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

Abstract

This invention provides novel resins with excellent dielectric properties, methods for manufacturing the resins, curable resin compositions, and cured products. A resin having the structural units described in group (1). R 1 Each can independently represent methylene, methyleneoxy, methyleneoxymethylene, or oxymethylene. R 2 and R 3 Each can independently represent a halogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl 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. R 4 R 5 and R 6 Each can 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.

Description

Technical Field

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

[0002] Vinyl compounds and other resins possess excellent dielectric properties, heat resistance, and low moisture absorption, making them suitable for use as materials in electronic devices that process high-frequency signals. Such vinyl compounds and methods for their manufacture are known, for example, in Patent Document 1 and Patent Document 2.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2015-189925

[0006] Patent Document 2: Japanese Patent Application Publication No. 01-108212 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] Moreover, with the technological innovations of recent years, there is a need for novel vinyl resins with excellent dielectric properties and their manufacturing methods.

[0009] The purpose of this invention is to solve the above-mentioned problems 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.

[0010] Solution for solving the problem

[0011] Based on the above-mentioned issues, the inventors conducted research and found that the above-mentioned issues can be solved by obtaining a resin with a specified structure.

[0012] Specifically, the above-mentioned problems were solved through the following methods.

[0013] <1> A resin having the structural units described in group (1).

[0014] Group (1)

[0015]

[0016] (In group (1), R) 1 Each can independently represent methylene, methyleneoxy, methyleneoxymethylene, or oxymethylene. R 2 and R 3Each can independently represent a halogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl 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. R 4 R 5 and R 6 Each of the following independently represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, a haloalkyl 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. x represents 0 or 1, and y and z independently represent numbers from 0 to 3. a, b, and c independently represent the molar ratio of the structural units, where a is a number greater than 1, b is a number greater than 0, and c is a number greater than 1. R 1 They can be arbitrarily bonded to each other to form a cross-linked structure. * indicates the bonding site with other structural units or end groups.

[0017] <2> according to <1> The resin, wherein, in group (1), R 4 R 5 and R 6 Each is an independent hydrogen atom.

[0018] <3> according to <1> or <2> The resin, wherein, in group (1), R 2 and R 3 Each is an alkyl group having 1 to 10 carbon atoms.

[0019] <4> according to <1> or <2> The resin, wherein, in group (1), R 2 and R 3 Each is an alkyl group having 1 to 5 carbon atoms.

[0020] <5> according to <1> ~ <4> The resin in any one of the following examples, wherein, in group (1), 0.2 ≤ a / (b+c) ≤ 5.

[0021] <6> according to <1> ~ <5> The resin of any one of the following groups, wherein the structural unit of group (1) contains at least one of the structural units of group (1-1), group (1-2), and group (1-3).

[0022] Group (1-1)

[0023]

[0024] In group (1-1), R 1 R 2 R 3 R 4 R 5 R 6x, y, z, a1, b and c are respectively related to R in group (1) 1 R 2 R 3 R 4 R 5 R 6 x, y, z, a, b, and c are synonyms. * indicates a bonding site with other structural units or end groups.

[0025] Group (1-2)

[0026]

[0027] (In group (1-2), R) 1 R 2 R 3 R 4 R 5 R 6 x, y, z, a2, b and c are respectively related to R in group (1) 1 R 2 R 3 R 4 R 5 R 6 x, y, z, a, b, and c are synonyms. * indicates a bonding site with other structural units or end groups.

[0028] Groups (1-3)

[0029]

[0030] (In groups (1-3), R) 1 R 2 R 3 R 4 R 5 R 6 x, y, z, a3, b and c are respectively related to R in group (1) 1 R 2 R 3 R 4 R 5 R 6 x, y, z, a, b, and c are synonyms. * indicates a bonding site with other structural units or end groups.

[0031] <7> according to <6> The resin wherein the structural unit of group (1) contains the structural unit of group (1-1).

[0032] <8> according to <1> ~ <7> The resin described in any one of the following examples has a number-average molecular weight (Mn) of 500 to 4,000 and a weight-average molecular weight (Mw) of 500 to 7,000.

[0033] <9> according to <1> ~ <8> The resin described in any one of the following statements, wherein the terminal group of the resin is selected from hydrogen atoms, hydroxyl groups, and hydroxymethyl groups.

[0034] <10> A resin is a reaction product of a resin having the structural units described in group (2) and a compound shown in formula (3).

[0035] Group (2)

[0036]

[0037] (In group (2), R) 1 Each can independently represent methylene, methyleneoxy, methyleneoxymethylene, or oxymethylene. R 2 and R 3 Each of the following independently represents a halogen atom, an alkyl group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a hydroxyalkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 12 carbon atoms. x represents 0 or 1, and y and z independently represent numbers from 0 to 3. a, b, and c independently represent the molar ratio of the structural units, where a is a number greater than 1, b is a number greater than 0, and c is a number greater than 1. R 1 They can be arbitrarily bonded to each other to form a cross-linked structure. * indicates the bonding site with other structural units or end groups.

[0038] Equation (3)

[0039]

[0040] (In equation (3), R) 4 R 5 and R 6 Each of these groups independently represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, a haloalkyl 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. L represents a halogen atom.

[0041] <11> according to <10> The resins described herein, wherein the resins having the structural units of group (2) have a hydroxyl equivalent of 200 to 400 g / eq.

[0042] <12> A method for manufacturing a resin, characterized by comprising the step of reacting a resin having the structural units described in group (2) with a compound represented by formula (3) in the presence of an alkaline compound.

[0043] Group (2)

[0044]

[0045] (In group (2), R) 1 Each can independently represent methylene, methyleneoxy, methyleneoxymethylene, or oxymethylene. R 2 and R 3 Each of the following independently represents a halogen atom, an alkyl group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a hydroxyalkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 12 carbon atoms. x represents 0 or 1, and y and z independently represent numbers from 0 to 3. a, b, and c independently represent the molar ratio of the structural units, where a is a number greater than 1, b is a number greater than 0, and c is a number greater than 1. R 1 They can be arbitrarily bonded to each other to form a cross-linked structure. * indicates the bonding site with other structural units or end groups.

[0046] Equation (3)

[0047]

[0048] (In equation (3), R) 4 R 5 and R 6 Each of these groups independently represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, a haloalkyl 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. L represents a halogen atom.

[0049] <13> according to <12> The method for manufacturing the resin, wherein, in formula (3), R 4 R 5 and R 6 is a hydrogen atom, and L is a chlorine atom.

[0050] <14> according to <12> or <13> The method for manufacturing the resin, wherein, in group (2), R 2 and R 3 Each is an alkyl group having 1 to 10 carbon atoms.

[0051] <15> according to <12> or <13> The method for manufacturing the resin, wherein, in group (2), R 2 and R 3 Each is an alkyl group having 1 to 5 carbon atoms.

[0052] <16> according to <12> ~ <15> The method for manufacturing the resin according to any one of the following, wherein, in group (2), 0.2 ≤ a / (b+c) ≤ 5.

[0053] <17> according to <12> ~ <16> The method for manufacturing the resin according to any one of the following, wherein the structural unit of group (2) contains at least one of the structural unit of group (2-1), the structural unit of group (2-2), and the structural unit of group (2-3).

[0054] Group (2-1)

[0055]

[0056] In group (2-1), R 1 R 2 R 3 x, y, z, a1, b, and c are respectively related to R in group (2). 1 R 2 R 3 x, y, z, a, b, and c are synonyms. * indicates a bonding site with other structural units or end groups.

[0057] Group (2-2)

[0058]

[0059] In group (2-2), R 1 R 2 R 3 x, y, z, a2, b, and c are respectively related to R in group (2). 1 R 2 R 3 x, y, z, a, b, and c are synonyms. * indicates a bonding site with other structural units or end groups.

[0060] Group (2-3)

[0061]

[0062] (In group (2-3), R) 1 R 2 R 3 x, y, z, a3, b, and c are respectively related to R in group (2). 1 R 2 R 3 x, y, z, a, b, and c are synonyms. * indicates a bonding site with other structural units or end groups.

[0063] <18> according to <17> The method for manufacturing the resin, wherein the structural unit of group (2) contains the structural unit of group (2-1).

[0064] <19> according to <12> ~ <18> The method for manufacturing the resin according to any one of the following methods, wherein the hydroxyl equivalent of the resin having the structural unit of group (2) is 200 to 400 g / eq.

[0065] <20> according to <12> ~ <19> The method for manufacturing the resin according to any one of the following, wherein the number-average molecular weight Mn of the resin having the structural unit of group (2) is 400 to 2,500 and the weight-average molecular weight Mw is 400 to 5,000.

[0066] <21> according to <12> ~ <20> The method for manufacturing the resin according to any one of the following methods, wherein the terminal group of the resin having the structural unit of group (2) is selected from hydrogen atoms, hydroxyl groups and hydroxymethyl groups.

[0067] <22> according to <12> ~ <21> The method for manufacturing the resin according to any one of the following, wherein the aforementioned alkaline compound contains at least one of an alkali metal alkoxide and an alkali metal hydroxide.

[0068] <23> according to <12> ~ <22> The method for manufacturing the resin according to any one of the following, wherein the resin to be manufactured is <1> ~ <11> The resin described in any one of the following statements.

[0069] <24> A curable resin composition containing <1> ~ <11> The resin described in any one of the following statements.

[0070] <25> according to <24> The curable resin composition further contains <1> ~ <11> Thermosetting compound other than the resin mentioned in any one of the above statements.

[0071] <26> according to <25> The curable resin composition, wherein the aforementioned thermosetting compound contains a variety selected from... <1> ~ <11> The compound having carbon-carbon unsaturated bonds other than any of the resins mentioned in any one of the above statements, and at least one of epoxy resins.

[0072] <27> A solidified substance, which is <24> ~ <26> The cured product of the curable resin composition described in any one of the above statements.

[0073] The effects of the invention

[0074] According to the present invention, novel resins with excellent dielectric properties, as well as methods for manufacturing the resins, curable resin compositions, and cured products can be provided. Detailed Implementation

[0075] The following describes in detail the method for implementing the present invention (hereinafter referred to as "this embodiment"). It should be noted that the following embodiment is an example for illustrating the present invention, and the present invention is not limited to this embodiment.

[0076] It should be noted that in this specification, "~" means that the values ​​recorded before and after it are used as the lower limit and upper limit values.

[0077] Unless otherwise specified, all physical property values ​​and characteristic values ​​in this specification are values ​​at 23°C.

[0078] In this specification, the description of groups (atomic groups) includes 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 description of unsubstituted and unsubstituted groups is preferred to be unsubstituted.

[0079] The resin of this embodiment is characterized in that it is a resin having the structural units described in group (1).

[0080] Group (1)

[0081]

[0082] (In group (1), R) 1 Each can independently represent methylene, methyleneoxy, methyleneoxymethylene, or oxymethylene. R 2 and R 3 Each can independently represent a halogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl 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. R 4 R 5 and R 6 Each of the following independently represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, a haloalkyl 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. x represents 0 or 1, and y and z independently represent numbers from 0 to 3. a, b, and c independently represent the molar ratio of the structural units, where a is a number greater than 1, b is a number greater than 0, and c is a number greater than 1. R 1 They can be arbitrarily bonded to form a cross-linked structure. * indicates the bonding site with other structural units or end groups.

[0083] By achieving this structure, resins with excellent dielectric properties can be obtained. Furthermore, high heat resistance can be maintained.

[0084] In group (1), R 1 Each can independently represent methylene, methyleneoxy, methyleneoxymethylene, or oxymethylene, preferably methylene or methyleneoxymethylene, more preferably methylene. R 1 They can be arbitrarily bonded together to form a cross-linked structure. As R 1 Cross-linked structures can be exemplified by the following structures.

[0085]

[0086] R 1 Preferably, no cross-linking structure is formed. n is a number greater than or equal to 1, typically a number between 1 and 10.

[0087] R 2 and R 3 Each of the following can be independently represented as a halogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl 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, with each of the following being preferably an alkyl group having 1 to 10 carbon atoms.

[0088] As R 2 and R 3 The halogen atom is preferably a fluorine atom or a chlorine atom.

[0089] As R 2 and R 3 The alkyl group having 1 to 10 carbon atoms is more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably methyl, ethyl, isopropyl, n-propyl, n-butyl or tert-butyl.

[0090] As R 2 and R 3 The alkyl halogroup having 1 to 10 carbon atoms is more preferably an alkyl group having 1 to 5 carbon atoms that is substituted with fluorine or chlorine atoms, and even more preferably fluoromethyl, chloromethyl, fluoroethyl or chloroethyl.

[0091] As R 2 and R 3 The hydroxyalkyl group having 1 to 10 carbon atoms is more preferably a hydroxyalkyl group having 1 to 5 carbon atoms, and even more preferably hydroxymethyl or hydroxyethyl.

[0092] As R 2 and R 3 The preferred aryl group is phenyl with 6 to 12 carbon atoms.

[0093] R 4 R 5 and R 6Each of the following can be independently represented: hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, haloalkyl group having 1 to 10 carbon atoms, hydroxyl group, hydroxyalkyl group having 1 to 10 carbon atoms, or aryl group having 6 to 12 carbon atoms. Each of the following can be independently represented: hydrogen atom, halogen atom (preferably chlorine atom or fluorine atom), methyl group, and hydrogen atom.

[0094] x represents 0 or 1, and may include both structural units where x is 0 and structural units where x is 1, but preferably includes at least structural units where x is 0. Furthermore, arrangements that include at least structural units where x is 1 can also be cited.

[0095] y and z each independently represent a number from 0 to 3. Preferably, y and z are each 1 or higher, and more preferably 2 or lower. By making y and z 1 or higher, better dielectric properties can be achieved.

[0096] In group (1), R is preferred. 1 Methylene, R 2 and R 3 Each is independently tert-butyl or methyl, R 4 R 5 and R 6 The form is a hydrogen atom, x is 1, and y and z are 1 or 2.

[0097] a, b, and c each independently represent the molar ratio of the structural unit. a is a number greater than or equal to 1, b is a number greater than or equal to 0, and c is a number greater than or equal to 1. The molar ratio of b to a is preferably 1:11 or greater, more preferably 1:23 or greater. Furthermore, the molar ratio of c to a is preferably 1:0.2 to 5, more preferably 1:0.25 to 3. Further, the molar ratio of b to c is preferably 1:18 or greater, more preferably 1:37 or greater.

[0098] When all structural units in this embodiment are set to 100, the total of a, b and c in terms of molar ratio is preferably 90 or more, more preferably 95 or more, and even more preferably all structural units except the end base are 100.

[0099] The structural unit described in group (1) preferably includes at least one of the structural units described in group (1-1), group (1-2), and group (1-3), and more preferably includes the structural unit described in group (1-1).

[0100] As will be described later, the resin of this embodiment can preferably be synthesized from a resin having the structural units described in group (2). For example, xylene resin, which is an inexpensive resin that can be synthesized from xylene and formaldehyde, can be cited as a representative example of a resin having the structural units described in group (2). When the resin of this embodiment is obtained using the xylene resin, a resin containing at least one of the structural units described in group (1-1), group (1-2), and group (1-3) can be obtained, and a resin containing the structural units described in group (1-1) is particularly preferred. That is, by producing a resin containing at least one of the structural units described in group (1-1), group (1-2), and group (1-3), the resin of this embodiment can be made into an industrially inexpensive and readily manufactured resin.

[0101] Group (1-1)

[0102]

[0103] In group (1-1), R 1 R 2 R 3 R 4 R 5 R 6 x, y, z, a1, b and c are respectively related to R in group (1) 1 R 2 R 3 R 4 R 5 R 6 x, y, z, a, b, and c are synonyms. * indicates the bonding location with other structural units or end bases.

[0104] Group (1-2)

[0105]

[0106] (In group (1-2), R) 1 R 2 R 3 R 4 R 5 R 6 x, y, z, a2, b and c are respectively related to R in group (1) 1 R 2 R 3 R 4 R 5 R 6 x, y, z, a, b, and c are synonyms. * indicates the bonding location with other structural units or end bases.

[0107] Groups (1-3)

[0108]

[0109] (In groups (1-3), R) 1 R 2 R 3 R 4 R 5 R 6 x, y, z, a3, b and c are respectively related to R in group (1) 1 R 2 R 3 R 4 R 5 R 6 x, y, z, a, b, and c are synonyms. * indicates the bonding location with other structural units or end bases.

[0110] The resin of this embodiment may contain only one type of structural unit from group (1), or it may contain two or more types. In the case of containing two or more types, the total amount is within the range described above.

[0111] The resin of this embodiment may also contain structural units other than those shown in group (1).

[0112] Furthermore, the structural units shown in group (1) of the resin in this embodiment can be randomly polymerized or block polymerized.

[0113] In group (1), * indicates the bonding position with other structural units or terminal groups. As terminal groups, they are preferably selected from hydrogen atoms, hydroxyl groups and hydroxymethyl groups, more preferably hydrogen atoms or hydroxyl groups, and even more preferably hydrogen atoms.

[0114] For the resin of this embodiment, in group (1), it is preferable that 0.2 ≤ a / (b+c) ≤ 5. By setting it to the lower limit or above, it tends to more effectively suppress thermal degradation caused by time. In addition, by setting it to the upper limit or below, the glass transition temperature tends to increase further. a / (b+c) is more preferably 0.2 or above, more preferably 0.23 or above, even more preferably 0.27 or above, and even more preferably 0.3 or above. In addition, a / (b+c) is more preferably 5 or below, more preferably 4 or below, even more preferably 3 or below, even more preferably 2.5 or below, and even more preferably 2.3 or below. The value of a / (b+c) can be determined by the value of a / (b+c) in group (2) described later.

[0115] In the resin of this embodiment, the weight-average molecular weight (Mw) is preferably 500 or more, more preferably 600 or more, further preferably 800 or more, even more preferably 1,000 or more, and even more preferably 2,000 or more. By setting it to the aforementioned lower limit value 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. In addition, in the resin of this embodiment, the weight-average molecular weight (Mw) is preferably 7,000 or less, more preferably 6,000 or less, further preferably 5,000 or less, even more preferably 4,000 or less, and even more preferably 3,500 or less. By setting it to the aforementioned upper limit value or below, the workability of the resin tends to be further improved due to the improvement of the resin's solvent solubility and the reduction of the resin's melt viscosity.

[0116] In the resin of this embodiment, the number average molecular weight (Mn) is preferably 500 or more, more preferably 600 or more, further preferably 700 or more, even more preferably 800 or more, and even more preferably 900 or more. By setting it to the aforementioned lower limit value 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. In addition, in the resin of this embodiment, the number average molecular weight (Mn) is preferably 4,000 or less, more preferably 3,500 or less, further preferably 3,000 or less, even more preferably 2,000 or less, and even more preferably 1,500 or less. By setting it to the aforementioned upper limit value or below, the workability of the resin tends to be further improved due to the improvement of the resin's solvent solubility and the reduction of the resin's melt viscosity.

[0117] The weight-average molecular weight and number-average molecular weight were determined according to the methods described in the examples described later.

[0118] The method for manufacturing the resin according to this embodiment is characterized by including a step of reacting a resin having the structural units described in group (2) with a compound shown in formula (3) in the presence of an alkaline compound. By manufacturing in this way, a resin with excellent dielectric properties can be obtained. Furthermore, a resin with excellent heat resistance can be obtained.

[0119] Group (2)

[0120]

[0121] (In group (2), R) 1 Each can independently represent methylene, methyleneoxy, methyleneoxymethylene, or oxymethylene. R 2 and R 3Each of the following independently represents a halogen atom, an alkyl group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a hydroxyalkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 12 carbon atoms. x represents 0 or 1, and y and z independently represent numbers from 0 to 3. a, b, and c independently represent the molar ratio of the structural units, where a is a number greater than 1, b is a number greater than 0, and c is a number greater than 1. R 1 They can be arbitrarily bonded to form a cross-linked structure. * indicates the bonding site with other structural units or end groups.

[0122] Equation (3)

[0123]

[0124] (In equation (3), R) 4 R 5 and R 6 Each of these groups independently represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, a haloalkyl 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. L represents a halogen atom.

[0125] First, let’s explain group (2) in detail.

[0126] In group (2), R 1 R 2 R 3 x, y, z, a, b and c are respectively related to R in group (1) 1 R 2 R 3 x, y, z, a, b, and c are synonyms, and their preferred ranges are also the same. The terminal groups in group (2) are the same as those in group (1). The preferred range of a / (b+c) in group (2) is also synonymous with the preferred range of a / (b+c) in group (1). a / (b+c) in group (2) is calculated based on the hydroxyl value of the obtained resin.

[0127] Furthermore, the structural unit described in preferred group (2) contains at least one of the structural units described in group (2-1), group (2-2), and group (2-3), and more preferably contains the structural unit described in group (2-1). By using a resin containing at least one of the structural units described in group (2-1), group (2-2), and group (2-3), a resin having the structural unit described in group (1) can be manufactured more cheaply.

[0128] Group (2-1)

[0129]

[0130] In group (2-1), R 1 R 2 R 3 x, y, z, a1, b, and c are respectively related to R in group (2). 1 R 2 R 3 x, y, z, a, b, and c are synonyms. * indicates the bonding location with other structural units or end bases.

[0131] Group (2-2)

[0132]

[0133] In group (2-2), R 1 R 2 R 3 x, y, z, a2, b, and c are respectively related to R in group (2). 1 R 2 R 3 x, y, z, a, b, and c are synonyms. * indicates the bonding location with other structural units or end bases.

[0134] Group (2-3)

[0135]

[0136] (In group (2-3), R) 1 R 2 R 3 x, y, z, a3, b, and c are respectively related to R in group (2). 1 R 2 R 3 x, y, z, a, b, and c are synonyms. * indicates the bonding location with other structural units or end bases.

[0137] In resins having the structural units described in group (2), the weight-average molecular weight (Mw) is preferably 400 or more, more preferably 600 or more, further preferably 700 or more, even more preferably 800 or more, even more preferably 850 or more, and still even more preferably 900 or more, and may also be 1000 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. In addition, in resins having the structural units described in group (2), the weight-average molecular weight (Mw) is preferably 5,000 or less, more preferably 4,000 or less, further preferably 3,500 or less, even more preferably 3,000 or less, and still even more preferably 2,500 or less. By setting it to the aforementioned upper limit or below, the workability of the resin tends to be further improved due to the improvement of the solvent solubility of the resin and the reduction of the melt viscosity of the resin.

[0138] In resins having the structural units described in group (2), the number-average molecular weight (Mn) is preferably 400 or more, more preferably 450 or more, even more preferably 500 or more, and may also be 600 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. In addition, in resins having the structural units described in group (2), the number-average molecular weight (Mn) is preferably 2,500 or less, more preferably 2,000 or less, even more preferably 1,500 or less, and even more preferably 1,000 or less. By setting it to the aforementioned upper limit or below, the workability of the resin tends to be further improved due to the improvement of the resin's solvent solubility and the reduction of the resin's melt viscosity.

[0139] The weight-average molecular weight and number-average molecular weight were determined according to the methods described in the examples below.

[0140] For resins having the structural units described in group (2), the hydroxyl equivalent is preferably 200 g / eq or more, more preferably 250 g / eq or more, even more preferably 270 g / eq or more, even more preferably 280 g / eq or more, even more preferably 290 g / eq or more, and further, it can be 300 g / eq or more, or 320 g / eq or more. By setting it to the aforementioned lower limit or above, the amount of hydroxyl groups reacting with the compound shown in formula (3) will not exceed the necessary amount, and the rate of change of the dielectric loss tangent caused by thermal degradation can be effectively reduced. For resins having the structural units described in group (2), the hydroxyl equivalent is preferably 400 g / eq or less, more preferably 395 g / eq or less, even more preferably 390 g / eq or less, even more preferably 385 g / eq or less, even more preferably 380 g / eq or less, and further, it can be 370 g / eq or less, or 360 g / eq or less. By setting it to the aforementioned upper limit or below, there is a tendency to obtain resins with excellent heat resistance and excellent dielectric properties.

[0141] That is, by introducing structures derived from compounds of formula (3) such as vinylbenzyl, the obtained resin has a higher Tg and excellent dielectric properties, making it ideal. However, it is prone to thermal degradation over time. Therefore, in applications where it is necessary to suppress thermal degradation over time, it is desirable to adjust the amount of hydroxyl groups in the raw materials as described above.

[0142] The hydroxyl equivalent was determined according to the description in the examples.

[0143] Next, equation (3) will be explained in detail.

[0144] Equation (3)

[0145]

[0146] (In equation (3), R) 4 R 5 and R 6 Each of these groups independently represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, a haloalkyl 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. L represents a halogen atom.

[0147] In equation (3), R 4 R 5 and R 6 respectively with R in equation (1) 4 R 5 and R 6 Similarly, the range of preferred options is also the same.

[0148] In formula (3), L represents a halogen atom, preferably a fluorine atom or a chlorine atom, and more preferably a chlorine atom.

[0149] In the resin manufacturing method of this embodiment, the resin having the structural unit described in group (2) and the compound shown in formula (3) may be used only one or more.

[0150] In the resin manufacturing method of this embodiment, the molar ratio of the phenolic hydroxyl groups of the resin having the structural unit described in group (2) to the compound shown in formula (3) added to the reaction system is preferably 1:1 to 1.3, more preferably 1:1 to 1.2.

[0151] In the resin manufacturing method of this embodiment, a resin having the structural units described in group (2) above is reacted with a compound shown in formula (3) in the presence of an alkaline compound. By using the alkaline compound, the reaction between the phenolic hydroxyl groups of the resin having the structural units described in group (2) above and the halomethyl groups of the compound shown in formula (3) is promoted.

[0152] The basic compound preferably contains at least one of an alkali metal alkoxide and an alkali metal hydroxide, more preferably an alkali metal hydroxide. Examples of alkali metals include lithium, potassium, and sodium, with sodium being preferred. Examples of alkali metal salts that constitute the alkali metal alkoxide include methoxy salts and ethoxy salts.

[0153] In the manufacturing method of this embodiment, the molar ratio of the phenolic hydroxyl groups of the resin having the structural unit described in group (2) to the total amount of alkali metal alkoxides and alkali metal hydroxides added to the reaction system is preferably 1:1 to 1:6, more preferably 1:1.1 to 1:4.

[0154] In the manufacturing method of this embodiment, when using an alkali metal hydroxide, a phase transfer catalyst may also be used. Tetrabutylammonium bromide can be used as an example of a phase transfer catalyst.

[0155] In the manufacturing method of this embodiment, the basic compound (especially alkali metal alkoxides and alkali metal hydroxides) can be added to the reaction system in one step or in two or more steps, preferably in two or more steps. By adding it in two or more steps, the reaction rate tends to be further improved.

[0156] In the manufacturing method of this embodiment, the reaction of the resin having the structural unit described in group (2) with the compound shown in formula (3) is preferably carried out at 40 to 100°C, and more preferably at 50 to 85°C.

[0157] In the manufacturing method of this embodiment, it is preferable to use a solvent when the resin having the structural unit described in group (2) reacts with the compound shown in formula (3).

[0158] The solvent can be appropriately determined based on the type of basic compound used.

[0159] When using an alkali metal hydroxide as the basic compound, the solvent can be, for example, an aromatic hydrocarbon (preferably toluene) and water. More specifically, it is preferable to use an aqueous solution of the aromatic hydrocarbon and the alkali metal hydroxide in the reaction system.

[0160] When using alkali metal alkoxides as basic compounds, aprotic polar solvents are preferred.

[0161] In the manufacturing method of this embodiment, it is preferable to separate and purify the resin obtained by reacting the resin having the structural units described in group (2) above with the compound shown in formula (3). The separation and purification can be carried out according to conventional methods.

[0162] For the resin manufactured by the resin manufacturing method of this embodiment, the resin of this embodiment described above is preferred. Therefore, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the resin manufactured by the resin manufacturing method of this embodiment are preferably within the same range as those of the resin of this embodiment described above.

[0163] <Application>

[0164] 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 contain thermosetting compounds other than the resin of this embodiment. Preferably, the aforementioned thermosetting compound contains at least one compound selected from compounds having carbon-carbon unsaturated bonds other than the resin of this embodiment and epoxy resins.

[0165] Furthermore, the aforementioned curable resin composition may contain one or more various additives. Examples of additives include flame retardants, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, dyes, pigments, thickeners, flow modifiers, lubricants, defoamers, dispersants, leveling agents, gloss agents, and polymerization inhibitors.

[0166] The cured product of this embodiment is formed by curing the above-described curable resin composition. Such a cured product has excellent heat resistance and excellent dielectric properties, and therefore is suitable for use as an insulating layer for printed circuit boards and a semiconductor packaging material.

[0167] Example

[0168] The present invention will be further described in detail below with examples. The materials, amounts, ratios, processing contents, processing order, etc., shown in the following examples can be appropriately modified as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0169] If the measuring instruments used in the embodiments are difficult to obtain due to production stoppages or other reasons, other devices with equivalent performance can be used for measurement.

[0170] <Determination of number-average molecular weight and weight-average molecular weight>

[0171] The number-average molecular weight and weight-average molecular weight of the resin were determined by gel permeation chromatography (GPC).

[0172] Analytical columns were connected using KF-801, KF-802, KF-803, and KF-804 instruments manufactured by Showa Denko Corporation, and a differential refractive index detector (RID-20A) manufactured by Shimadzu Corporation was used for detection. 80 mg of the resin (xylene resin, vinyl compound) used as the analyte was dissolved in 2 mL of tetrahydrofuran as the eluent, and the injection volume into the column was set to 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 constructed using standard polystyrene PStQuick MP-N manufactured by Tosoh Corporation, and the converted molecular weight of polystyrene was estimated.

[0173] <Determination of the hydroxyl equivalent of the raw material resin>

[0174] The hydroxyl equivalent of the raw material phenol-modified xylene resin was determined in accordance with JIS K0070-92-7.1.

[0175] <Determination of Hydroxyl Equivalent in Resins (Vinyl Compounds)>

[0176] The hydroxyl equivalent of the resin (vinyl compound) was determined using 2,6-dimethylphenol (2,6-xylenol) as a standard. IR analysis (liquid cell method; cell length = 1 mm) was performed in a solvent using dried dichloromethane. The results were based on a 3600 cm⁻¹ solution. -1 The absorption intensity is then determined.

[0177] Equipment used: Nicolet 6700FT-IR

[0178] < 1 H-NMR Analysis

[0179] Confirmed: Resin (vinyl compound) through 1 ¹H-NMR analysis revealed a peak at the benzyl position near 4.70 ppm and peaks at the vinyl positions near 5.25 ppm and 5.75 ppm after the reaction. Further IR analysis of the phenolic hydroxyl groups in the phenol-modified xylene resin at 3600 cm⁻¹... -1 The nearby peaks disappear in vinyl compounds.

[0180] Equipment used: Bruker 500MHz NMR Avance III HD

[0181] <Synthetic Example 1: Synthesis of p-tert-butylphenol (PTBP) modified xylene resin>

[0182] In a 0.5L detachable flask equipped with a thermometer, Liebig condenser, stirrer, and steam inlet, 300.0g of xyleneformaldehyde resin (a product of Fudow Co., Ltd., "Nikanol G") and 0.16g (0.84mmol) of p-toluenesulfonic acid monohydrate (a product of FUJIFILM Wako Pure Chemical Corporation) were added. The mixture was heated to 180°C under a steam flow while stirring. The mixture was stirred at this temperature for 2 hours to deacetalize the xyleneformaldehyde resin. The generated formaldehyde was distilled off the system. After deacetalization, 200.0g (1.33mol) of p-tert-butylphenol (a product of DIC Corporation) was added, and the mixture was reacted at 180°C for 2 hours while dehydrating. After the reaction, 0.16g (2.66mmol) of urea was added to stop the reaction. After the reaction was stopped, the temperature was raised to 230°C under steam flow, and unreacted p-tert-butylphenol was removed by distillation to obtain 409.6 g of p-tert-butylphenol-modified xylene-formaldehyde resin, a brown solid. The number-average molecular weight of the obtained resin was 962, the weight-average molecular weight was 2,112, and the hydroxyl equivalent was 346 g / eq.

[0183] <Synthetic Example 2: Synthesis of 2,6-xylenol-modified xylene resin (1)>

[0184] In a 0.5L detachable flask equipped with a thermometer, Liebig condenser, stirrer, and steam inlet, 300.0g of xyleneformaldehyde resin (Fudow Co., Ltd. product, "Nikanol G"), 0.84g (8.57mmol) of maleic anhydride, and 0.14g (0.74mmol) of p-toluenesulfonic acid monohydrate (FUJIFILM Wako Pure Chemical Corporation product) were added. The mixture was stirred and heated to 180°C under a steam flow. The mixture was stirred at this temperature for 2 hours to deacetalize the xyleneformaldehyde resin. The generated formaldehyde was distilled off the system. After deacetalization, 150.0g (1.23mol) of 2,6-xylenol (Mitsubishi Gas Chemical Co., Ltd. product) was added, and the mixture was dehydrated while the temperature was raised to 200°C. The reaction was carried out at this temperature for 2 hours. After the reaction, 0.13g (2.16mmol) of urea was added to stop the reaction. After the reaction was stopped, the temperature was raised to 230°C under steam, and unreacted 2,6-xylenol was removed by distillation, yielding 365.7 g of brown solid 2,6-xylenol-modified xyleneform resin. The number-average molecular weight of the obtained resin was 796, the weight-average molecular weight was 1,929, and the hydroxyl equivalent was 373 g / eq.

[0185] <Synthetic Example 3: Synthesis of 2,6-xylenol-modified xylene resin (2)>

[0186] In a 0.5L detachable flask equipped with a thermometer, Liebig condenser, stirrer, and steam inlet, 300.0g of xylene-formaldehyde resin (Fudow Co., Ltd. product, "Nikanol G"), 0.84g (8.57mmol) of maleic anhydride, and 0.16g (0.84mmol) of p-toluenesulfonic acid monohydrate (FUJIFILM Wako Pure Chemical Corporation product) were added. The mixture was stirred and heated to 180°C under a steam flow. The mixture was stirred at this temperature for 2 hours to deacetalize the xylene-formaldehyde resin. The generated formaldehyde was distilled off the system. After deacetalization, 220.6g (1.81mol) of 2,6-xylenol (Mitsubishi Gas Chemical Co., Ltd. product) was added, and the mixture was heated to 200°C while dehydrating. The reaction was carried out at the same temperature for 2 hours. After the reaction, 0.16g (2.66mmol) of urea was added to stop the reaction. After the reaction was stopped, the temperature was raised to 230℃ under steam, and unreacted 2,6-xylenol was removed by distillation, yielding 405.8 g of brown solid 2,6-xylenol-modified xyleneform resin. The number-average molecular weight of the obtained resin was 557, the weight-average molecular weight was 900, and the hydroxyl equivalent was 289 g / eq.

[0187] <Example 1>

[0188] In a 300 mL four-necked flask equipped with a stirrer, thermometer, and reflux tube, 30.2 g (equivalent to 87.2 mmol of hydroxyl moles) of p-tert-butylphenol-modified xylene resin obtained in Synthesis Example 1, 120.6 g of N,N-dimethylacetamide (manufactured by FUJIFILM Wako Pure Chemical Corporation), and 15.2 g (96.2 mmol) of chloromethylstyrene (manufactured by AGC Seimei Chemical Co., Ltd., "CMS-P") were added under a nitrogen atmosphere, and the mixture was heated and stirred to 50 °C. The reaction temperature was maintained at 50 °C, and 18.3 g (96.0 mmol) of sodium methoxide (manufactured by Tokyo Chemical Industry Co., Ltd., 28.3% by mass methanol solution) was added dropwise, and the mixture was stirred for 70 minutes. Then, 1.88 g (9.85 mmol) of sodium methoxide was added dropwise, and the mixture was stirred at 70 °C for 1 hour. The reaction was stopped by adding 1.37 g (11.9 mmol) of phosphoric acid (manufactured by FUJIFILM WakoPure Chemical Corporation, concentration: 85.6% by mass) and 2.59 g of N,N-dimethylacetamide. After 70 minutes of filtration, the mixture was filtered using filter paper No. 5A (manufactured by Kiriyama Corporation) and a Kiriyama funnel SB-60 (manufactured by Kiriyama Corporation, diameter 60 mm). 69.4 g of N,N-dimethylacetamide was added to the filtrate, and the resulting mixture was then added dropwise to 182.6 g of pure water for solidification. The filtered solid was washed with pure water and then further washed with methanol. The solid was washed again with pure water and methanol, and then dried under reduced pressure to obtain 33.8 g of the target vinyl compound. The number-average molecular weight of the obtained vinyl compound was 1,126, and the weight-average molecular weight was 2,391.

[0189] The cured material was prepared according to the following method. Furthermore, the glass transition temperature and dielectric properties of the obtained cured material were measured and are shown in Table 1.

[0190] <Preparation of solidified materials>

[0191] The cured product is produced by placing the vinyl compound obtained above into a mold with a length of 100 mm and a width of 30 mm, and holding it at 200°C for 1.5 hours using a vacuum press.

[0192] Equipment used: Kitagawa Seiki Co., Ltd. 5-segment stamping press VH2-1630

[0193] <Determination of the glass transition temperature of cured products>

[0194] The obtained cured material was cut into pieces 5 mm wide and 40 mm long, and dynamic viscoelasticity was measured. The glass transition temperature of the cured material was the peak temperature of the obtained dynamic elastic modulus. The unit is expressed in °C.

[0195] Equipment used: DMS6100 and EXSTAR6000 manufactured by Seiko Instruments Inc.

[0196] Heating rate: 5℃ / minute

[0197] Frequency: Sine wave, 10Hz

[0198] <Determination of Dielectric Properties of Cured Materials>

[0199] Regarding the dielectric constant and dielectric loss tangent of the cured material, the values ​​at 10 GHz were measured using the cavity resonator perturbation method after the cured material was cut into pieces with a thickness of 1 mm, a width of 0.8 mm, and a length of 100 mm. Furthermore, to evaluate its resistance to heat oxidation degradation, the dielectric constant and dielectric loss tangent were measured at 10 GHz after the cut cured material was heated at 200°C in air for 1 hour. The rate of change of the dielectric loss tangent was calculated using the following formula.

[0200] Change rate of dielectric loss tangent (%) = ((Dielectric loss tangent after heating / Dielectric loss tangent before heating) - 1) × 100 (%)

[0201] Equipment used: Agilent Technologies 8722ES Network Analyzer

[0202] <Example 2>

[0203] In Example 1, 30.7 g of 2,6-xylenol-modified xylene resin (equivalent to 82.4 mmol in hydroxyl moles) obtained in Synthesis Example 2 was used instead of 30.2 g of p-tert-butylphenol-modified xylene resin. The amount of N,N-dimethylacetamide added was changed from 120.6 g to 122.6 g, the amount of chloromethylstyrene added was changed from 15.2 g to 14.4 g (90.8 mmol), the amount of sodium methoxide added was changed from 18.3 g to 17.7 g (92.9 mmol), the amount of additional sodium methoxide added was changed from 1.88 g to 1.64 g (8.59 mmol), the amount of phosphoric acid added was changed from 1.37 g to 1.19 g (10.4 mmol), and the amount of additional N,N-dimethylacetamide added was changed from 2.59 g to 2.23 g. Otherwise, the reaction and purification were carried out in the same manner as in Example 1 to obtain 37.5 g of the target vinyl compound. The obtained vinyl compound had a number-average molecular weight of 975 and a weight-average molecular weight of 2,217. Cured products were prepared according to the aforementioned curing conditions.

[0204] Similar to Example 1, the glass transition temperature and dielectric properties of the cured material were measured and are shown in Table 1.

[0205] <Example 3>

[0206] In a reaction vessel equipped with a stirrer, thermometer, and reflux duct, 26.7 g (equivalent to 92.4 mmol in hydroxyl molars) of the 2,6-xylenol-modified xylene resin obtained in Synthesis Example 3, 185.1 g of toluene (manufactured by FUJIFILM Wako PureChemical Corporation), and 27.2 g (327 mmol) of sodium hydroxide aqueous solution (manufactured by Kanto Chemical Co., Ltd., concentration: 48% by mass) were added, and the mixture was heated and stirred to 70°C. Maintaining the reaction temperature at 70°C, 8.63 g (17.7 mmol) of tetrabutylammonium bromide (manufactured by LionAkuzo Co., Ltd., concentration: 66% by mass) and 14.8 g (92.8 mmol) of chloromethylstyrene (manufactured by AGC Seimei Chemical Co., Ltd., "CMS-P") were added, and the mixture was stirred for 170 minutes. The organic layer and aqueous phase were separated, and the organic layer was washed four times with 1.4% sulfuric acid aqueous solution and then with warm water at 70°C. The obtained solution was concentrated and diluted with 155 g of 2-butanone (manufactured by FUJIFILM WakoPure Chemical Corporation), then added dropwise to methanol for solidification. The filtered solid was washed with pure water, then further washed with methanol, and then washed again with pure water and methanol. The solid was dried under reduced pressure to obtain 29.8 g of the target vinyl compound. The number average molecular weight of the obtained vinyl compound was 1,134, and the weight average molecular weight was 3,363. A cured product was prepared according to the aforementioned curing conditions.

[0207] Similar to Example 1, the glass transition temperature and dielectric properties of the cured material were measured and are shown in Table 1.

[0208] [Table 1]

[0209]

Claims

1. A resin having the structural units described in group (1), Group (1) In group (1), R 1 Each independently represents methylene, methyleneoxy, methyleneoxymethylene, or oxymethylene; R 2 and R 3 Each can independently represent an 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; R 4 R 5 and R 6 Each of the following independently represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, a haloalkyl 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; x represents 0 or 1, y and z independently represent numbers from 0 to 3; a, b, and c independently represent the molar ratio of the structural units, where a is a number greater than 1, b is a number greater than 0, and c is a number greater than 1; R 1 They can be arbitrarily bonded to each other to form a cross-linked structure; * indicates the bonding site with other structural units or end groups. The molar ratio of c to a is 1:0.2 to 5. When all structural units are set to 100, the total of a, b and c is more than 90 in terms of molar ratio.

2. The resin according to claim 1, wherein, In group (1), R 4 R 5 and R 6 Each is an independent hydrogen atom.

3. The resin according to claim 1 or 2, wherein, In group (1), R 2 and R 3 Each is an alkyl group having 1 to 10 carbon atoms.

4. The resin according to claim 1 or 2, wherein, In group (1), R 2 and R 3 Each is an alkyl group having 1 to 5 carbon atoms.

5. The resin according to claim 1 or 2, wherein, In group (1), 0.2 ≤ a / (b+c) ≤ 5.

6. The resin according to claim 1 or 2, wherein, The structural unit of group (1) includes at least one of the structural unit of group (1-1), the structural unit of group (1-2), and the structural unit of group (1-3). Group (1-1) In group (1-1), R 1 R 2 R 3 R 4 R 5 R 6 x, y, z, a1, b and c are respectively related to R in group (1) 1 R 2 R 3 R 4 R 5 R 6 x, y, z, a, b, and c are synonyms; * indicates the bonding position with other structural units or end groups. Group (1-2) In group (1-2), R 1 R 2 R 3 R 4 R 5 R 6 x, y, z, a2, b and c are respectively related to R in group (1) 1 R 2 R 3 R 4 R 5 R 6 x, y, z, a, b, and c are synonyms; * indicates the bonding position with other structural units or end groups. Groups (1-3) In groups (1-3), R 1 R 2 R 3 R 4 R 5 R 6 x, y, z, a3, b and c are respectively related to R in group (1) 1 R 2 R 3 R 4 R 5 R 6 x, y, z, a, b, and c are synonyms, and * indicates the bonding position with other structural units or end bases.

7. The resin according to claim 6, wherein, The structural unit described in group (1) contains the structural unit described in group (1-1).

8. The resin according to claim 1 or 2, wherein the number average molecular weight (Mn) is 500 to 4,000 and the weight average molecular weight (Mw) is 500 to 7,000.

9. The resin according to claim 1 or 2, wherein, The terminal group of the resin is selected from hydrogen atoms, hydroxyl groups, and hydroxymethyl groups.

10. A resin, which is a reaction product of a resin having the structural units described in group (2) and a compound represented by formula (3), Group (2) In group (2), R 1 Each independently represents methylene, methyleneoxy, methyleneoxymethylene, or oxymethylene; R 2 and R 3 Each of the following independently represents an alkyl group with 1 to 10 carbon atoms, a hydroxyalkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 12 carbon atoms; x represents 0 or 1, y and z independently represent numbers from 0 to 3; a, b, and c independently represent the molar ratio of the structural units, where a is a number greater than 1, b is a number greater than 0, and c is a number greater than 1; R 1 They can be arbitrarily bonded to each other to form a cross-linked structure; * indicates the bonding site with other structural units or end groups. The molar ratio of c to a is 1:0.2 to 5. When all structural units are set to 100, the total of a, b, and c, expressed as a molar ratio, is over 90. Equation (3) In equation (3), R 4 R 5 and R 6 Each of the following can be independently represented: hydrogen atom, halogen atom, alkyl group with 1 to 10 carbon atoms, haloalkyl group with 1 to 10 carbon atoms, hydroxyl group, hydroxyalkyl group with 1 to 10 carbon atoms or aryl group with 6 to 12 carbon atoms, and L represents halogen atom.

11. The resin according to claim 10, wherein, The hydroxyl equivalent of the resin having the structural unit described in group (2) is 200-400 g / eq.

12. A method for manufacturing a resin, characterized in that, The step includes reacting a resin having the structural units described in group (2) with a compound shown in formula (3) in the presence of a basic compound. Group (2) In group (2), R 1 Each independently represents methylene, methyleneoxy, methyleneoxymethylene, or oxymethylene; R 2 and R 3 Each of the following independently represents an alkyl group with 1 to 10 carbon atoms, a hydroxyalkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 12 carbon atoms; x represents 0 or 1, y and z independently represent numbers from 0 to 3; a, b, and c independently represent the molar ratio of the structural units, where a is a number greater than 1, b is a number greater than 0, and c is a number greater than 1; R 1 They can be arbitrarily bonded to each other to form a cross-linked structure; * indicates the bonding site with other structural units or end groups. The molar ratio of c to a is 1:0.2 to 5. When all structural units are set to 100, the total of a, b, and c, expressed as a molar ratio, is over 90. Equation (3) In equation (3), R 4 R 5 and R 6 Each of the following can be independently represented: hydrogen atom, halogen atom, alkyl group with 1 to 10 carbon atoms, haloalkyl group with 1 to 10 carbon atoms, hydroxyl group, hydroxyalkyl group with 1 to 10 carbon atoms or aryl group with 6 to 12 carbon atoms, and L represents halogen atom.

13. The method for manufacturing the resin according to claim 12, wherein, In equation (3), R 4 R 5 and R 6 is a hydrogen atom, and L is a chlorine atom.

14. The method for manufacturing the resin according to claim 12 or 13, wherein, In group (2), R 2 and R 3 Each is an alkyl group having 1 to 10 carbon atoms.

15. The method for manufacturing the resin according to claim 12 or 13, wherein, In group (2), R 2 and R 3 Each is an alkyl group having 1 to 5 carbon atoms.

16. The method for manufacturing the resin according to claim 12 or 13, wherein, In group (2), 0.2 ≤ a / (b+c) ≤ 5.

17. The method for manufacturing the resin according to claim 12 or 13, wherein, The structural unit of group (2) contains at least one of the structural unit of group (2-1), the structural unit of group (2-2), and the structural unit of group (2-3). Group (2-1) In group (2-1), R 1 R 2 R 3 x, y, z, a1, b and c are respectively related to R in group (2) 1 R 2 R 3 x, y, z, a, b, and c are synonyms; * indicates the bonding position with other structural units or end groups. Group (2-2) In group (2-2), R 1 R 2 R 3 x, y, z, a2, b and c are respectively related to R in group (2) 1 R 2 R 3 x, y, z, a, b, and c are synonyms; * indicates the bonding position with other structural units or end groups. Group (2-3) In group (2-3), R 1 R 2 R 3 x, y, z, a3, b and c are respectively related to R in group (2) 1 R 2 R 3 x, y, z, a, b, and c are synonyms, and * indicates the bonding position with other structural units or end bases.

18. The method for manufacturing the resin according to claim 17, wherein, The structural unit described in group (2) contains the structural unit described in group (2-1).

19. The method for manufacturing the resin according to claim 12 or 13, wherein, The hydroxyl equivalent of the resin having the structural unit described in group (2) is 200-400 g / eq.

20. The method for manufacturing the resin according to claim 12 or 13, wherein, The number-average molecular weight Mn of the resin having the structural unit of group (2) is 400 to 2,500, and the weight-average molecular weight Mw is 400 to 5,000.

21. The method for manufacturing the resin according to claim 12 or 13, wherein, The end groups of the resin having the structural units of group (2) are selected from hydrogen atoms, hydroxyl groups and hydroxymethyl groups.

22. The method for manufacturing the resin according to claim 12 or 13, wherein, The alkaline compound contains at least one of an alkali metal alkoxide and an alkali metal hydroxide.

23. The method for manufacturing the resin according to claim 12 or 13, wherein, The resin to be manufactured is the resin according to any one of claims 1 to 11.

24. A curable resin composition comprising the resin according to any one of claims 1 to 11.

25. The curable resin composition according to claim 24, wherein, It further contains a thermosetting compound other than the resin according to any one of claims 1 to 11.

26. The curable resin composition according to claim 25, wherein, The thermosetting compound contains at least one compound having carbon-carbon unsaturated bonds other than the resins of any one of claims 1 to 11 and epoxy resins.

27. A cured product, which is a cured product of the curable resin composition according to any one of claims 24 to 26.

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