the description of groups (atomic groups) in this specification, a notation that does not indicate substituted or unsubstituted includes both groups (atomic groups) that have no substituents and groups (atomic groups) that have substituents. For example, "alkyl group" includes not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups). In this specification, when a notation that does not indicate substituted or unsubstituted is used, unsubstituted is preferred. If the measurement method, etc., of the specifications shown in this specification differ depending on the year, they will be based on the specifications as of January 1, 2021, unless otherwise specified.

[0008] The resin of this embodiment has the structural units described in group (1). A cured product of such a resin has excellent dielectric properties. Furthermore, a resin with excellent heat resistance can be obtained. In particular, by including the third structural unit from the left in group (1) as a structural unit containing a vinyl group, it becomes possible to produce the resin industrially at lower cost. Furthermore, when purifying the resin after synthesis, it can be purified with water, which is industrially advantageous. Group (1) (In group (1), R １ R each independently represents a methylene group, a methyleneoxy group, a methyleneoxymethylene group, or an oxymethylene group. ２ represents an alkyl group having 1 to 3 carbon atoms. ３ , R ４ and R ５ R each independently represents 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. ６ , R ７ and R ８R each independently 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. 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. 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 structural unit, a is a number of 1 or more, b is a number of 0 or more, c is a number of 1 or more, and d is a number of 0 or more. R １ may be bonded to each other to form a crosslinked structure. * indicates the bonding position with other structural units or terminal groups.)

[0009] In group (1), R １ R each independently represents a methylene group, a methyleneoxy group, a methyleneoxymethylene group, or an oxymethylene group, preferably a methylene group or a methyleneoxymethylene group, and more preferably a methylene group. １ may be bonded to each other to form a crosslinked structure. １ Examples of the crosslinked structure include the following structures: R １ Preferably, n does not form a crosslinked structure. n is a number of 1 or more, and is usually a number of 1 to 10.

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

[0011] R ３ , R ４ and R ５ R 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, and each independently is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.３ ~R ５ The halogen atom as R is preferably a fluorine atom or a chlorine atom. ３ ~R ５ The alkyl group having 1 to 10 carbon atoms as R is more preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, an i-propyl group, an n-propyl group, an n-butyl group, or a t-butyl group, and even more preferably a t-butyl group. ３ ~R ５ The halogenated alkyl group having 1 to 10 carbon atoms as R is more preferably an alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom or a chlorine atom, and even more preferably a fluoromethyl group, a chloromethyl group, a fluoroethyl group, or a chloroethyl group. ３ ~R ５ The hydroxyalkyl group having 1 to 10 carbon atoms as R is more preferably a hydroxyalkyl group having 1 to 5 carbon atoms, and even more preferably a hydroxymethyl group or a hydroxyethyl group. ３ ~R ５ The aryl group having 6 to 12 carbon atoms as the aryl group is preferably a phenyl group.

[0012] R ６ , R ７ and R ８ each independently 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, and each independently preferably represents a hydrogen atom, a halogen atom (preferably a chlorine atom or a fluorine atom), or a methyl group. More preferably, R ６ is a methyl group, and R ７ and R ８ is a hydrogen atom.

[0013] R ９represent 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, and are each independently 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 more preferably a methyl group or a phenyl group.

[0014] v represents 0 or 1, and may include both a structural unit where v is 0 and a structural unit where v is 1, and preferably includes at least a structural unit where v is 0. Also included are embodiments that include at least a structural unit where v is 1. w represents a number from 1 to 3, preferably 2 or more, and preferably 3 or less. x, y, and z each independently represent a number from 0 to 3, preferably 1 or more, and preferably 2 or less, and more preferably 1.

[0015] In group (1), R １ is a methylene group, R ２ is a methyl group, R ３ ~R ５ are each independently a t-butyl group, and R ６ is a methyl group, and R ７ and R ８ is a hydrogen atom, and R ９ is a methyl group or a phenyl group, w is 2 or 3, x is 1 or 2, and y and z are each 1 or 2.

[0016] a, b, c, and d each independently represent the molar ratio of the structural 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. The molar ratio of b:a is preferably 1:0.8 or greater, and more preferably 1:3.5 or greater. There is no particular upper limit to the molar ratio of b:a, but ideally b is 0, and it may be 1:100 or less. The molar ratio of (c + d):a is preferably 1:0.05 to 1:7, and more preferably 1:0.4 to 1:3. Furthermore, the molar ratio of b:(c + d) is preferably 1:1.5 or greater, and more preferably 1:3 or greater. There is no particular upper limit to the molar ratio of b:(c + d), but it may be 1:100 or less. The molar ratio of d:c is preferably 1:0.25 or greater, and more preferably 1:0.67 or greater. There is no particular upper limit to the molar ratio of d:c, but ideally d is 0, and it may be 1:100 or less. When all structural units in this embodiment are taken as 100, the sum of a, b, c, and d is preferably 90 or more, more preferably 95 or more, in terms of molar ratio, and even more preferably all structural units excluding terminal groups are 100.

[0017] The structural units described in group (1) preferably include at least one of the structural units described in group (1-1), the structural units described in group (1-2), the structural units described in group (1-3), and the structural units described in group (1-4), and more preferably include at least the structural units described in group (1-1) or the structural units described in group (1-4). As described below, the resin of this embodiment is preferably a reaction product of at least a compound represented by formula (2) with a raw resin having a structural unit described in group (4). Furthermore, the resin of this embodiment may be a reaction product of at least one of a compound represented by formula (2) and a compound represented by formula (3) with a raw resin having a structural unit described in group (4). Representative examples of raw resins having a structural unit described in group (4) include xylene resin, which is an inexpensive resin that can be synthesized from xylene and formaldehyde, and mesitylene resin, which is an inexpensive resin synthesized from mesitylene and formaldehyde. When these raw resins are used to obtain the resin of this embodiment, a resin containing at least one of the structural units described in group (1-1), the structural units described in group (1-2), the structural units described in group (1-3), and the structural units described in group (1-4) is obtained. In particular, when a xylene resin is used, a resin containing the structural units described in group (1-1) is preferentially obtained. Furthermore, when a mesitylene resin is used, a resin containing the structural units described in group (1-4) is preferentially obtained. The resin of this embodiment can be made into a resin containing at least one of the structural units described in group (1-4) (e.g., mesitylene resin), thereby increasing the curing initiation temperature of the resin. That is, by using a resin containing at least one of the structural units described in group (1-1), the structural units described in group (1-2), the structural units described in group (1-3), and the structural units described in group (1-4), the resin of this embodiment can be made into an industrially inexpensive, easy-to-produce, and immediately feasible resin.

[0018] Group (1-1) (In group (1-1), R １ , R ３ , R ４ , R ５ , R ６ , R７ , R ８ , R ９ , v, x, y, z, a1, b, c and d are R in group (1), respectively. １ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , v, x, y, z, a, b, c and d. * indicates the bonding position with other structural units or terminal groups.) Group (1-2) (In group (1-2), R １ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , v, x, y, z, a2, b, c and d are R in group (1), respectively. １ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , v, x, y, z, a, b, c and d. * indicates the bonding position with other structural units or terminal groups.) Group (1-3) (In group (1-3), R １ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , v, x, y, z, a3, b, c and d are R in group (1), respectively. １ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , v, x, y, z, a, b, c and d. * indicates the bonding position with other structural units or terminal groups.) Group (1-4) (In group (1-4), R １ , R３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , v, x, y, z, a4, b, c and d are R in group (1), respectively. １ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , v, x, y, z, a, b, c, and d. * indicates the bonding position with other structural units or terminal groups.)

[0019] The resin of the present embodiment may contain only one type of each structural unit in group (1), or may contain two or more types. When two or more types are contained, the total amount falls within the above range.

[0020] The resin of this embodiment may contain a structural unit other than the structural units represented in group (1). Furthermore, in the resin of this embodiment, the structural units represented in group (1) may be randomly polymerized or block polymerized.

[0021] In group (1), * indicates the bonding position with another structural unit or terminal group. The terminal group is preferably selected from a hydrogen atom, a hydroxyl group, and a hydroxymethyl group, more preferably a hydrogen atom or a hydroxyl group, and even more preferably a hydrogen atom.

[0022] The resin of this embodiment preferably has a phenolic hydroxyl group content of 0.5 mmol / g or less, more preferably 0.3 mmol / g or less, even more preferably 0.2 mmol / g or less, even more preferably 0.1 mmol / g or less, and even more preferably 0.05 mmol / g or less. By setting the content below the upper limit, a resin with even better low dielectric properties can be obtained. The lower limit of the phenolic hydroxyl group content is preferably 0 mmol / g, but it is practical to set it to more than 0 mmol / g.

[0023] Furthermore, in the resin of this embodiment, the content of the group represented by the following in group (1) 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 making it equal to or greater than the above lower limit, a resin with better curability can be obtained. Furthermore, a resin with better heat resistance and dielectric properties tends to be obtained. The upper limit is not particularly limited, but can be, for example, 5.0 mmol / g or less. (R in the above group ６ ~R ８ is R in group (1). ６ ~R ８ is synonymous with

[0024] In the resin of this embodiment, the weight-average molecular weight (Mw) is preferably 500 or more, more preferably 1,000 or more, even more preferably 3,000 or more, even more preferably 4,000 or more, and even more preferably 7,000 or more. By setting the weight-average molecular weight at or above the lower limit, the toughness and flexibility of the resin are improved, and cracking during molding and the occurrence of cracks in the molded product can be more effectively suppressed. Furthermore, in the resin of this embodiment, the weight-average molecular weight (Mw) is preferably 30,000 or less, more preferably 20,000 or less, even more preferably 18,000 or less, even more preferably 16,000 or less, and may even be 15,000 or less. Setting the weight-average molecular weight at or below the upper limit tends to improve the solvent solubility of the resin and reduce the melt viscosity of the resin, thereby further improving the handleability of the resin.

[0025] In the resin of this embodiment, the number average molecular weight (Mn) is preferably 500 or more, more preferably 800 or more, even more preferably 1,000 or more, even more preferably 1,200 or more, and even more preferably 1,700 or more. By setting the Mn at or above the lower limit, the toughness and flexibility of the resin are improved, and cracking during molding and the occurrence of cracks in the molded product can be more effectively suppressed. Furthermore, in the resin of this embodiment, the number average molecular weight (Mn) is preferably 10,000 or less, more preferably 8,000 or less, even more preferably 7,000 or less, even more preferably 6,000 or less, and may even be 4,500 or less. Setting the Mn at or below the upper limit tends to improve the solvent solubility of the resin and reduce the melt viscosity of the resin, thereby further improving the handleability of the resin. The weight average molecular weight and number average molecular weight are measured according to the method described in the Examples below.

[0026] The method for producing a resin according to the present embodiment is characterized by comprising reacting at least a compound represented by formula (2) with a raw resin having a structural unit described in group (4) in the presence of a basic compound. By producing the resin in this manner, a resin having excellent dielectric properties can be obtained. Furthermore, a resin having excellent heat resistance can be obtained. Furthermore, a compound represented by formula (3) may also be reacted. Formula (2) (In formula (2), R ６ , R ７ and R ８ each independently 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.) Group (4) (In group (4), R １ R each independently represents a methylene group, a methyleneoxy group, a methyleneoxymethylene group, or an oxymethylene group. ２ represents an alkyl group having 1 to 3 carbon atoms. ３ , R ４ and R ５each independently represents 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. 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 structural units, where a is a number of 1 or more, b is a number of 0 or more, c is a number of 1 or more, and d is a number of 0 or more. R １ may be bonded to each other to form a crosslinked structure. * indicates the bonding position with other structural units or terminal groups.)

[0027] Formula (3) (In formula (3), 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.

[0028] First, the details of group (4) will be described. In group (4), R １ , R ２ , R ３ , R ４ , R ５ , v, w, x, y, z, a, b, c and d are R in group (1), respectively. １ , R ２ , R ３ , v, w, x, y, z, a, b and c have the same meanings and preferred ranges. The terminal groups in group (4) are the same as the terminal groups in group (1).

[0029] Furthermore, the structural units described in group (4) preferably include at least one of the structural units described in group (4-1), the structural units described in group (4-2), the structural units described in group (4-3), and the structural units described in group (4-4), and more preferably include a structural unit described in group (4-1) or group (4-4). By using a raw material resin containing at least one of the structural units described in group (4-1), the structural units described in group (4-2), the structural units described in group (4-3), and the structural units described in group (4-4), it becomes possible to produce a resin having a structural unit described in group (1) more inexpensively. Group (4-1) (In group (4-1), R １ , R ３ , R ４ , R ５ , v, x, y, z, a1, b, c and d are R in group (4), respectively. １ , R ３ , R ４ , R ５ , v, x, y, z, a, b, c and d. * indicates the bonding position with other structural units or terminal groups.) Group (4-2) (In group (4-2), R １ , R ３ , R ４ , R ５ , v, x, y, z, a2, b, c and d are R in group (4), respectively. １ , R ３ , R ４ , R ５ , v, x, y, z, a, b, c and d. * indicates the bonding position with other structural units or terminal groups.) Group (4-3) (In group (4-3), R １ , R ３ , R ４ , R ５ , v, x, y, z, a3, b, c and d are R in group (4), respectively. １ , R ３ , R ４ , R ５ , v, x, y, z, a, b, c and d. * indicates the bonding position with other structural units or terminal groups.) Group (4-4) (In group (4-4), R １ , R ３ , R ４ , R ５ , v, x, y, z, a4, b, c and d are R in group (4), respectively. １ , R ３ , R ４ , R ５ , v, x, y, z, a, b, c, and d. * indicates the bonding position with other structural units or terminal groups.)

[0030] For raw resins containing structural units described in group (4), the weight-average molecular weight (Mw) is preferably 400 or more, more preferably 600 or more, even more preferably 800 or more, even more preferably 1,000 or more, even more preferably 2,000 or more, even more preferably 3,000 or more, and may even be 5,000 or more. By setting the Mw at or above the lower limit, the toughness and flexibility of the resin are improved, and cracks during molding and the occurrence of cracks in molded products can be more effectively suppressed. Furthermore, for raw resins containing structural units described in group (4), the weight-average molecular weight (Mw) is preferably 30,000 or less, more preferably 20,000 or less, even more preferably 16,000 or less, even more preferably 12,000 or less, and even more preferably 10,000 or less. Setting the Mw at or below the upper limit tends to improve the solvent solubility of the resin and reduce the melt viscosity of the resin, thereby further improving the handleability of the resin.

[0031] For raw resins containing structural units described in group (4), the number-average molecular weight (Mn) is preferably 400 or more, more preferably 600 or more, even more preferably 800 or more, and may be 1,000 or more. By setting the Mn at or above the lower limit, the toughness and flexibility of the resin are improved, and cracks during molding and the occurrence of cracks in molded products can be more effectively suppressed. Furthermore, for raw resins containing structural units described in group (4), the number-average molecular weight (Mn) is preferably 5,000 or less, more preferably 4,000 or less, even more preferably 3,500 or less, and even more preferably 2,500 or less. Setting the Mn at or below the upper limit tends to improve the solvent solubility of the resin and reduce the melt viscosity of the resin, thereby further improving the handleability of the resin. The weight-average molecular weight and number-average molecular weight are measured according to the method described in the Examples below.

[0032] The raw resin having the structural unit described in group (4) preferably has a hydroxyl value of 100 g / mol or more, more preferably 130 g / mol or more, even more preferably 160 g / mol or more, even more preferably 190 g / mol or more, and even more preferably 210 g / mol or more. By setting the hydroxyl value at or above the lower limit, the amount of hydroxyl groups reacting with the compound represented by formula (2) does not increase more than necessary, and the dielectric properties tend to be further improved. The raw resin having the structural unit described in group (4) also preferably has a hydroxyl value of 600 g / mol or less, more preferably 550 g / mol or less, even more preferably 500 g / mol or less, even more preferably 450 g / mol or less, even more preferably 400 g / mol or less, and may even be 360 ​​g / mol or less. By setting the hydroxyl value at or below the upper limit, a resin with excellent heat resistance and excellent dielectric properties tends to be obtained. That is, by introducing a structure derived from the compound represented by formula (2), the resulting resin has a high Tg, but tends to have poor dielectric properties. Therefore, it is desirable to adjust the amount of hydroxyl groups in the raw material as described above. The hydroxyl equivalent is measured as described in the Examples.

[0033] Next, the details of formula (2) will be described. (In formula (2), R ６ , R ７ and R ８ each independently 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.

[0034] In formula (2), R ６ , R ７ and R ８ are R in group (1), respectively. ６ , R ７ and R ８ The same definition and preferred range are also applicable.

[0035] In the resin production method of this embodiment, the raw material resin having the structural unit described in group (4) and the compound represented by formula (2) may each be used alone or in combination of two or more types. In the resin production method of this embodiment, the molar ratio of the phenolic hydroxyl group in the raw material resin having the structural 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 resin production method of this embodiment, at least a compound represented by formula (2) is reacted with a raw resin having a structural unit described in group (4) in the presence of a basic compound. The use of a basic compound promotes the reaction between the phenolic hydroxyl groups of the raw resin having a structural unit described in group (4) and the compound represented by formula (2). The basic compound is preferably selected from at least one of potassium carbonate, rubidium carbonate, and cesium carbonate. The use of these basic compounds as catalysts effectively promotes the reaction between the raw resin having a structural unit described in group (4) and the compound represented by formula (2), while also increasing the yield of the resulting compound. In this embodiment, of potassium carbonate, rubidium carbonate, and cesium carbonate, potassium carbonate and cesium carbonate are preferred, with potassium carbonate being more preferred. The form of potassium carbonate, rubidium carbonate, and cesium carbonate is not particularly limited, but is preferably in powder form. Furthermore, the potassium carbonate, rubidium carbonate, and cesium carbonate are preferably in the form of fine powder (average particle size of approximately 10 to 200 μm). When a powder is used, the specific surface area becomes large, and the reactivity can be increased.

[0037] In the production method of this embodiment, the basic compound is preferably used in an amount of 1.0 mole (mol / mol-OH) or more, more preferably 2.5 moles or more, and preferably 10.0 moles or less, more preferably 7.0 moles or less, per mole of hydroxyl groups in the raw resin having the structural units described in group (4). By using an amount equal to or greater than the lower limit, the reactivity of the hydroxyl groups in the raw resin having the structural units described in group (4) with the compound represented by formula (2) tends to be further improved. By using an amount equal to or less than the upper limit, the effect of reducing production costs tends to be further improved. In the production method of this embodiment, only one basic compound may be used, or two or more basic compounds may be used. When two or more basic compounds are used, the total amount preferably falls within the above range.

[0038] In the method for producing a resin according to the present embodiment, a compound represented by formula (3) may be reacted with a raw material resin having a compound represented by formula (2) and a structural unit described in group (4). By reacting the compound represented by formula (3), it reacts with the phenolic hydroxyl groups in the resin that did not react with the compound represented by formula (2), thereby lowering the hydroxyl value of the resulting resin and resulting in a resin with excellent dielectric properties. Formula (3) (In formula (3), 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.

[0039] In formula (3), R ９ is R in group (1). ９ The same applies to the preferred range.

[0040] In the production method of this embodiment, the reaction between the raw material resin having a structural unit described in group (4) and the compound represented by formula (2) is preferably carried out at 40 to 110°C, more preferably at 50 to 90°C.

[0041] In the production method of this embodiment, it is preferable to use a solvent when reacting the raw material resin having the structural unit described in group (4) with the compound represented by formula (2). The solvent can be used without any particular limitation, but an aprotic solvent is preferable, and at least one of an aromatic hydrocarbon solvent and an ether solvent is more preferable. By using an aprotic solvent, O derived from a phenolic hydroxyl group can be easily obtained. － The effect on the

[0042] In the production method of this embodiment, it is preferable to separate and purify the resin obtained after the reaction of the raw material resin having the structural units described in group (4) above with the compound represented by formula (2). Separation and purification can be performed according to a conventional method. In this embodiment, purification can be performed using water or a solvent mainly composed of water (e.g., 70% by mass or more of the solvent is water). Furthermore, after purification with water or the like, washing with alcohol (e.g., methanol) may be performed. The resin produced by the resin production method of this embodiment is preferably the resin of this embodiment described above. Therefore, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin produced by the resin production method of this embodiment are preferably in the same ranges as the weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin of this embodiment described above, respectively.

[0043] <Applications> The resin of this embodiment can be used as a curable resin composition. The curable resin composition may consist solely of one or more resins of this embodiment, or may further contain a thermosetting compound other than the resin of this embodiment. The thermosetting compound preferably includes at least one compound other than the resin of this embodiment selected from a compound having a carbon-carbon unsaturated bond group and an epoxy resin. Furthermore, the curable resin composition may contain one or more additives. Examples of additives include curing initiators, flame retardants, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, flow control agents, lubricants, antifoaming agents, dispersants, leveling agents, gloss agents, and polymerization inhibitors.

[0044] Examples of the curing initiator include di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, diisopropyl peroxydicarbonate, t-butylperoxyisopropyl carbonate, dimyristyl peroxycarbonate, 1,1,3,3-tetramethylbutyl neodecanoate, α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, and t-butylperoxy. butylperoxylaurate, t-butylperoxy-2-ethylhexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, 2,2-bis(t-butylperoxy)butene, t-butylperoxybenzoate, n-butyl-4,4-bis(t-butylperoxy)valerate, di-t-butylperoxyisophthalate, dicumyl peroxide, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3-bis(t-butylperoxydiisopropyl)benzene, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3. When the curable resin composition of this embodiment contains a curing initiator, the amount thereof is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and even more preferably 1.0 part by mass or more, relative to 100 parts by mass of the resin of this embodiment, and is preferably 10.0 parts by mass or less, more preferably 5.0 parts by mass or less, even more preferably 3.0 parts by mass or less, and even more preferably 2.0 parts by mass or less. The curable resin composition of this embodiment may contain only one type of curing initiator, or may contain two or more types.When two or more types are contained, the total amount is preferably within the above range.

[0045] The cured product of the present embodiment is obtained by curing the curable resin composition. Such a cured product has excellent heat resistance and dielectric properties, and is therefore suitable for use as an insulating layer for printed wiring boards and as a material for semiconductor packages.

[0046] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be changed as appropriate 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. If the measuring instruments used in the examples are difficult to obtain due to discontinuation or the like, measurements can be made using other instruments with equivalent performance.

[0047] <Measurement 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 by gel permeation chromatography (GPC). KF-801, KF-802, KF-803, and KF-804 manufactured by Showa Denko K.K. were used in combination as analytical columns, and a differential refractometer RID-20A manufactured by Shimadzu Corporation was used for detection. 10 mg of the resin to be measured was dissolved in 3 g of tetrahydrofuran as an eluent, and the injection amount into the column was 20 μL. Analysis was performed at an eluent flow rate of 1 mL / min and a column temperature of 40°C. A molecular weight calibration curve was created using standard polystyrene PStQuick MP-N manufactured by Tosoh Corporation, and the polystyrene-equivalent molecular weight was estimated.

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

[0049] <Hydroxyl Group Content of Resin> The phenolic hydroxyl group content of the resin was measured by proton nuclear magnetic resonance spectroscopy ( １The modification rate of phenolic hydroxyl groups was calculated by H-NMR analysis. Specifically, the peak area of ​​the protons of phenolic hydroxyl groups around 4.2 to 5.4 ppm was calculated by the following formula, where the peak area of ​​the protons of p-tert-butyl groups around 1.07 to 1.24 ppm was set to 9, and the reduction rate [%] before and after the reaction was defined as the modification rate of phenolic hydroxyl groups [%]. (Hydroxyl group content of resin [mmol / g]) = (Hydroxyl group content of raw material resin [mmol / g]) × (100 - (modification rate [%])) / 100. Instrument used: AVANCE III 500 (500 MHz), manufactured by Bruker.

[0050] <Methacrylic group content> The methacrylic group content can be determined by proton nuclear magnetic resonance spectroscopy ( １ The methacrylic group content was calculated by H-NMR analysis. Specifically, the methacrylation rate [%] was calculated by multiplying the peak area of ​​one of the methacrylic group terminal protons around 5.4 to 5.8 ppm by 100, assuming that the peak area of ​​the p-tert-butyl group protons around 1.07 to 1.24 ppm is 9. The methacrylic group content [mmol / g] was calculated based on the obtained methacrylation rate, the modification rate of phenolic hydroxyl groups, the hydroxyl group content of the raw resin, and the molecular weight of the modified substituent. In addition, the peak of the phenolic hydroxyl group of the phenol-modified xylene resin or phenol-modified mesitylene resin around 4.2 to 5.4 ppm disappeared after the reaction, confirming that the reaction had progressed completely. Equipment used: AVANCE III 500 (500 MHz) manufactured by Bruker

[0051] Synthesis Example 1 Synthesis of p-tert-butylphenol (PTBP)-modified xylene resin (1) A 0.5 L separable flask equipped with a thermometer and a stirrer was charged with 200.0 g of xylene formaldehyde resin (manufactured by Fudor 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 paratoluenesulfonic acid monohydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and the temperature was raised to 90 ° C. Further, the temperature was raised to 220 ° C. over 5 hours while dehydrating, and the reaction was allowed to proceed. Next, 0.09 g (1.50 mmol) of urea (Tokyo Chemical Industry Co., Ltd.) was added to stop the reaction, and 411.4 g of p-tert-butylphenol-modified xylene resin was obtained. The number average molecular weight, weight average molecular weight and hydroxyl value of the resulting resin were measured according to the conditions described above and are shown in Table 1.

[0052] Synthesis Example 2: Synthesis of p-tert-butylphenol (PTBP)-modified xylene resin (2) A 0.5 L separable flask equipped with a thermometer and a stirrer was charged with 250.0 g of xylene formaldehyde 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 paratoluenesulfonic acid monohydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and the temperature was raised to 115 ° C. Further, the temperature was raised to 180 ° C. over 6 hours while dehydrating, and the reaction was allowed to proceed. Next, 0.14 g (2.33 mmol) of urea (Tokyo Chemical Industry Co., Ltd.) was added to stop the reaction, and 375.2 g of p-tert-butylphenol-modified xylene resin was obtained. The number average molecular weight, weight average molecular weight and hydroxyl value of the resulting resin were measured according to the conditions described above and are shown in Table 1.

[0053] Synthesis Example 3: Synthesis of mesitylene formaldehyde resin A 1.0 L separable flask with a bottom that could be opened was charged with 621.6 g of a 37% by weight aqueous formalin solution (7.66 mol as formaldehyde, manufactured by Mitsubishi Gas Chemical Company, Inc.). While stirring, 132.9 g (1.33 mol) of 98% by weight sulfuric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 459.7 g (3.82 mol) of mesitylene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added, and the mixture was refluxed at approximately 100°C under atmospheric pressure for 4 hours. Next, 335 g of mesitylene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added as a diluent solvent. After standing, the separated upper oil phase was retained and the lower aqueous phase was removed. The oil phase was neutralized and washed with water, and unreacted raw materials were removed by distillation under reduced pressure to obtain 578.6 g of mesitylene formaldehyde resin. The number-average molecular weight and weight-average molecular weight of the resulting resin were measured according to the conditions described above and are shown in Table 1.

[0054] Synthesis Example 4 Synthesis of p-tert-butylphenol (PTBP)-modified mesitylene resin (1) A thermometer and a 0.5 L separable flask equipped with a stirrer were charged with 200.0 g of the mesitylene formaldehyde resin obtained in Synthesis Example 3, 163.1 g (1.09 mol) of p-tert-butylphenol (DIC Corporation), and 0.42 g (0.22 mmol) of paratoluenesulfonic acid monohydrate (Fujifilm Wako Pure Chemical Industries, Ltd.), and the temperature was raised to 115 ° C. Further, the temperature was raised to 200 ° C. over 1 hour while dehydrating, and the reaction was allowed to proceed. Next, 0.05 g (0.83 mmol) of urea (Tokyo Chemical Industry Co., Ltd.) was added to stop the reaction, and 346.1 g of p-tert-butylphenol-modified mesitylene resin was obtained. The number average molecular weight, weight average molecular weight and hydroxyl value of the resulting resin were measured according to the conditions described above and are shown in Table 1.

[0055] Synthesis Example 5 Synthesis of p-tert-butylphenol (PTBP)-modified mesitylene resin (2)> A 0.5-liter separable flask equipped with a thermometer and a stirrer was charged with 100.3 g of the mesitylene formaldehyde resin obtained in Synthesis Example 3, 134.1 g (0.89 mol) of p-tert-butylphenol (DIC Corporation), 9.32 g of 92% paraformaldehyde (Mitsubishi Gas Chemical Company, Inc.), and 0.28 g (0.15 mmol) of paratoluenesulfonic acid monohydrate (Fujifilm Wako Pure Chemical Industries, Ltd.), and the temperature was raised to 90 ° C. Further, the temperature was raised to 220 ° C. over 5 hours while dehydrating, and the reaction was allowed to proceed. Next, 0.04 g (0.67 mmol) of urea (Tokyo Chemical Industry Co., Ltd.) was added to stop the reaction, and 251.6 g of p-tert-butylphenol-modified mesitylene resin was obtained. The number average molecular weight, weight average molecular weight and hydroxyl value of the resulting resin were measured according to the conditions described above and are shown in Table 1.

[0056]

[0057] Example 1: A 300 mL four-neck flask equipped with a stirrer, thermometer, and reflux condenser was charged with 22.0 g (96.2 mmol in terms of the number of moles of hydroxyl groups) of the p-tert-butylphenol-modified xylene resin obtained in Synthesis Example 1, 190 g of tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 66.5 g (481 mmol) of potassium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., average particle size 150 μm or less), and 11.2 g (72.7 mmol) of methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) under a nitrogen atmosphere, and the mixture was allowed to react at 70°C for 24 hours. Further, 18.1 g (177 mmol) of acetic anhydride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added, and the mixture was allowed to react at 70°C for 24 hours. The reaction solution was air-cooled and then filtered through a 0.45 μm filter. The resulting solution was solidified by adding it dropwise to purified water. The solidified product was recovered and washed with purified water and then with methanol. The resulting solid was washed again with purified water and methanol, and then dried under reduced pressure to obtain 23.1 g of the desired methacrylic compound. The number-average molecular weight, weight-average molecular weight, and methacrylic group content of the resulting methacrylic compound were measured according to the conditions described above, and the results are shown in Table 2. A cured product was produced according to the following method. The dielectric properties, glass transition temperature, and 5% weight loss temperature of the resulting cured product were also measured, and the results are shown in Table 2.

[0058] <Preparation of Cured Product> A cured product was prepared by adding 1.5 parts by mass of Perbutyl (registered trademark) P (manufactured by NOF Corporation) to the methacrylic compound obtained above, placing the mixture in a mold 100 mm long and 30 mm wide, and vacuum hot pressing it at 200°C for 1.5 hours under a pressure of 1.92 MPa. Equipment used: 5-stage press VH2-1630 manufactured by Kitagawa Seiki Co., Ltd.

[0059] <Measurement of Dielectric Properties of Cured Product> The obtained cured product was cut into a piece having a thickness of 1 mm, a width of 0.8 mm, and a length of 100 mm, and the dielectric constant and dielectric loss tangent of the cured product were measured at 10 GHz by a cavity resonance perturbation method after drying at 120°C for 1 hour. Equipment used: Agilent 8722ES Network Analyzer

[0060] <Measurement of Glass Transition Temperature of Cured Product> The glass transition temperature of the cured product was determined by cutting the obtained cured product into a piece 5 mm wide and 40 mm long, subjecting the cut piece to dynamic viscoelasticity measurement, and taking the peak temperature of the dynamic modulus of elasticity obtained. The unit is °C. Equipment used: DMA7100 manufactured by Hitachi High-Tech Science Corporation Heating rate: 5°C / min Frequency: sine wave, 10 Hz

[0061] <Measurement of 5% weight loss temperature of cured product> The 5% weight loss temperature of the cured product was determined by cutting the obtained cured product into approximately 10 mg pieces, simultaneously measuring thermogravimetry and differential thermal analysis, and determining the temperature at which the weight decreased by 5%. The unit was expressed in °C. Equipment used: STA7200 manufactured by Hitachi High-Tech Science Corporation. Heating rate: 10°C / min.

[0062] Example 2 The reaction and purification were carried out in the same manner as in Example 1, except that the amount of potassium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., average particle size 150 μm or less) charged was changed to 66.4 g (480 mmol), the amount of methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) charged was changed to 12.4 g (80.5 mmol), and the amount of acetic anhydride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) charged was changed to 14.9 g (146 mmol), yielding 21.6 g of the target methacrylic compound. The number-average molecular weight, weight-average molecular weight, and methacrylation rate of the resulting methacrylic compound were measured according to the conditions described above and are shown in Table 2. The dielectric properties, glass transition temperature, and 5% weight loss temperature of the cured product prepared in the same manner as in Example 1 were measured and are shown in Table 2.

[0063] Example 3 In Example 1, the amount of p-tert-butylphenol-modified xylene resin charged was changed to 22.1 g (96.3 mmol in terms of the number of moles of hydroxyl groups), the amount of tetrahydrofuran (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) charged was changed to 191 g, the amount of potassium carbonate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., average particle size 150 μm or less) charged was changed to 66.6 g (482 mmol), the amount of methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) charged was changed to 12.3 g (79.7 mmol), and the amount of acetic anhydride (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) charged was changed to 15.3 g (150 mmol). Except for this, the reaction and purification were carried out in the same manner as in Example 1, and 23.8 g of the target methacrylic compound was obtained. The number average molecular weight, weight average molecular weight, and methacrylation rate of the obtained methacrylic compound were measured according to the conditions described above and are shown in Table 2. The dielectric properties, glass transition temperature, and 5% weight loss temperature of the cured product prepared in the same manner as in Example 1 were measured and are shown in Table 2.

[0064] Example 4 The reaction and purification were carried out in the same manner as in Example 1, except that the amount of potassium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., average particle size 150 μm or less) charged was changed to 66.5 g (481 mmol), the amount of methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) charged was changed to 13.7 g (88.8 mmol), and the amount of acetic anhydride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) charged was changed to 11.8 g (115 mmol), yielding 23.9 g of the target methacrylic compound. The number-average molecular weight, weight-average molecular weight, and methacrylation rate of the resulting methacrylic compound were measured according to the conditions described above and are shown in Table 2. The dielectric properties, glass transition temperature, and 5% weight loss temperature of the cured product prepared in the same manner as in Example 1 were measured and are shown in Table 2.

[0065] Example 5 In Example 1, the p-tert-butylphenol-modified xylene resin obtained in Synthesis Example 1 was replaced with 22.6 g (66.4 mmol in terms of the number of moles of hydroxyl groups) of the p-tert-butylphenol-modified xylene resin obtained in Synthesis Example 2, the amount of tetrahydrofuran (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was changed to 200 g, the amount of potassium carbonate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., average particle size 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 Wako Pure Chemical Industries, Ltd.) was changed to 8.1 g (79.5 mmol), and the reaction and purification were carried out in the same manner as in Example 1, yielding 20.7 g of the target methacrylic compound. The number average molecular weight, weight average molecular weight, and methacrylation rate of the resulting methacrylic compound were measured according to the conditions described above, and the results are shown in Table 2. The dielectric properties and 5% weight loss temperature of the cured product prepared in the same manner as in Example 1 were measured, and the results are shown in Table 2.

[0066] Example 6 In Example 1, the amount of p-tert-butylphenol-modified xylene resin charged was changed to 17.1 g (74.5 mmol in terms of the number of moles of hydroxyl groups), the amount of tetrahydrofuran (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) charged was changed to 223 g, the amount of potassium carbonate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., average particle size 150 μm or less) charged was changed to 60.4 g (437 mmol), the amount of methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) charged was changed to 10.4 g (67.3 mmol), and 26.7 g (118 mmol) of benzoic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of acetic anhydride (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) Reaction and purification were carried out in the same manner as in Example 1, and 21.4 g of the target methacrylic compound was obtained. The number average molecular weight, weight average molecular weight, and methacrylation rate of the resulting methacrylic compound were measured according to the conditions described above, and the results are shown in Table 3. The dielectric properties, glass transition temperature, and 5% weight loss temperature of the cured product prepared in the same manner as in Example 1 were measured, and the results are shown in Table 3.

[0067] Example 7 In Example 1, the p-tert-butylphenol-modified xylene resin obtained in Synthesis Example 1 was replaced with 22.2 g (70.5 mmol in terms of the number of moles of hydroxyl groups) of the p-tert-butylphenol-modified mesitylene resin obtained in Synthesis Example 4, the amount of tetrahydrofuran (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was changed to 200 g, the amount of potassium carbonate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., average particle size 150 μm or less) 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 Wako Pure Chemical Industries, Ltd.) was changed to 5.77 g (56.5 mmol), and the reaction and purification were carried out in the same manner as in Example 1, yielding 24.4 g of the target methacrylic compound. The number average molecular weight, weight average molecular weight, and methacrylation rate of the resulting methacrylic compound were measured according to the conditions described above, and the results are shown in Table 3. The dielectric properties, glass transition temperature, and 5% weight loss temperature of the cured product prepared in the same manner as in Example 1 were measured, and the results are shown in Table 3.

[0068] Example 8 In Example 1, the p-tert-butylphenol-modified xylene resin obtained in Synthesis Example 1 was replaced with 15.0 g (59.8 mmol in terms of the number of moles of hydroxyl groups) of the p-tert-butylphenol-modified mesitylene resin obtained in Synthesis Example 5, the amount of tetrahydrofuran (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was changed to 136 g, the amount of potassium carbonate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., average particle size 150 μm or less) 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 Wako Pure Chemical Industries, Ltd.) was changed to 4.88 g (47.8 mmol), and the reaction and purification were carried out in the same manner as in Example 1, yielding 16.6 g of the target methacrylic compound. The number average molecular weight, weight average molecular weight, and methacrylation rate of the resulting methacrylic compound were measured according to the conditions described above, and the results are shown in Table 3. The dielectric properties, glass transition temperature, and 5% weight loss temperature of the cured product prepared in the same manner as in Example 1 were measured, and the results are shown in Table 3.

[0069] Reference Example 1 A mixture of SA9000 (manufactured by SABIC), a common polyphenylene ether terminated with methacrylic groups, and 1.5 parts by mass of Perbutyl (registered trademark) P (manufactured by NOF Corporation) was added, and a cured product was prepared in the same manner as in Example 1. The dielectric properties, glass transition temperature, and 5% weight loss temperature of the obtained cured product were measured, and the results are shown in Table 3.

[0070]

[0071]

Claims

1. A resin having a structural unit described in group (1). Group (1) 【Chemistry 1】 (In group (1), R １ R each independently represents a methylene group, a methyleneoxy group, a methyleneoxymethylene group, or an oxymethylene group. ２ represents an alkyl group having 1 to 3 carbon atoms. ３ , R ４ and R ５ R each independently represents 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. ６ , R ７ and R ８ R each independently 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. 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. 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 a molar ratio of a structural unit, where a is a number of 1 or more, b is a number of 0 or more, c is a number of 1 or more, and d is a number of 0 or more. １ may be bonded to each other to form a crosslinked structure. * indicates the bonding position with other structural units or terminal groups.)

2. In group (1), R ６ is a methyl group, R ７ and R ８ The resin according to claim 1 , wherein is a hydrogen atom.

3. In group (1), R ３ , R ４ and R ５ are each independently an alkyl group having 1 to 10 carbon atoms.

4. In group (1), R ３ , R ４ and R ５ are each independently an alkyl group having 1 to 5 carbon atoms.

5. The resin according to claim 1 or 2, wherein the resin has a phenolic hydroxyl group content of 0.5 mmol / g or less.

6. The resin according to claim 1 or 2, wherein the content of the group represented by the following formula in the resin group (1) is 1.0 mmol / g or more. 【Chemistry 2】 (R in the above group ６ ~R ８ is R in group (1). ６ ~R ８ (Same meaning as above.)

7. The resin according to claim 1 or 2, wherein the structural unit described in group (1) includes at least one of the structural units described in group (1-1), the structural units described in group (1-2), the structural units described in group (1-3), and the structural units described in group (1-4). Group (1-1) 【Chemistry 3】 (In group (1-1), R １ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , v, x, y, z, a1, b, c and d are R in group (1), respectively. １ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , v, x, y, z, a, b, c and d are synonymous. * indicates the bonding position with other structural units or terminal groups.) Group (1-2) 【Chemistry 4】 (In group (1-2), R １ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , v, x, y, z, a2, b, c and d are R in group (1), respectively. １ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , v, x, y, z, a, b, c and d are synonymous. * indicates the bonding position with other structural units or terminal groups.) Group (1-3) 【Chemistry 5】 (In group (1-3), R １ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , v, x, y, z, a3, b, c and d are R in group (1), respectively. １ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , v, x, y, z, a, b, c and d are synonymous. * indicates the bonding position with other structural units or terminal groups.) Group (1-4) 【Chemistry 6】 (In group (1-4), R １ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , v, x, y, z, a4, b, c and d are R in group (1), respectively. １ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , v, x, y, z, a, b, c and d are synonymous. * indicates the bonding position with other structural units or terminal groups.)

8. The resin according to claim 7, wherein the structural unit described in group (1) comprises a structural unit described in group (1-1) or a structural unit described in group (1-4).

9. The resin according to claim 1 or 2, having a number average molecular weight (Mn) of 500 to 6,000 and a weight average molecular weight (Mw) of 500 to 15,000.

10. 3. The resin according to claim 1, wherein the end groups of the resin are selected from hydrogen atoms, hydroxyl groups and hydroxymethyl groups.

11. A resin which is a reaction product of at least a compound represented by formula (2) with a raw material resin having a structural unit described in group (4). Formula (2) 【Chemistry 7】 (In formula (2), R ６ , R ７ and R ８ each independently 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. Group (4) 【Chemistry 8】 (In group (4), R １ R each independently represents a methylene group, a methyleneoxy group, a methyleneoxymethylene group, or an oxymethylene group. ２ represents an alkyl group having 1 to 3 carbon atoms. ３ , R ４ and R ５ each independently represents 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, 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 a molar ratio of a structural unit, where a is a number of 1 or more, b is a number of 0 or more, c is a number of 1 or more, and d is a number of 0 or more. １ may be bonded to each other to form a crosslinked structure. * indicates the bonding position with other structural units or terminal groups.)

12. A method for producing a resin, comprising reacting at least a compound represented by formula (2) with a raw material resin having a structural unit described in group (4) in the presence of a basic compound. Formula (2) 【Chemistry 9】 (In formula (2), R ６ , R ７ and R ８ each independently 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. Group (4) 【Chemistry 10】 (In group (4), R １ R each independently represents a methylene group, a methyleneoxy group, a methyleneoxymethylene group, or an oxymethylene group. ２ represents an alkyl group having 1 to 3 carbon atoms. ３ , R ４ and R ５ each independently represents 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, 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 a molar ratio of a structural unit, where a is a number of 1 or more, b is a number of 0 or more, c is a number of 1 or more, and d is a number of 0 or more. １ may be bonded to each other to form a crosslinked structure. * indicates the bonding position with other structural units or terminal groups.)

13. In formula (2), R ６ is a methyl group, R ７ and R ８ The method for producing a resin according to claim 12, wherein is a hydrogen atom.

14. In group (4), R ３ , R ４ and R ５ The method for producing a resin according to claim 12 or 13, wherein each of the is independently an alkyl group having 1 to 10 carbon atoms.

15. In group (4), R ３ , R ４ and R ５ The method for producing a resin according to claim 12 or 13, wherein each of the is independently an alkyl group having 1 to 5 carbon atoms.

16. The method for producing a resin according to claim 12 or 13, wherein the raw material resin has a hydroxyl value of 100 to 600 g / mol.

17. The structural unit described in group (4) includes at least one of the structural units described in group (4-1), the structural unit described in group (4-2), the structural unit described in group (4-3), and the structural unit described in group (4-4). The method for producing a resin according to claim 12 or 13. Group (4-1) 【Chemistry 11】 (In group (4-1), R １ , R ３ , R ４ , R ５ , v, x, y, z, a1, b, c and d are R in group (4), respectively. １ , R ３ , R ４ , R ５ , v, x, y, z, a, b, c and d are synonymous. * indicates the bonding position with other structural units or terminal groups.) Group (4-2) 【Chemistry 12】 (In group (4-2), R １ , R ３ , R ４ , R ５ , v, x, y, z, a2, b, c and d are R in group (4), １ , R ３ , R ４ , R ５ , v, x, y, z, a, b, c and d are synonymous. * indicates the bonding position with other structural units or terminal groups.) Group (4-3) 【Chemistry 13】 (In group (4-3), R １ , R ３ , R ４ , R ５ , v, x, y, z, a3, b, c and d are R in group (4), １ , R ３ , R ４ , R ５ , v, x, y, z, a, b, c and d are synonymous. * indicates the bonding position with other structural units or terminal groups.) Group (4-4) 【Chemistry 14】 (In group (4-4), R １ , R ３ , R ４ , R ５ , v, x, y, z, a4, b, c and d are R in group (4), respectively. １ , R ３ , R ４ , R ５ , v, x, y, z, a, b, c and d are synonymous. * indicates the bonding position with other structural units or terminal groups.)

18. The method for producing a resin according to claim 17, wherein the structural unit described in group (4) includes a structural unit described in group (4-1) or a structural unit described in group (4-4).

19. The method for producing a resin according to claim 12 or 13, wherein the raw material resin having the structural 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.

20. The method for producing a resin according to claim 12 or 13, wherein the end group of the raw material resin having the structural unit described in group (4) is selected from a hydrogen atom, a hydroxyl group, and a hydroxymethyl group.

21. The method for producing a resin according to claim 12 or 13, wherein the basic compound includes at least one of potassium carbonate, rubidium carbonate, and cesium carbonate.

22. The method for producing a resin according to claim 12, wherein the produced resin is the resin according to claim 1.

23. A curable resin composition comprising the resin of claim 1, 2 or 11.

24. The curable resin composition according to claim 23, further comprising a thermosetting compound other than the resin according to claim 1.

25. The curable resin composition according to claim 23, wherein the thermosetting compound comprises at least one selected from a compound having a carbon-carbon unsaturated bond group other than the resin according to claim 1 and an epoxy resin.

26. A cured product of the curable resin composition according to claim 23.

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