Episulfide resin, curable resin composition, and cured film

Abstract

To provide an episulfide resin capable of achieving both low-temperature curability and long-term stability, a curable resin composition using the episulfide resin, and a cured film using the curable resin composition. [Solution] The above problems are solved by an episulfide resin characterized by having a constituent unit represented by general formula (1) and a constituent unit represented by general formula (2), a curable resin composition using the episulfide resin, and a cured film using the curable resin composition.

Description

[Technical Field]

[0001] The present invention relates to an episulfide resin that exhibits excellent low-temperature curability and long-term stability, a curable resin composition using the episulfide resin, and a cured film. [Background technology]

[0002] In recent years, from the perspectives of reducing environmental impact, lowering costs, and expanding the range of equipment components, there has been a demand for curable compositions that can be cured at low temperatures in various fields. However, generally, curing at low temperatures requires highly active catalysts, compounds, initiators, etc., which significantly reduces stability over time. Therefore, from the perspective of workability, there is a need for a one-component curable composition that can achieve both low-temperature curing and stability over time.

[0003] On the other hand, episulfide resins are resins having a structure in which the oxygen atoms in the epoxy groups of epoxy resins are replaced with sulfur atoms. Because they possess excellent properties such as high heat resistance, moisture resistance, transparency, refractive index, and strength, they can be applied to a wide range of uses, including optical materials, electronic materials, adhesives, and display materials. Furthermore, it is known that episulfide resins exhibit greater ring strain and improved curability compared to epoxy resins because the atomic radius of the sulfur atom is larger than that of the oxygen atom. Therefore, attempts have been made to achieve both low-temperature curability and long-term stability using episulfide resins. (Patent Documents 1-4) [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 11-209689 [Patent Document 2] Japanese Patent Publication No. 2020-164628 [Patent Document 3] Japanese Patent Publication No. 2003-128787 [Patent Document 4] Japanese Patent Publication No. 2002-53668 [Overview of the project] [Problems to be Solved by the Invention]

[0005] However, the resins described in Patent Documents 1 to 4 have low-temperature curability due to the too-high reactivity of episulfide, but are inferior in stability over time, and the two cannot be achieved simultaneously. Further, when episulfide is used in applications such as optical materials, electronic materials, and display materials, high transparency is required. In view of these situations, an object of the present invention is to provide an episulfide resin capable of achieving both low-temperature curability, stability over time, and transparency, a curable resin composition using the episulfide resin, and a cured film using the curable resin composition. [Means for Solving the Problems]

[0006] As a result of intensive studies to solve the above problems, it has been found that the above problems can be solved by the following embodiments, and the present invention has been completed. <1> The present invention relates to an episulfide resin having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).

[0007] General formula (1) [Chemical formula]

[0008] [In general formula (1), ring D represents an aliphatic ring having 5 to 10 carbon atoms, A represents a unit having 2 to 30 carbon atoms including a thiirane ring, B represents a direct bond or a divalent linking group, E represents an oxygen atom, a sulfur atom, a divalent linking group containing an oxygen atom or a divalent linking group containing a sulfur atom, and n represents an integer of 1 or more.] ​​​​​​​​​​​​[In general formula (2), ring F represents an aliphatic ring having 5 to 10 carbon atoms, J represents a direct bond or a divalent linking group, G represents a direct bond or a divalent linking group, I represents an oxygen atom, a sulfur atom, a divalent linking group containing an oxygen atom, or a divalent linking group containing a sulfur atom, L and K each independently represent a hydrogen atom or a monovalent organic group, Y represents a hydrogen atom or a methyl group, and m represents an integer of 1 or more.]

[0011] <2> The present invention relates to a material with a weight-average molecular weight of 1,000 to 1,000,000. <1> Regarding the episulfide resin described.

[0012] <3> The present invention comprises 50 to 99% by mass of a constituent unit represented by general formula (1) and 1 to 30% by mass of a constituent unit represented by general formula (2). <1> or <2> Regarding the episulfide resin described.

[0013] <4> The present invention <1> ~ <3> This invention relates to a curable resin composition comprising an episulfide resin as described in any one of the items, and a curing initiator.

[0014] <5> The present invention contains 0.001 to 100% by mass of a curing initiator based on the mass of the episulfide resin. <4> This relates to the curable resin composition described.

[0015] <6> The present invention <4> or <5> This relates to a cured film formed using the curable resin composition described above. [Effects of the Invention]

[0016] The present invention provides an episulfide resin capable of achieving both low-temperature curability and long-term stability, a curable resin composition using the episulfide resin, and a cured film using the curable resin composition. [Modes for carrying out the invention]

[0017] <<Episulfide resin>> The episulfide resin of the present invention is characterized by having a constituent unit represented by the following general formula (1) and a constituent unit represented by the following general formula (2). By having the above constituent units, the episulfide resin of the present invention exhibits excellent low-temperature curability, long-term stability, and transparency. The present invention will be described in detail below.

[0018] General formula (1) [ka]

[0019] [In general formula (1), ring D represents an aliphatic ring having 5 to 10 carbon atoms, A represents a unit having 2 to 30 carbon atoms including a thiirane ring, B represents a direct bond or a divalent linking group, E represents an oxygen atom, a sulfur atom, a divalent linking group containing an oxygen atom, or a divalent linking group containing a sulfur atom, and n represents an integer of 1 or more.]

[0020] General formula (2) [ka]

[0021] [In general formula (2), ring F represents an aliphatic ring having 5 to 10 carbon atoms, J represents a direct bond or a divalent linking group, G represents a direct bond or a divalent linking group, I represents an oxygen atom, a sulfur atom, a divalent linking group containing an oxygen atom, or a divalent linking group containing a sulfur atom, L and K each independently represent a hydrogen atom or a monovalent organic group, Y represents a hydrogen atom or a methyl group, and m represents an integer of 1 or more.]

[0022] In general formulas (1) and (2), ring D and ring F are each independently aliphatic rings having 5 to 10 carbon atoms. By having a rigid structure such as aliphatic rings having 5 to 10 carbon atoms in the episulfide resin, reactivity can be controlled and stability over time can be imparted. Preferably, each is independently an aliphatic ring having 5 to 8 carbon atoms, and more preferably an aliphatic ring having 5 to 7 carbon atoms.

[0023] In general formula (1), A is a unit having 2 to 30 carbon atoms and containing a thiirane ring. From the viewpoint of low-temperature curability and stability over time, it is preferably 2 to 20 carbon atoms, more preferably 2 to 10, and even more preferably 2 to 5, with 2 being particularly preferred from the viewpoint of low-temperature curability. For example, it may be a monovalent substituent containing a thiirane ring. The substituents are not particularly limited, but examples include alkyl groups, alkenyl groups, ether groups, ester groups, alkylene ether groups, cycloalkyl groups, aryl groups, phenyl groups, urea groups, urethane groups, carbonate groups, thioether groups, thioester groups, thiourethane groups, thiourea groups, thiocarbonate groups, and alkylenthioether groups.

[0024] In general formula (2), K and L each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited and includes, for example, an optionally substituted alkyl group, an optionally substituted alkynyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkyl group, an optionally substituted oxyalkyl group, an optionally substituted thioalkyl group, and an optionally substituted aryl group. Optional substituents include, for example, alkyl groups, alkenyl groups, cycloalkyl groups, oxyalkyl groups, thioalkyl groups, aryl groups, hydroxyl groups, carboxyl groups, halogen atoms, mercapto groups, ester groups, thioester groups, and acyl groups, and may have multiple substituents. Preferably, K and L are groups having 30 or fewer carbon atoms, such as a hydrogen atom, an optionally substituted alkyl group, an optionally substituted oxyalkyl group, an optionally substituted thioalkyl group, or an optionally substituted aryl group. More preferably, they are a hydrogen atom, an alkyl group, an oxyalkyl group, or a thioalkyl group, and even more preferably, a hydrogen atom. In general formula (2), K and L are hydrogen atoms or the monovalent organic groups described above, which is preferable because it provides excellent low-temperature curability, long-term stability, and transparency.

[0025] In general formulas (1) and (2), B, J, and G each independently represent a direct bond or a divalent linking group. Examples of the above divalent linking groups include ester bonds, optionally substituted alkylene groups, optionally substituted oxyalkylene groups, optionally substituted thioalkylene groups, optionally substituted arylene groups, optionally substituted alkelen groups, and optionally substituted cycloalkylene groups, and multiple of the above may be linked together. Examples of optionally substituted groups include alkyl groups, alkenyl groups, cycloalkyl groups, oxyalkyl groups, thioalkyl groups, aryl groups, hydroxyl groups, carboxyl groups, halogen atoms, mercapto groups, ester groups, thioester groups, acyl groups, carbamate groups, thiocarbamate groups, urea groups, thiourea groups, carbonate groups, thiocarbonate groups, (meth)acrylate groups, ether groups, thioether groups, and cycloalkenyl groups, and multiple substituents may be present. In general formulas (1) and (2), B, J, and G are preferred because they are directly bonded or are the divalent linking groups described above, resulting in excellent low-temperature curability, long-term stability, and transparency.

[0026] B and J are each independently preferably directly bonded or a divalent linking group having 1 to 30 carbon atoms, more preferably directly bonded or a divalent linking group having 1 to 15 carbon atoms, even more preferably directly bonded or an alkylene group having 1 to 10 carbon atoms, even more preferably directly bonded or an alkylene group having 1 to 5 carbon atoms, and particularly preferably directly bonded.

[0027] G is preferably a directly bonded or divalent linking group having 1 to 30 carbon atoms, more preferably a group formed by linking a directly bonded, ester bonded, or thioester bonded with an alkylene group having 1 to 25 carbon atoms which may have substituents, an alkylene group having 1 to 25 carbon atoms which may have substituents, a group formed by linking an ester bonded or thioester bonded with an alkenyl group having 1 to 25 carbon atoms which may have substituents, an oxyalkylene group having 1 to 25 carbon atoms which may have substituents, a thioalkylene group having 1 to 25 carbon atoms which may have substituents, or an alkenylene group having 1 to 25 carbon atoms which may have substituents, and even more preferably a group formed by linking a directly bonded, ester bonded, or thioester bonded with an alkylene group having 1 to 20 carbon atoms which may have substituents, or a substituted group The group is preferably an alkylene group having 1 to 20 carbon atoms, a group formed by linking an ester bond or a thioester bond with an alkenyl group having 1 to 20 carbon atoms which may have substituents, an alkylene group having 1 to 20 carbon atoms which may have substituents, a thioalkylene group having 1 to 20 carbon atoms which may have substituents, or an oxyalkylene group having 1 to 20 carbon atoms which may have substituents. More preferably, the group is directly bonded, or formed by linking an ester bond with an alkylene group having 1 to 15 carbon atoms which may have substituents, or an alkenylene group having 1 to 15 carbon atoms which may have substituents, or an alkylene group having 1 to 15 carbon atoms which may have substituents. More preferably, the group is directly bonded, or formed by linking an ester bond with an alkylene group having 1 to 5 carbon atoms which may have substituents. From the viewpoint of stability over time, the direct bond is particularly preferred. Preferably, substituents that may be present include alkyl groups, alkenyl groups, cycloalkyl groups, oxyalkyl groups, thioalkyl groups, aryl groups, hydroxyl groups, carboxyl groups, mercapto groups, ester groups, thioester groups, carbamate groups, thiocarbamate groups, phenyl groups, (meth)acrylate groups, urea groups, carbonate groups, ether groups, thioether groups, thiourea groups, thiocarbonate groups, cycloalkenyl groups, and the like. Particularly preferred substituents are alkyl groups, hydroxyl groups, carboxyl groups, mercapto groups, ester groups, thioester groups, carbamate groups, thiocarbamate groups, phenyl groups, aryl groups, and (meth)acrylate groups, and there may be multiple substituents.

[0028] In general formulas (1) and (2), E and I each independently represent an oxygen atom, a sulfur atom, a divalent linking group containing an oxygen atom, or a divalent linking group containing a sulfur atom. The fact that E and I are the aforementioned atoms or divalent linking groups gives the curable resin composition of the present invention excellent low-temperature curability, long-term stability, and transparency. E and I are each preferably independently an oxygen atom, a sulfur atom, an oxyalkyl group having 1 to 30 carbon atoms which may have substituents, or an thioalkyl group having 1 to 30 carbon atoms which may have substituents; more preferably an oxygen atom, a sulfur atom, an oxyalkyl group having 1 to 10 carbon atoms, or an thioalkyl group having 1 to 10 carbon atoms; even more preferably an oxygen atom, a sulfur atom, an oxyalkyl group having 1 to 5 carbon atoms, or an thioalkyl group having 1 to 5 carbon atoms; and even more preferably an oxygen atom and a sulfur atom, with oxygen being particularly preferred from the viewpoint of low-temperature curability.

[0029] The general formula (1) is preferably general formula (3).

[0030] General formula (3) [ka]

[0031] [In general formula (3), ring RA represents an aliphatic ring having 5 to 10 carbon atoms, TA represents a direct bond or a divalent linking group, UA represents an oxygen atom, a sulfur atom, a divalent linking group containing an oxygen atom, or a divalent linking group containing a sulfur atom, XA is a direct bond or a divalent linking group having 1 to 28 carbon atoms, QA and ZA each independently represent a hydrogen atom or a monovalent organic group having 1 to 28 carbon atoms, the sum of the carbon atoms in XA, QA, and ZA is 28 or less, and na represents an integer of 1 or more.]

[0032] In general formula (3), the ring RA can be described by referring to the description of ring D in general formula (1) above.

[0033] In general formula (3), UA can be derived from the description of E in general formula (1) above.

[0034] In general formula (3), TA can be derived from the description of B in general formula (1) above.

[0035] In general formula (3), QA and ZA each independently represent a hydrogen atom or a monovalent organic group having 1 to 28 carbon atoms. The monovalent organic group is not particularly limited and includes, for example, an optionally substituted alkyl group, an optionally substituted alkynyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkyl group, an optionally substituted oxyalkyl group, an optionally substituted thioalkyl group, and an optionally substituted aryl group. Optional substituents include, for example, alkyl groups, alkenyl groups, cycloalkyl groups, oxyalkyl groups, thioalkyl groups, aryl groups, hydroxyl groups, carboxyl groups, halogen atoms, mercapto groups, ester groups, thioester groups, and acyl groups, and may have multiple substituents. QA and ZA are more preferably a hydrogen atom, an alkyl group, an oxyalkyl group, or a thioalkyl group, and even more preferably a hydrogen atom.

[0036] In general formula (3), XA is a directly bonded or divalent linking group having 1 to 28 carbon atoms, preferably a directly bonded or divalent linking group having 1 to 18 carbon atoms from the viewpoint of low-temperature curability and stability over time, more preferably a directly bonded or divalent linking group having 1 to 8 carbon atoms, even more preferably a directly bonded or divalent linking group having 1 to 3 carbon atoms, and particularly preferably a directly bonded in the viewpoint of low-temperature curability. The divalent linking group is not particularly limited, but examples include alkylene groups, alkenylene groups, alkylylene groups, cycloalkylene groups, ether groups, ester groups, alkylene ether groups, arylene groups, phenylene groups, thioether groups, thioester groups, alkylentioether groups, urea groups, urethane groups, carbonate groups, thiourethane groups, thiourea groups, thiocarbonate groups, etc., and may be combinations thereof, and may have substituents. The alkylene group, alkynyl group, alkenylene group, or alkynylene group may be linear, branched, cyclic, or a combination thereof. Among the divalent linking groups, alkylene groups, alkenylene groups, ether groups, ester groups, alkylene ether groups, thioether groups, thioester groups, alkylentioether groups, urea groups, urethane groups, carbonate groups, thiourethane groups, thiourea groups, and thiocarbonate groups are preferred, and particularly preferred are alkylene groups, alkynyl groups, alkenylene groups, ether groups, ester groups, alkylene ether groups, thioether groups, thioester groups, alkylentioether groups, urea groups, urethane groups, carbonate groups, thiourethane groups, thiourea groups, and thiocarbonate groups.

[0037] In general formula (3), the sum of the number of carbon atoms in XA, QA, and ZA is 28 or less. For example, XA may be directly bonded, and QA and ZA may be hydrogen atoms, and the sum of the number of carbon atoms may be 0.

[0038] In general formulas (1), (2), and (3), the total number of carbon atoms in B and E, the total number of carbon atoms in I and J, and the total number of carbon atoms in TA and UA are not particularly limited, but each is independently preferably 0 to 60, more preferably 0 to 30, even more preferably 0 to 15, and most preferably 0 to 8.

[0039] As general formula (2), any of general formulas (4-1), (4-2), or (4-3) is preferred.

[0040] General formula (4-1)

[0041] [ka]

[0042] [In general formula (4-1), ring WB represents an aliphatic ring having 5 to 10 carbon atoms, VB represents a direct bond or a divalent linking group, βB represents a direct bond or a divalent linking group containing one or more selected from the group consisting of alkylene, alkenylene, ether, alkylene ether, thioether, alkylentione ether, ester, thioester, carbamate, urea, thiocarbamate, thiourea, carbonate, and thiocarbonate groups, αB represents an oxygen atom, a sulfur atom, a divalent linking group containing an oxygen atom, or a divalent linking group containing a sulfur atom, γB represents a hydrogen atom or a methyl group, and mb represents an integer of 1 or more.]

[0043] In general formula (4-1), the description of ring F in general formula (2) above can be used for ring WB.

[0044] In general formula (4-1), αB can be derived from the description in general formula (2)I above.

[0045] In general formula (4-1), VB can be derived from the description of general formula (2)J above.

[0046] In general formula (4-1), γB can be derived from the description of general formula (2)Y above.

[0047] In general formula (4-1), βB represents a direct bond or a divalent linking group comprising one or more selected from the group consisting of alkylene groups, alkenylene groups, ether groups, alkylene ether groups, thioether groups, alkylentione ether groups, ester groups, thioester groups, carbamate groups, urea groups, thiocarbamate groups, thiourea groups, carbonate groups, and thiocarbonate groups. From the viewpoint of low-temperature curability and stability over time, βB is preferably a direct bond or a divalent linking group having 1 to 30 carbon atoms, more preferably a direct bond or a divalent linking group having 1 to 25 carbon atoms, even more preferably a direct bond or a divalent linking group having 1 to 15 carbon atoms, and even more preferably a direct bond or a divalent linking group having 1 to 5 carbon atoms, and from the viewpoint of stability over time, it is particularly preferably a direct bond.

[0048] General formula (4-2)

[0049] [ka]

[0050] In general formula (4-2), the ring WC represents an aliphatic ring having 5 to 10 carbon atoms, VC represents a direct bond or a divalent linking group, and δC and ηC are each independently directly bonded or contain one or more selected from the group consisting of alkylene groups, alkenylene groups, ether groups, alkylene ether groups, thioether groups, alkylentioether groups, ester groups, thioester groups, carbamate groups, urea groups, thiocarbamate groups, thiourea groups, carbonate groups, thiocarbonate groups, and cycloalkylene groups. εC represents a divalent linking group, εC represents a monovalent organic group containing any of the following: hydroxyl group, mercapto group, (meth)acrylate group, ester group, alkenyl group, ether group, alkylene ether group, thioether group, alkylentioether group, carbamate group, thiocarbamate group, carbonate group, or thiocarbonate group, αC represents an oxygen atom, sulfur atom, a divalent linking group containing an oxygen atom, or a divalent linking group containing a sulfur atom, γC represents a hydrogen atom or a methyl group, and mc represents an integer of 1 or more.

[0051] In general formula (4-2), the ring WC can be described by referring to the description of ring F in general formula (2) above.

[0052] In general formula (4-2), αC can be derived from the description of I in general formula (2) above.

[0053] In general formula (4-2), VC can be derived from the description of J in general formula (2) above.

[0054] In general formula (4-2), γC can be derived from the description of Y in general formula (2) above.

[0055] In general formula (4-2), the divalent linking groups of δC and ηC are preferably divalent linking groups containing any of an alkylene group, alkenylene group, ether group, alkylene ether group, thioether group, alkylentioether group, ester group, or thioester group, and more preferably divalent linking groups containing any of an alkenyl group, ether group, alkylene ether group, or ester group. The divalent linking group may have two or more of these groups.

[0056] In general formula (4-2), δC may be, for example, a direct bond or a divalent linking group having 1 to 29 carbon atoms, and is particularly preferred to be a direct bond.

[0057] In general formula (4-2), ηC may be a direct bond or a divalent linking group having 1 to 29 carbon atoms. From the viewpoint of low-temperature curability and stability over time, it is preferably a divalent linking group having 1 to 15 carbon atoms, and more preferably a divalent linking group having 1 to 5 carbon atoms.

[0058] In general formula (4-2), the monovalent organic group of εC is preferably a monovalent organic group comprising any of a hydroxyl group, a mercapto group, a (meth)acrylate group, an ester group, an ether group, an alkylene ether group, a thioether group, an alkylentioether group, a carbamate group, a thiocarbamate group, a carbonate group, or a thiocarbonate group; more preferably a monovalent organic group comprising any of a hydroxyl group, a mercapto group, a (meth)acrylate group, an ester group, a carbamate group, or a thiocarbamate group; and even more preferably a monovalent organic group comprising any of a hydroxyl group or a mercapto group.

[0059] In general formula (4-2), the total number of carbon atoms in δC, ηC, and εC is preferably 1 to 29, preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5, from the viewpoint of low-temperature curability and stability over time.

[0060] General formula (4-3)

[0061] [ka]

[0062] In general formula (4-3), ring WD represents an aliphatic ring with 5 to 10 carbon atoms, and VD represents a direct bond or a divalent linking group. δD and ηD each independently represent a direct bond or a divalent linking group containing one or more selected from the group consisting of alkylene groups, alkenylene groups, ether groups, alkylene ether groups, thioether groups, alkylentioether groups, ester groups, thioester groups, carbamate groups, urea groups, thiocarbamate groups, thiourea groups, carbonate groups, thiocarbonate groups, and cycloalkylene groups. LD represents *-COO-, *-COS-, *-NHCOO-, *-NHCOS- (where * represents a coupling with εD), εD is a monovalent organic group comprising one or more selected from the group consisting of a hydroxyl group, a mercapto group, a (meth)acrylate group, an ester group, a thioester group, an alkylene group, an alkenylene group, an ether group, an alkylene ether group, a thioether group, an alkylentioether group, a carbamate group, a thiocarbamate group, a carbonate group, a thiocarbonate group, a cycloalkylene group, a cycloalkenylene group, an aryl group, an arylene group, a phenyl group, a phenylene group, and a carboxyl group. αD represents an oxygen atom, a sulfur atom, a divalent linking group containing an oxygen atom, or a divalent linking group containing a sulfur atom; γD represents a hydrogen atom or a methyl group; and md represents an integer of 1 or more.

[0063] In general formula (4-3), the ring WD can be described by referring to the description of ring F in general formula (2) above.

[0064] In general formula (4-3), αD can be derived from the description of I in general formula (2) above.

[0065] In general formula (4-3), VD can be derived from the description of J in general formula (2) above.

[0066] In general formula (4-3), γD can be derived from the description of Y in general formula (2) above.

[0067] In general formula (4-3), the divalent linking groups δD and ηD are preferably divalent linking groups containing any of an alkylene group, alkenylene group, ether group, alkylene ether group, thioether group, alkylentioether group, ester group, thioester group, or cycloalkylene group, and more preferably divalent linking groups containing any of an alkylene group, alkenyl group, ether group, alkylene ether group, ester group, or cycloalkylene group. The divalent linking group may have two or more of these groups.

[0068] In general formula (4-3), δD may be, for example, a direct bond or a divalent linking group having 1 to 28 carbon atoms, and is particularly preferred to be a direct bond.

[0069] In general formula (4-3), ηD may be a direct bond or a divalent atom with 1 to 28 carbon atoms. From the viewpoint of low-temperature curability and long-term stability, the linking group is preferably a divalent group having 1 to 15 carbon atoms, and more preferably a divalent linking group having 1 to 5 carbon atoms.

[0070] In general formula (4-3), εD is preferably a monovalent organic group containing any of a hydroxyl group, a (meth)acrylate group, a carboxyl group, or an alkylene group.

[0071] In general formula (4-3), the total number of carbon atoms in δD, ηD, LD, and εD is 1 to 29, preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5, from the viewpoint of low-temperature curability and long-term stability.

[0072] The episulfide resin of the present invention preferably contains 50% by mass or more of the constituent unit represented by general formula (1) from the viewpoint of low-temperature curability, long-term stability, and transparency. More preferably, it contains 55% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more from the viewpoint of low-temperature curability. Also from the same viewpoint, it preferably contains 99% by mass or less of the constituent unit represented by general formula (1), for example, 50-99% by mass, 55-99% by mass, 70-99% by mass, or 80-99% by mass. Furthermore, the episulfide resin of the present invention preferably contains 1% by mass or more of the constituent unit represented by general formula (2) from the viewpoint of low-temperature curability, long-term stability, and transparency. In particular, from the viewpoint of long-term stability, it preferably contains 55% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and especially preferably 10% by mass or less of the constituent unit represented by general formula (2), for example, 1 to 55% by mass, 1 to 30% by mass, 1 to 20% by mass, or 1 to 10% by mass. The proportion of the above constituent units in episulfide resin can be determined by NMR (nuclear magnetic resonance) or IR (infrared spectroscopy) analysis.

[0073] The episulfide resin preferably has a weight-average molecular weight (Mw) of 1,000 or more. Furthermore, from the viewpoint of low-temperature curability and long-term stability, it is preferably 1,000,000 or less, more preferably 500,000 or less, even more preferably 100,000 or less, and particularly preferably 50,000 or less. For example, it may be 1,000 to 1,000,000, 1,000 to 500,000, 1,000 to 100,000, or 1,000 to 50,000.

[0074] In this specification, the weight-average molecular weight (Mw) can be determined by calculating the polystyrene equivalent value obtained by GPC (gel permeation chromatography). Specifically, the resin can be dissolved in tetrahydrofuran to prepare a 1% by mass solution, and then measured using the following apparatus and measurement conditions. Equipment: HLC-8420-GPC system (manufactured by Tosoh Corporation) Columns: TSK-GELGuardColumnSuperHZ-L and two TSK-GELSUPERHZM-N columns connected in series. Leaching solvent: Tetrahydrofuran Standard material: Polystyrene (manufactured by Tosoh Corporation) Flow rate: 0.35mL / min, Sample solution usage: 10 μL Column temperature: 40°C

[0075] From the viewpoint of transparency, the episulfide equivalent (mmol / g) of the episulfide resin is preferably 7.0 mmol / g or less, more preferably 6.5 mmol / g or less. Also from the same viewpoint, it is preferably 0.5 mmol / g or more, more preferably 1.0 mmol / g or more, more preferably 2.0 mmol / g or more, more preferably 3.5 mmol / g or more, and even more preferably 4.0 mmol / g or more. For example, it may be 0.5 to 7.0 mmol / g, 1.0 to 7.0 mmol / g, 2.0 to 7.0 mmol / g, 3.5 to 6.5 mmol / g, or 4.0 to 6.5 mmol / g or more.

[0076] The episulfide resin of the present invention may contain other constituent units in addition to the constituent units represented by general formula (1) and general formula (2), as long as the effects of the present invention are not impaired. The episulfide resin of the present invention may or may not contain other constituent units, may contain only one type of other constituent unit, or may contain two or more types.

[0077] Other constituent units may include, but are not limited to, (meth)acrylate groups, epoxy groups, episulfide groups, mercapto groups, amino groups, hydroxyl groups, carboxyl groups, oxetane groups, blocked isocyanate groups, allyl groups, vinyl groups, phenyl groups, aryl groups, alkyl groups, alkanoyl groups, alkenyl groups, alkenylene groups, alkynyl groups, alkylene groups, or functional groups having an alicyclic skeleton. From the viewpoint of long-term stability, (meth)acrylate groups and alkyl groups are preferred.

[0078] <Method for producing episulfide resin> The method for producing the episulfide resin of the present invention is not particularly limited, and can be obtained by a production method comprising, for example, a first step of ring-opening polymerization using a monomer represented by the following general formula (5), a second step of epoxidizing the obtained polymer using an oxidizing agent or the like, and a third step of converting the epoxidized epoxy resin into episulfide.

[0079] [First step] In the first step, ring-opening polymerization is carried out using a monomer represented by the following general formula (5). The monomer may be used individually or in combination of two or more types.

[0080] General formula (5) [ka]

[0081] [In general formula (5), ring T represents an aliphatic ring having 5 to 10 carbon atoms, Q represents a direct bond or a divalent linking group, R represents an oxygen atom, a sulfur atom, a divalent linking group having an oxygen atom, or a divalent linking group having a sulfur atom, U represents a direct bond or a divalent linking group, Z represents a hydrogen atom or a methyl group, and V and W each independently represent a hydrogen atom or a monovalent organic group.]

[0082] In general formula (5), ring T is an aliphatic ring having 5 to 10 carbon atoms, preferably an aliphatic ring having 5 to 8 carbon atoms, and more preferably an aliphatic ring having 5 to 7 carbon atoms.

[0083] In general formula (5), Q and U each independently represent a direct bond or a divalent linking group. Examples of the above-mentioned divalent linking groups include ester bonds, optionally substituted alkylene groups, optionally substituted oxyalkylene groups, optionally substituted thioalkylene groups, optionally substituted arylene groups, optionally substituted alkelen groups, and optionally substituted cycloalkylene groups, and multiple of the above may be linked together. Examples of substituents that may be present include alkyl groups, alkenyl groups, cycloalkyl groups, oxyalkyl groups, thioalkyl groups, aryl groups, hydroxyl groups, carboxyl groups, halogen atoms, mercapto groups, ester groups, thioester groups, acyl groups, carbamate groups, and thiocarbamate groups, and there may be multiple substituents. Q is preferably a direct bond or a divalent linking group having 1 to 10 carbon atoms, more preferably a direct bond or a divalent linking group having 1 to 5 carbon atoms, and more preferably a direct bond. U can be represented by the description of G in general formula (2) described above. Preferably, it is a direct bond or a divalent linking group having 1 to 30 carbon atoms, more preferably a direct bond or a divalent linking group having 1 to 25 carbon atoms, even more preferably a direct bond or a divalent linking group having 1 to 10 carbon atoms, and particularly preferably a direct bond.

[0084] In general formula (5), R represents an oxygen atom, a sulfur atom, a divalent linking group having an oxygen atom, or a divalent linking group having a sulfur atom, and the number of atoms in R is preferably 25 or less, more preferably 15 or less, even more preferably 10 or less, and particularly preferably 5 or less. The descriptions of Q and U above can be used as a divalent linking group. R preferably represents an oxygen atom, a sulfur atom, or a divalent linking group having an oxygen atom, more preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom.

[0085] In general formula (5), the total number of Q and R atoms is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10.

[0086] In general formula (5), V and W each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited and includes, for example, an optionally substituted alkyl group, an optionally substituted alkynyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkyl group, an optionally substituted oxyalkyl group, an optionally substituted thioalkyl group, and an optionally substituted aryl group. Optional substituents include, for example, alkyl groups, alkenyl groups, cycloalkyl groups, oxyalkyl groups, thioalkyl groups, aryl groups, hydroxyl groups, carboxyl groups, halogen atoms, mercapto groups, ester groups, thioester groups, and acyl groups, and may have multiple substituents. Preferably, V and W are groups having 30 or fewer carbon atoms, such as a hydrogen atom, an optionally substituted alkyl group, an optionally substituted oxyalkyl group, an optionally substituted thioalkyl group, or an optionally substituted aryl group. More preferably, they are a hydrogen atom, an alkyl group, an oxyalkyl group, or a thioalkyl group, and even more preferably, a hydrogen atom.

[0087] (Monomer represented by general formula (5)) The monomer represented by general formula (5) is not particularly limited, and examples include vinylcyclohexene oxide, vinylcyclopentene oxide, vinylcycloheptane oxide, 3,4-epoxycyclohexanecarboxylate allyl, (epoxycyclohexyl)methyl acrylate, vinylcyclohexene sulfide, vinylcyclopentene sulfide, vinylcycloheptane sulfide, 3,4-episulfidecyclohexanecarboxylate allyl, (episulfidecyclohexyl)methyl acrylate, and the like. From the viewpoint of reactivity, compounds having an unsaturated group containing a carbon-carbon double bond at the terminal are preferred, and compounds having a carbon-carbon double bond at the terminal are preferred.

[0088] The monomer represented by general formula (5) is preferably a compound having a heterocyclic skeleton containing 3 to 10 sulfur or oxygen atoms, more preferably a compound having a heterocyclic skeleton containing 3 to 5 sulfur or oxygen atoms, even more preferably a compound having one of the following skeletons: epoxy, episulfide, oxetane, or thiumane, even more preferably a compound having one of the following skeletons: epoxy or episulfide, and even more preferably an epoxy skeleton.

[0089] The first step, ring-opening polymerization, may involve copolymerizing monomers other than those represented by general formula (5), or copolymerizing monomers having any functional group. By copolymerizing monomers having any functional group, a desired functional group can be introduced into the episulfide resin. Furthermore, another functional group may be introduced by further modification using the introduced functional group, epoxy group, or episulfide group. Modification can be performed before or after any of the steps.

[0090] (Polymerization initiator) In the first step, an organic compound having active hydrogen may be used as a polymerization initiator. Examples of the organic compound having active hydrogen include alcohols, phenols, carboxylic acids, amines, and thiols, preferably alcohols, carboxylic acids, and thiols, and more preferably alcohols.

[0091] Examples of alcohols include aliphatic alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, and methoxybutanol; aromatic alcohols such as benzyl alcohol; and polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, propylene glycol monomethyl ether, butanediol, pentanediol, hexanediol, neopentyl glycol, neopentyl glycol ester of oxypivalate, cyclohexanedimethanol, glycerin, diglycerin, polyglycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Preferably, the alcohols are aliphatic or polyhydric alcohols, and more preferably polyhydric alcohols. The aliphatic alcohols are preferably methanol, ethanol, propanol, hexanol, and octanol. The polyhydric alcohols are preferably trimethylolpropane, pentaerythritol, dipentaerythritol, ethylene glycol, propylene glycol butanediol, and hexanediol.

[0092] Examples of phenols include phenol, cresol, catechol, pyrogallol, hydroquinone, hydroquinone monomethyl ether, bisphenol A, bisphenol F, 4,4'-dihydroxybenzophenone, bisphenol S, phenol resins, and cresol novolac resins.

[0093] Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, fatty acids from animal and vegetable oils, fumaric acid, maleic acid, adipic acid, dodecane di acid, trimellitic acid, pyromellitic acid, polyacrylic acid, phthalic acid, isophthalic acid, and terephthalic acid. Compounds having both hydroxyl and carboxyl groups, such as lactic acid, citric acid, and oxycaproic acid, may also be used.

[0094] Examples of amines include monomethylamine, dimethylamine, monoethylamine, diethylamine, propylamine, monobutylamine, dibutylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, dodecylamine, 4,4'-diaminodiphenylmethane, isophoronediamine, toluenediamine, hexamethylenediamine, xylenediamine, diethylenetriamine, triethylenetetramine, and ethanolamine.

[0095] The thiols are not particularly limited, but for example, the thiol compounds listed in the (hardening components) section of [Other Components] described later can be used, and mercaptos and thiophenols are preferred. As for mercaptos, polyvalent mercaptos are preferably used. Examples of the above polyvalent mercaptos include 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, trimethylolpropanetris (mercaptopropionate), dipentaerythritol hexakis (mercaptopropionate), pentaerythritol tetrakis (mercaptopropionate), pentaerythritol tetrakis (mercaptobutyrate), trimethylolpropanetris (mercaptobutyrate), pentaerythritol tetrapropanthol, pentaerythritol tripropanthol, and trimethylolpropanedipropanthol.

[0096] Examples of organic compounds having active hydrogen other than those mentioned above include polyvinyl alcohol, polyvinyl acetate partial hydrolysate, starch, cellulose, cellulose acetate, cellulose acetate butyrate, hydroxyethylcellulose, acrylic polyol resin, styrene-allyl alcohol copolymer resin, styrene-maleic acid copolymer, alkyd resin, polyester polyol resin, polyester carboxylic acid resin, polycaprolactone polyol resin, polypropylene polyol, and polytetramethylene glycol. Furthermore, organic compounds having active hydrogen may also have unsaturated bonds in their skeletons, and examples of such compounds include allyl alcohol, acrylic acid, methacrylic acid, and tetrahydrophthalic acid.

[0097] (Polymerization catalyst) For the first step of ring-opening polymerization, it is preferable to use a polymerization catalyst. The polymerization catalyst is not particularly limited, but examples include Lewis acids or their complexes such as BF3, ZnCl2, AlCl3, SnCl4, mineral acids such as sulfuric acid and phosphoric acid, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, dimethylaminopyridine, methylaminopyridine, pyridine, triethylenediamine, piperidine, guanidine, imidazole, methylimidazole, 2-ethyl-4-methylimidazole, alkylamine, diazabicyclononene, diazabicycloundecene, diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, guanidine, acetoguanamine, and ben. Amines such as zoguanamine, ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-S-triazine, trimethylamine, triethanolamine, N,N-dimethyloctylamine, N-benzyldimethylamine, N-methylmorpholine, hexa(N-methyl)melamine, 2,4,6-tris(dimethylaminophenol), tetramethylguanidine, m-aminophenol, and their derivatives and salts, as well as curing initiators described later, can be used, but Lewis acids such as BF3, ZnCl2, AlCl3, and SnCl, or their complexes, are preferably used. The amount of polymerization catalyst is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.1 to 3% by mass, relative to the total amount of monomers.

[0098] (Reaction temperature) The reaction temperature is not particularly limited and may be, for example, -100°C to 150°C, preferably -100°C to 100°C.

[0099] (solvent) Ring-opening polymerization may be carried out in a solvent or without a solvent, but it is preferable to carry it out in the presence of a solvent. As for the solvent, for example, the solvents described in the section on episulfide reactions described later can be used, and solvents that do not contain active hydrogen are preferred, more preferably ketone solvents, ester solvents, ether solvents, aromatic solvents, aliphatic solvents, and alicyclic solvents, and even more preferably ketone solvents, ester solvents, aromatic solvents, and alicyclic solvents.

[0100] The first step, ring-opening polymerization, may involve cleavage at either the Q or R bond of the general formula (5) used as a raw material. While not particularly limited, general formula (5) can be used with epoxides, episulfides, etc., as the reaction site for ring-opening polymerization. For example, in ring-opening polymerization of general formula (5), cleavage can occur at either the Q'-C or R'-C bond, as shown below. [ka]

[0101] Generally, the fact that both α-cleavage and β-cleavage can occur in ring-opening polymerization is explained in detail, for example, in "Basic Polymer Chemistry, 2nd Edition (2020)" p28 (The Society of Polymer Science, Japan) and "Warren's Organic Chemistry (Vol. 1), 2nd Edition (2015)" pp447-448 (Tokyo Kagaku Dojin).

[0102] [Second process] In the second step, the polymer having vinyl groups obtained in the first step is treated with an oxidizing agent or the like to epoxidize it.

[0103] (Oxidizing agent) The oxidizing agents are not particularly limited, but include, for example, oxygen-containing gases, inorganic peroxides such as hydrogen peroxide, sodium peroxide, and potassium peroxysulfate; and organic peroxides such as peracetic acid, perbenzoic acid, m-chloroperbenzoic acid, p-nitroperbenzoic acid, magnesium monoperoxyphthalate, peroxymaleic acid, peroxytrifluoroacetic acid, peroxyphthalic acid, peroxylauric acid, tert-butyl hydroperoxide, cumene hydroperoxide, menthyl hydroperoxide, 1-methylhexane hydroperoxide, dimethyldioxirane, and methyltrifluoromethyldioxirane.

[0104] The amount of oxidizing agent used is not particularly limited and can be appropriately selected considering the amount of vinyl groups to be epoxidized. For example, the amount of oxidizing agent used may be 90 to 500 equivalents, or 95 to 300 equivalents, when the amount of vinyl groups to be converted to epoxy groups is considered to be 100 equivalents. Being within this range is preferable from the viewpoint of ensuring that the epoxidation reaction proceeds smoothly and from the viewpoint of economy.

[0105] (catalyst) Epoxylation reactions using oxidizing agents may use catalysts as needed. Examples of catalysts include metal compounds containing tungsten, molybdenum, vanadium, titanium, rhenium, ruthenium, etc.; aldehydes such as acetaldehyde, isobutyraldehyde, isovaleraldehyde, and trimethylacetaldehyde; α-aminophosphonic acids such as α-aminomethylphosphonic acid and α-aminoethylphosphonic acid; and quaternary onium salts such as trioctylmethylammonium chloride, trioctylethylammonium bromide, dilauryldimethylammonium iodide, and stearyldimethylbenzylammonium hydrogen phosphate.

[0106] (solvent) The epoxidation reaction may be carried out in a solvent or without a solvent, but it is preferable to carry it out in the presence of a solvent. As the solvent, one that does not react with the above-mentioned oxidizing agent can be used, for example, the solvents described in the episulfide reaction section below can be used. Preferably, the solvents are ketone solvents, ester solvents, ether solvents, aromatic solvents, aliphatic solvents, alicyclic solvents, halogen solvents, and amide solvents, and more preferably ketone solvents, ester solvents, aliphatic solvents, alicyclic solvents, halogen solvents, and amide solvents.

[0107] (Reaction temperature) The reaction temperature for the epoxidation reaction can be appropriately selected depending on the oxidizing agent, catalyst, and solvent used. Preferably, it is 0 to 150°C, more preferably 0 to 100°C.

[0108] [Third step] In the third step, the epoxy structure of the epoxy resin obtained in the second step is converted to episulfide. The epoxy structure converted to episulfide may be a part of the epoxy resin, and the converted episulfide resin may retain the epoxy structure. Examples of thiatting agents used in the conversion to episulfide include thiocyanates and thioureas. These thiatting agents may be used individually or in combination of two or more.

[0109] (Chia-inducing agent) Examples of thiocyanates include lithium thiocyanate, sodium thiocyanate, potassium thiocyanate, rubidium thiocyanate, cesium thiocyanate, silver thiocyanate, cobalt thiocyanate, mercuric thiocyanate, thallium thiocyanate, cuprous thiocyanate, lead dithiocyanate, nickel dithiocyanate, barium dithiocyanate, ammonium thiocyanate, and guanidine thiocyanate. Sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate are preferred due to their easy availability and excellent reactivity.

[0110] Examples of thioureas include thiourea, N,N'-dimethylthiourea, N,N,N',N'-tetramethylthiourea, N,N'-diethylthiourea, propylthiourea, N,N'-diisopropylthiourea, N,N'-dibutylthiourea, N-methyl-N'-(2-methyl-2-propenyl)thiourea, N-phenylthiourea, N,N'-diphenylthiourea, 1-methyl-2-imidazolidinthione, 1-benzyl-2-thiourea, N-(3,5-dimethylphenyl)thiourea, N-(2,6-dimethylphenyl)thiourea, N-(2,3-di Methylphenyl)thiourea, N-(2,4,6-trimethylphenyl)thiourea, N,N'-bis(2-methylphenyl)thiourea, N,N'-bis(3,5-dimethylphenyl)thiourea, N,N'-bis(2,6-dimethylphenyl)thiourea, N,N'-bis(2,4,6-trimethylphenyl)thiourea, N-(2-chlorophenyl)thiourea, N-(3-chlorophenyl)thiourea, N-(4-chlorophenyl)thiourea, N-(3,4-dichlorophenyl)thiourea, N-(3,5-dichlorophenyl)thiourea, N-(2,6-dichlorophenyl)thiourea N-(2,4,6-trichlorophenyl)thiourea, N,N'-bis(2-chlorophenyl)thiourea, N,N'-bis(3,5-dichlorophenyl)thiourea, N,N'-bis(2,6-dichlorophenyl)thiourea, N-(2-fluorophenyl)thiourea, N-(3-fluorophenyl)thiourea, N-(4-fluorophenyl)thiourea, N-[2-(trifluoromethyl)phenyl]thiourea, N-[3-(trifluoromethyl)phenyl]thiourea, N-[4-(trifluoromethyl)phenyl]thiourea, N- (2,6-difluorophenyl)thiourea, N-(2,4-difluorophenyl)thiourea, N-(2,3-difluorophenyl)thiourea, N-(2,4,6-trifluorophenyl)thiourea, N,N'-bis(2-fluorophenyl)thiourea, N,N'-bis(2,6-difluorophenyl)thiourea, N,N'-bis(2,4,6-trifluorophenyl)thiourea, N-(2-cyanophenyl)thiourea, N-(3-cyanophenyl)thiourea, N-(4-cyanophenyl)thiourea, N-(3,5-dicyanophenyl)thiourea, N,N'-bis(4-cyanophenyl)thiourea, N,N'-bis(3,5-dicyanophenyl)thiourea, N-(2-methoxyphenyl)thiourea, N-(3-methoxyphenyl)thiourea, N-(4-methoxyphenyl)thiourea, N-(2,6-dimethoxyphenyl)thiourea, N-(3,5-dimethoxyphenyl)thiourea, N-(2,4,6-tridimethoxyphenyl)thiourea, N,N'-bis(4-methoxyphenyl)thiourea, N,N' Examples include bis(2,6-dimethoxyphenyl)thiourea, N,N'-bis(2,4,6-tridimethoxyphenyl)thiourea, N-(2-nitrophenyl)thiourea, N-(3-nitrophenyl)thiourea, N-(4-nitrophenyl)thiourea, N-(3,5-dinitrophenyl)thiourea, and N,N'-bis(3,5-dinitrophenyl)thiourea. From the viewpoint of economy and reactivity, thioureas are preferred, and thiourea is more preferred.

[0111] The amount of thiazing agent used is not particularly limited and can be appropriately selected considering the amount of epoxy to be episulfidized. For example, the amount of thiazing agent used may be 90 to 500 equivalents, or 95 to 300 equivalents, when the amount of epoxy groups to be converted to episulfide is considered to be 100 equivalents. Being within this range is preferable from the viewpoint of ensuring that the episulfidation reaction proceeds smoothly and from the viewpoint of economy.

[0112] The episulfide reaction may be carried out in either a solvent or a solvent-free environment, but it is preferable to carry it out in the presence of a solvent. As solvents, for example, methanol, ethanol, propanol, isopropyl alcohol, butanol, isobutanol, sec-butanol, tert-butanol, pentanol, 3-methyl-1,3-butanediol, 1,3-butanediol, 1,3-butylene glycol, octanediol, 2,4-diethylpentanediol, butylethylpropanediol, 2-methyl-1,3-propanediol, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, isodecanol, isotridecanol, 3-methoxy-3-methyl-1-butanol, 2-methoxybutanol, 3-methoxybutanol, cyclohexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, benzyl alcohol, methylcyclohexanol, ethylene glycol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, ethylene glycol Diethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monotert-butyl ether, ethylene glycol monopropyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, 1,Alcohol-based solvents such as 3-butylene glycol, propylene glycol n-propyl ether, propylene glycol n-butyl ether, diethylene glycol monoethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, and tripropylene glycol n-butyl ether; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 4-heptanone, 3,5,5-trimethyl-2-cyclohexen-1-one, and 3,3,5-trimethylcyclohexanone; methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, ethyl 3-ethoxypropionate, ethyl lactate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and dipropylene glycol Ester solvents such as methyl ether acetate, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, propylene glycol monomethyl acetate, propylene glycol dimethyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, cyclohexanol acetate, propylene glycol diacetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol diacetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, etc.; diethyl ether, dipropyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1,Ether-based solvents such as 3-dioxolane, dioxane, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, dimethoxymethane, and dimethoxyethane; aromatic solvents such as benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, n-butylbenzene, sec-butylbenzene, and tert-butylbenzene; alicyclic solvents such as methylcyclohexane, cycloheptane, and cyclohexane; pentane and hexane Aliphatic solvents such as heptane, octane, isohexane, isooctane, and isononane; halogenated solvents such as dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, m-dichlorobenzene, and 1,2,3-trichloropropane; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and dimethylacetamide; nitrile solvents such as acetonitrile, propionitrile, and benzonitrile; and water.

[0113] These solvents may be used individually or in mixtures of two or more. In particular, it is preferable to use an alcohol-based solvent, or a mixture of an alcohol-based solvent and two or more other solvents, and more preferably a mixture of an alcohol-based solvent and two or more other solvents. Preferred alcohol-based solvents are methanol, ethanol, propanol, isopropyl alcohol, and butanol.

[0114] (Reaction aid) In the episulfide reaction, reaction aids such as crown ethers and porous adsorbents may be used to promote the reaction between the epoxy resin and the thiazing agent. One reaction aid may be used alone, or two or more may be used in combination, preferably a combination of crown ether and porous adsorbent.

[0115] [Crown Ether] The crown ether can be any macrocyclic compound having heteroatoms such as oxygen, nitrogen, or sulfur, and from an economic standpoint, a crown ether containing an oxygen atom as a heteroatom is preferred. The crown ether may be used alone or in combination of two or more types. The mixing ratio of the crown ether to the epoxy resin (mass of crown ether / mass of epoxy resin) is preferably 1 / 50 to 1 / 5000, more preferably 1 / 100 to 1 / 3000, and even more preferably 1 / 300 to 1 / 2000.

[0116] [Porous adsorbent] The porous adsorbent can be a conventional porous adsorbent or an inorganic porous adsorbent, such as activated carbon, zeolite, molecular sieve, amorphous silica, silica gel, bentonite, activated alumina, or activated clay. These porous adsorbents may be used individually or in combination of two or more. Molecular sieves are particularly preferred.

[0117] The molecular sieve may be of any type, such as 3A, 4A, 5A, or 13X. The average pore size of the molecular sieve is not particularly limited, but is preferably 1 to 50 Å, more preferably 2 to 20 Å. The shape of the porous adsorbent is not particularly limited, but examples include powder, granular, cylindrical, spherical (perfectly spherical, nearly spherical, etc.), ellipsoidal, polygonal (pyramidal, tetragonal, rectangular, etc.), plate-like, rod-like, fibrous, and irregular shapes. The molecular sieves may be of the same shape or a combination of different shapes.

[0118] The mixing ratio of the porous adsorbent to the epoxy resin (mass of porous adsorbent / mass of epoxy resin) is preferably 1 / 0.01 to 1 / 1000, more preferably 1 / 0.1 to 1 / 500, and even more preferably 1 / 1 to 1 / 100.

[0119] (Reaction temperature, etc.) The reaction temperature for the episulfide reaction is not particularly limited, but is preferably -100 to 150°C, and more preferably 10 to 80°C. The reaction time for the episulfide reaction is not particularly limited, but is preferably 1 to 100 hours, and more preferably 3 to 50 hours. The episulfide reaction may be carried out under normal pressure, under pressurized or reduced pressure. It may also be carried out under an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, or in the presence of oxygen such as air.

[0120] An episulfide resin is obtained by the episulfide reaction described above. After the episulfide reaction is completed, the obtained episulfide resin may be separated and purified. Examples of separation and purification methods include washing with water, acid washing, alkaline washing, filtration, concentration, extraction, liquid-liquid washing, crystallization, recrystallization, column chromatography, and combinations thereof.

[0121] (Introduction of functional groups) The process for producing episulfide resin may further include a step of modifying the resin and introducing a desired functional group into the resin. For example, a method for introducing the desired functional group is: (1) A method of introducing functional groups for reaction sites by copolymerizing arbitrary monomers in the first step, and introducing the desired functional group using some or all of the functional groups as reaction sites. (2) A method in which the carbon-carbon double bond of the epoxy resin precursor obtained in the first step is used as a reaction site to introduce the desired functional group, and the remaining carbon-carbon double bond is converted to episulfide through the second and third steps. (3) A method in which a portion of the epoxy resin obtained in the second step is used as a reaction site to introduce the desired functional group, and the remaining epoxy is converted to episulfide in the third step, and (4) A method is to introduce the desired functional group by using a portion of the episulfide converted in the third step as a reaction site. The functional groups introduced as reaction sites at the carbon-carbon double bond in (2), the epoxy in part of the epoxy resin in (3), and part of the episulfide in (4) may be functional groups for reaction sites, and some or all of these functional groups may be used as reaction sites to introduce the desired functional group.

[0122] Examples of target functional groups include carboxyl groups, hydroxyl groups, mercapto groups, amino groups, ethylenically unsaturated bonds, alkyl groups, alkenyl groups, alkynyl groups, epoxy groups, episulfide groups, oxetane groups, aziridine groups, ether groups, and thioether groups.

[0123] The functional group used for the reaction site is not particularly limited, but for example, epoxy groups, episulfide groups, oxetane groups, thietan groups, etc. of resins may be used. In this case, two patterns of cleavage, α-cleavage and β-cleavage, can occur, but they are not distinguished.

[0124] (Reaction aid) The process for producing episulfide resin may further include reaction accelerators as reaction aids. Reaction accelerators are not particularly limited and include, for example, inorganic acids such as nitric acid, sulfuric acid, hydrochloric acid, and phosphoric acid; organic acids such as acetic acid and propionic acid; bases such as methylaminopyridine, dimethylaminopyridine, triethylamine, diazabicycloundecene, diazabicyclooctane, hexamethylenetetramine, and dimethylbenzylamine; metal complexes such as dibutyltin dilaurate and dioctyltin dilaurate; salts such as tetrabutylammonium chloride, trimethylbenzylammonium chloride, and potassium acetate; crown ethers, and porous adsorbents.

[0125] The method for introducing other constituent units into the episulfide resin is not particularly limited, but in addition to the method described above (introduction of functional groups), any monomer may be copolymerized and introduced in the first step.

[0126] In this case, the monomer used is not particularly limited, but compounds having epoxy groups, episulfide groups, oxetane groups, thietan groups, tetrahydrofurfuryl groups, furfuryl groups, thiophene groups, tetrahydrothiophene groups, etc., can be used. Furthermore, although not particularly limited, the monomer used may also contain, in addition to the functional groups listed above, any of the following functional groups: (meth)acrylate group, mercapto group, amino group, hydroxyl group, carboxyl group, blocked isocyanate group, allyl group, vinyl group, phenyl group, aryl group, alkyl group, alkanoyl group, alkenyl group, alkynyl group, alkylene group, functional group having an alicyclic skeleton, etc.

[0127] <Curable resin composition> The curable resin composition of the present invention contains the episulfide resin described above and a curing initiator.

[0128] [Curing Initiator] Examples of curing initiators include acid initiators, base initiators, radical initiators, and other initiators. The curing initiator may be used as is or in a latent form. Latent curing initiators are preferred because they can be generated by light, heat, etc., and heat is particularly preferred. One type of curing initiator may be used alone or two or more types may be used in mixture. Preferably, the mixture contains at least one selected from the group consisting of acid initiators and base initiators, more preferably an acid initiator, a base initiator, a combination of an acid initiator and a radical initiator, or a combination of a base initiator and a radical initiator, and even more preferably a base initiator or a combination of a base initiator and a radical initiator.

[0129] The curing initiator content is preferably 0.001 to 100% by mass, more preferably 0.01 to 75% by mass, even more preferably 0.05 to 50% by mass, and most preferably 0.05 to 30% by mass, based on the mass of the episulfide resin. This range of curing initiator content is particularly preferable because it provides excellent low-temperature curability, long-term stability, and transparency.

[0130] (Base initiator) The base initiator is not particularly limited as long as it is a basic compound involved in the curing reaction, but examples include amines, pyridines, imidazoles, guanidines, and amidines. These may be used individually or in combination of two or more. Preferably, pyridines, imidazoles, guanidines, and amidines are used, more preferably pyridines, guanidines, and amidines, and still more preferably pyridines. In this specification, the basic compound involved in the curing reaction may be either a basic compound that acts as a catalyst for the curing reaction, or a basic compound (KA) having two or more amino groups in one molecule that can react with episulfide in a 1:1 ratio, as described later.

[0131] The amines are not particularly limited, but include ethylamine, n-propylamine, sec-propylamine, n-butylamine, sec-butylamine, isobutylamine, t-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, laurylamine, mystyrylamine, 1,2-dimethylhexylamine, 3-pentylamine, 2-ethylhexylamine, allylamine, aminoethanol, 1-aminopropanol, 2-aminopropanol, aminobutanol, aminopentanol, aminohexanol, 3-ethoxypropylamine, 3-propoxypropylamine, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 3-(2-ethylhexyloxy)propylamine, aminocyclopentane, aminocyclohexane, aminonorbornene, aminomethylcyclohexane, benzylamine, phenethylamine, α-phenylethylamine, naphthylamine N, furfurylamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, dimethylaminopropylamine, diethylaminopropylamine, bis-(3-aminopropyl) ether, 1,2-bis-(3-aminopropoxy)ethane, 1,3-bis-(3- Aminopropoxy)-2,2'-dimethylpropane, aminoethylethanolamine, 1,2-bisaminocyclohexane, 1,3-bisaminocyclohexane, 1,4-bisaminocyclohexane, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, 1,3-bisaminoethylcyclohexane, 1,4-bisaminoethylcyclohexane, 1,3-bisaminopropylcyclohexane, 1,4-bisaminopropylcyclohexane, hydrogenated 4,4'-Diaminodiphenylmethane, 2-Aminopiperidine, 4-Aminopiperidine, 2-Aminomethylpiperidine, 4-Aminomethylpiperidine, 2-Aminoethylpiperidine, 4-Aminoethylpiperidine, N-Aminoethylpiperidine, N-Aminopropylpiperidine, N-Aminoethylmorpholine, N-Aminopropylmorpholine, Isophoronediamine, Menthanediamine, 1,4-Bisaminopropylpiperazine, o-Phenylenediamine, m-Phenylenediamine, p-Phenylenediamine, 2,4-Tolylenediamine, 2,6-Tolylenediamine, 2,4-Toluenediamine, m-aminobenzylamine, 4-chloro-o-phenylenediamine, tetrachloro-p-xylylenediamine, 4-methoxy-6-methyl-m-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, benzidine, 4,4'-bis(o-toluidine), dianisidine, 4,4'-diaminodiphenylmethane, 2,2-(4,4'-diaminodiphenyl)propane, 4,4'-diaminodiphenyl Ether, 4,4'-thiodianiline, 4,4'-diaminodiphenylsulfone, 4,4'-diaminoditolylsulfone, methylenebis(o-chloroaniline), 3,9-bis(3-aminopropyl)2,4,8,10-tetraoxaspiro[5,5]undecane, diethylenetriamine, iminobispropylamine, methyliminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-aminoethylpiperazine, N-aminopropylpiperazine Razine, 1,4-bis(aminoethylpiperazine), 1,4-bis(aminopropylpiperazine), bis(3,4-diaminophenyl)sulfone, diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, di-n-pentylamine, di-3-pentylamine, dihexylamine, di(2-ethylhexyl)amine, methylhexylamine, diallylamine, pyrrolidine, piperidine, 2-picoline, 3-picoline, 4-picoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-Lupetidine, diphenylamine, aniline, N-methylaniline, N-ethylaniline, dibenzylamine, methylbenzylamine, dinaphthylamine, pyrrole, indoline, indole, morpholine, N,N'-dimethylethylenediamine, N,N'-dimethyl-1,2-diaminopropane, N,N'-dimethyl-1,3-diaminopropane, N,N'-dimethyl-1,2-diaminobutane, N,N'-dimethyl-1,3-diaminobutane, N,N'-dimethyl-1,4-diaminobutane, N,N'-dimethyl-1,5-diaminopentane, N, N'-dimethyl-1,6-diaminohexane, N,N'-dimethyl-1,7-diaminoheptane, N,N'-diethylethylenediamine, N,N'-diethyl-1,2-diaminopropane, N,N'-diethyl-1,3-diaminopropane, N,N'-diethyl-1,2-diaminobutane, N,N'-diethyl-1,3-diaminobutane, N,N'-diethyl-1,4-diaminobutane, N,N'-diethyl-1,6-diaminohexane, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2,6-dimethylpiperazine, homopiperazine , 1,1-di-(4-piperidyl)methane, 1,2-di-(4-piperidyl)ethane, 1,3-di-(4-piperidyl)propane, 1,4-di-(4-piperidyl)butane, tetramethylguanidine, trimethylamine, triethylamine, tri-n-propylamine, tri-isopropylamine, tri-1,2-dimethylpropylamine, tri-3-methoxypropylamine, tri-n-butylamine, tri-isobutylamine, tri-sec-butylamine, tri-pentylamine, tri-3-pentylamine, tri-n-hexylamine, tri-n -Octylamine, tri-2-ethylhexylamine, tri-dodecylamine, tri-laurylamine, tricyclohexylamine, N,N-dimethylhexylamine, N-methyldihexylamine, N,N-dimethylcyclohexylamine, N,N-dicyclohexylmethylamine, N-methyldicyclohexylamine, triethanolamine, tribenzylamine, N,N-dimethylbenzylamine, diethylbenzylamine, triphenylamine, N,N-dimethylamino-p-cresol, N,N-dimethylaminomethylphenol, 2-(N,N-dimethylaminomethyl)phenol, N,N-dimethylaniline, N,N-diethylaniline, N-methylmorpholine, N-methylpiperidine, 2-(2-dimethylaminoethoxy)-4-methyl-1,3,2-dioxabornane, tetramethylethylenediamine, pyrazine, N,N'-dimethylpiperazine, N,N'-bis((2-hydroxy)propyl)piperazine, hexamethylenetetramine, N,N,N',N'-tetramethyl-1,3-butanamine, 2-dimethylamino -2-Hydroxypropane, Diethylaminoethanol, N,N,N-Tris(3-dimethylaminopropyl)amine, 2,4,6-Tris(N,N-dimethylaminomethyl)phenol, Heptamethylisobiguanide, n-Propylthioamine, i-Butylamine, 1,3-Bis-(3-aminopropoxy)-2,2'-Dimethylpropane, Hydrogenated 4,4'-Diaminodiphenylmethane, 4,4'-Bis(o-Toluidine), 4,4'-Diaminodiphenylmethane, 2,2-(4,4'- Diaminodiphenyl)propane, 4,4'-diaminodiphenyl ether, 4,4'-thiodianiline, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminoditolylsulfone, 2,6-diaminopyridine, N,N'-dimethylethylenediamine, N,N'-dimethyl-1,2-diaminopropane, N,N'-dimethyl-1,3-diaminopropane, N,N'-dimethyl-1,2-diaminobutane, N,N'-dimethyl-1,3-diaminobutane, N,N'-dimethyl-1,4- Diaminobutane, N,N'-dimethyl-1,5-diaminopentane, N,N'-dimethyl-1,6-diaminohexane, N,N'-dimethyl-1,7-diaminoheptane, N,N'-diethylethylenediamine, N,N'-diethyl-1,2-diaminopropane, N,N'-diethyl-1,3-diaminopropane, N,N'-diethyl-1,2-diaminobutane, N,N'-diethyl-1,3-diaminobutane, N,N'-diethyl-1,4-diaminobutane, N,N'-diethyl-1,6-Diaminohexane, tri-iso-propylamine, tri-iso-butylamine, toridodecylamine, trilaurylamine, tricyclohexylamine, dicyclohexylethylamine, monocyclohexyldiethylamine, N,N-diethylethanolamine, N-ethyldiethanolamine, pyridine, quinoline, N,N'-dimethylpiperazine, N,N'-bis((2-hydroxy)propyl)piperazine, N,N,N',N'-tetramethyl-1,3-butanamine, 2,4,6-tris(dimethylaminomethyl)phenol, diamine Nopropane, methylpropanediamine, dimethylpropanediamine, diaminobutane, diaminopentane, diaminomethylpentane, butylethylpentanediamine, hexanediamine, dimethylhexanediamine, trimethylhexamethylenediamine, diaminoheptane, diaminooctane, nonanediamine, diaminodecane, undecanediamine, dodecanediamine, diaminocyclohexane, bis(aminocyclohexyl)methane, bis(aminomethylcyclohexyl)methane, bis(aminoethylcyclohexyl)methane, bis(aminodimethyl Lucyclohexyl)methane, bis(aminoethylmethylcyclohexyl)methane, aminoaminomethyltrimethylcyclohexane, methyldiaminocyclohexane, bis(aminomethyl)cyclohexane, bis(aminomethyl)bicycloheptane, bis(aminomethyl)tricyclodecane, diaminotrimethylcyclohexane, bis(aminopropyl)tetraoxaspirowndecane, diaminobenzene, diaminobenzophenone, diaminodiphenyl ether, diaminodiphenylmethane, diaminodiphenyl sulfide, diaminodiphenyl sulf N, diaminofluorene, diaminonaphthalene, diaminopyridine, diaminotoluene, xylylenediamine, diaminomethylbicycloheptane, diaminomethylcyclohexane, aminobutylpiperidine, dioctylamine, N-methylallylamine, dicyclohexylamine, N-ethylbenzylamine, N,N'-dimethyldiaminopropane, N,N'-dimethyldiaminobutane, N,N'-dimethyldiaminopentane, N,N'-dimethyldiaminohexane, N,N'-dimethyldiaminoheptane, N,N'-diethyldiaminopropane, N,N'-Diethyldiaminobutane, N,N'-Diethyldiaminopentane, N,N'-Diethyldiaminohexane, N,N'-Diethyldiaminoheptane, N,N'-Dibutylethylenediamine, N,N'-Dibutyldiaminopropane, N,N'-Dibutyldiaminobutane, N,N'-Dibutyldiaminopentane, N,N'-Dibutyldiaminohexane, N,N'-Dibutyldiaminoheptane, N,N'-Diethylhexanediamine, Methylethylaminomethylethylaminomethyltrimethylcyclohexane, Dipropylenetriamine N,N-(aminoethyl)propanediamine, N,N'-bis(aminopropyl)ethylenediamine, N,N'-bis-(aminopropyl)diaminobutane, N5-(aminopropyl)methylpentanediamine, N3-(aminopentyl)pentanediamine, N5-(aminoethylpropyl)methylpentanediamine, N,N'-bis-(aminoethylpropyl)methylpentanediamine, cyclohexylmethyl(methylpropyl)pentanediamine, N,N'-dialkylxylylenediamine, bis((N-alkylamino)si, Chlorohexyl)methane, dimethylthiotoluylenediamine, diethyltoluylenediamine, tetraethyldiaminodiphenylmethane, tetraethyldichlorodiaminodiphenylmethane, diisopropyldimethyldiaminodiphenylmethane, tetraisopropyldiaminodiphenylmethane, diaminodiphenylsulfone, pentaethylenehexamine (PEHA) and higher homologues of linear polyethyleneamines, polyethylene polyamines having ethyleneamine units, polycyanoethylation, cyanobutylation, and hydrogenation of di- and polyamines. Products obtained by amination: piperazine, dimethylpiperazine, homopiperazine, di-(piperidyl)methane, di-(piperidyl)ethane, di-(piperidyl)propane, di-(piperidyl)butane, tetramethylguanidine, diethylenetriamine, hexamethylenediamine, xylenediamine, hydroxyphenylglycine, bisaminomethylcyclohexane, methylenebiscyclohexaneamine, products of amination of polyoxyalkylenediol, polyoxyalkylene polyamine, polyether polyamine, polyoxy Alkylenediamine, polyoxyalkylenediamine, polyetheramine, polyoxyalkyleneamine, alkylpolyetheramine diamino-diethyltoluene, dimethylthiotoluenediamine, mono- and poly-methyl-,-ethyl-, and / or-isopropyl-substituted methylenediphenylamine, (aminoethyl)aminopropylamine, bis-hexamethylenediamine, triethylenetetramine, tetraethylenepentamine, diethanolamine, (methylamino)ethanol, (ethylamino)ethanol, (butylamino)ethanol, (cyclohexylamino)ethanol, amino-N-(aminophenyl)benzenesulfonamide, methylenedianthranilic acid, dimethyl(methylenedianthranilate), propylenebis(aminobenzoate), butylenebis(aminobenzoate), polytetramethyleneoxidebis(aminobenzoate), N-butylhexanediamine, phenylenediamine, dichlorodiaminodiphenylmethane, bis(aminophenylthio)ethane, N,N'-dialkylphenylenediamine, N,N'-Dialkyldiaminodiphenylmethane, Methylpropyl (chlorodiaminobenzoate), Butyl (chlorodiaminobenzoate), Aminomethyloctanediamine, Tris(aminomethyl)benzene, Tris(aminomethyl)cyclohexane, Tris-(aminoethyl)amine, Tris(aminopropyl)amine, Bis(aminoethyl) ether, Dioxaoctanediamine, Dioxadecanediamine, Dioxadodecanediamine, Trioxatridecanediamine, Bis(aminopropyl)polytetrahydrofuran, Polytetrahydrofrangamine, N,N'-Bis-(aminopropyl)piperazine, N,N-Bis-(aminopropyl)-methylamine, N,N-Bis-(aminopropyl)ethylamine, N,N-Bis-(aminopropyl)propylamine, N,N-Bis-(aminopropyl)cyclohexylamine, N,N-Bis(aminopropyl)ethylhexylamine, N,N-Bis(aminopropyl)dodecylamine, N,N-Bis(aminopropyl)taloalkylamine Tris(aminoethyl)amine, N-methylethanediamine, N-ethylethanediamine, N-butylethanediamine, N-hexylethanediamine, N-(ethylhexyl)ethanediamine, N-cyclohexylethanediamine, N((dimethylamino)propyl)diaminopropane, N((dimethylamino)ethyl)propanediamine, N-methylpropanediamine, N-ethylpropanediamine, N-butylpropanediamine, N-hexylpropanediamine, N-(ethylhexyl) Ropanediamine, N-dodecylpropanediamine, N-cyclohexylpropanediamine, methylaminopentylamine, ethylaminopentylamine, butylaminopentylamine, hexylaminopentylamine, (ethylhexyl)aminopentylamine, dodecylaminopentylamine, cyclohexylaminopentylamine, N-cocoalkylpropanediamine, N-oleylpropanediamine, N-taloalkyl-1,3-propanediamine, N-(C16-22-alkyl)-1,3-Propanediamine, Coco-alkyldipropylenetriamine, Oleyldipropylenetriamine, Tallo-alkyldipropylenetriamine, Oleyltripropylenetetramine, Tallo-alkyltripropylenetetramine, Bishexamethylenetriamine, Pentaethylenehexamine, Polyethylene polyamine having 5-7 ethyleneamine units, Aminoethanol, Aminopropanol, Aminobutanol, Aminomethylpropanol, Aminopentanol, Aminohexanol, Aminoheptanol, Aminooctanol, Aminodecanol, Aminododecanol, Aminopropyldiethanolamine, Aminoethylhydroxyethylbenzene, Aminomethyltrimethylcyclohexanol, Diethylene glycol, Dipropylene glycol, Dibutylene glycol, α-(2-Hydroxymethyl-ethyl)-ω-(2-AminomethylEpoxy)Poly(Oxy(methyl-1,2-Ethanediyl), N-Hydroxyethylpropanediamine, N-Hydroxypropylpropanediamine, N3-Hydroxyethylpentanediamine, Aminoethanethiol, Aminopropanthiol, Aminobutanethiol, Aminohexanethiol, Aminooctanthiol, Aminodecanethiol, Aminododecanethiol, Aminopropyltrimethoxysilane, Aminopropyldimethoxymethylsilane, N-Aminoethylaminopropyltrimethoxysilane, N-Aminoethylaminopropylmethyldimethoxysilane, N-Aminoethyl[(trimethoxysilyl)propyl]ethylenediamine, Aminomethylpropyltrimethoxysilane, Aminobutyltrimethoxysilane, Aminobutyldimethoxymethylsilane, Aminomethylbutyltrimethoxysilane, Aminodimethylbutyltrimethoxysilane, Aminodimethylbutyldimethoxymethylsilane, Aminoethyltrimethoxysilane, Aminoethyldimethoxymethylsilane, Aminomethyltrimethoxy Examples include sisilane, aminomethyldimethoxymethylsilane, aminomethyl-methoxydimethylsilane, aminooxaheptyldimethoxymethylsilane, ammerido, dimethylpiperazine, benzyldimethylamine, (dimethylaminomethyl)phenol, diethylenetriamine, triethylenetetramine, tris(dimethylaminomethyl)phenol, triethylenediamine, aminomethoxymethyltriazine, diethylaminopropylamine, tetraethylenepentamine, diproprendiamine, hexamethylenediamine, aminoethylpiberazine, dimethyldiaminodicyclohexylmethane, bis(aminocyclohexyl)methane, mensendiamine, isophoronediamine, bisaminomethylcyclohexane, xylylenediamine, xylylenediamine polymer, metaphenylenediaminediaminodiphenylmethane, diaminodiphenylsulfone, amine adduct derivatives, ketimine, polyamidoamine, aminomethoxy(trifluoromethyl)triazine, etc. These may be used individually or in combination of two or more.

[0132] The base initiator may include, for example, a basic compound (KA) having two or more amino groups in one molecule, in which the episulfide group in the episulfide resin and the amino group in the base initiator can react in a 1:1 ratio. As basic compounds (KA), among the above compounds, polyoxyalkylene polyamine, polyether polyamine, polyoxyalkylenediamine, polyoxyalkylentriamine, polyetheramine, polyoxyalkyleneamine, alkyl polyetheramine diamino-diethyltoluene, melamine, ethyldiaminotriazine, diaminotriazine, diaminoxyltriazine, benzoguanamine, acetoguanamine, diaminodiethylaminotriazine, diaminodiallylaminotriazine, methoxymethyl(methylamino)triazine, diaminobutylaminotriazine, ammelin, ethylenediamine, diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminoheptane, diaminooctane, bis-(aminopropyl)ether, bis-(aminopropoxy)ethane, bis-(aminopropoxy)-dimethylpropane, aminoethylethanolamine, bisaminocyclohexane, bisaminomethylcyclohexane, bisaminoethyl Examples include cyclohexane, bisaminopropylcyclohexane, hydrogenated diaminodiphenylmethane, diaminodiphenylmethane, aminopiperidine, aminomethylpiperidine, aminoethylpiperidine, aminopropylpiperidine, isophoronediamine, toluenediamine, xylenediamine, hydrogenated xylenediamine, diethylenetriamine, triethylenetetramine, triethylenetetramine, tris(dimethylaminomethyl)phenol, triethylenediamine, aminomethoxymethyltriazine, diethylaminopropylamine, tetraethylenepentamine, diproprendiamine, hexamethylenediamine, aminoethylpeverazine, dimethyldiaminodicyclohexylmethane, bis(aminocyclohexyl)methane, mensendiamine, bisaminomethylcyclohexane, xylylenediamine, xylylenediamine polymer, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, amine adducts, ketimines, and polyamidoamines.

[0133] The amount of the above compound, exemplified as a basic compound (KA), added to the curable resin composition is preferably 0.001 to 1200 parts per 100 parts of episulfide resin, more preferably 0.01 to 600 parts, even more preferably 0.05 to 300 parts, and particularly preferably 0.05 to 150 parts, from the viewpoint of low-temperature curability.

[0134] Examples of pyridines include diaminopyridine, pyridine, methylaminopyridine, dimethylaminopyridine, quinoline, and (N-pyrrolidino)pyridine. These may be used individually or in combination of two or more. Methylaminopyridine and dimethylaminopyridine are particularly preferred, and methylaminopyridine is even more preferred.

[0135] Imidazoles are not particularly limited to imidazole, but include imidazole, N-methylimidazole, 2-methylimidazole, 4-methylimidazole, N-ethylimidazole, 2-ethylimidazole, 4-ethylimidazole, N-butylimidazole, 2-butylimidazole, N-undecylimidazole, 2-undecylimidazole, N-phenylimidazole, 2-phenylimidazole, N-benzylimidazole, and 2-benzylimidazole. 1-benzyl-2-methylimidazole, N-(2'-cyanoethyl)-2-methylimidazole, N-(2'-cyanoethyl)-2-undecylimidazole, N-(2'-cyanoethyl)-2-phenylimidazole, 3,3-bis-(2-ethyl-4-methylimidazolyl)methane, 2-methylimidazoline, 2-phenylimidazoline, 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydro Xy-3-butoxypropyl)-2-methylimidazoline, 2,4-dimethylimidazoline, 2-ethylimidazoline, 2-ethyl-4-methylimidazoline, 2-benzylimidazoline, 2-(o-tolyl)-imidazoline, tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4-tetramethylene-bis-imidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4 Examples include -tetramethylene-bis-4-methylimidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline, 1,2-phenylene-bis-imidazoline, 1,3-phenylene-bis-imidazoline, 1,4-phenylene-bis-imidazoline, 1,4-phenylene-bis-4-methylimidazoline, adducts of alkylimidazole and isocyanuric acid, condensates of alkylimidazole and formaldehyde, etc.

[0136] The guanidines are not particularly limited, but examples include guanidine, tetramethylguanidine, arginine, diphenylguanidine, triphenylguanidine, dicyclohexylmorpholine carboxymidoamide, acetoguanamine, benzoguanamine, dicyandiamide, cyanoguanidine, 1,3-di-o-tolylguanidine, and dimethylguanidine. Tetramethylguanidine and dicyclohexylmorpholine carboxymidoamide are particularly preferred.

[0137] Examples of amidines, though not particularly limited, include 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, 6-dibutylamino-1,8-diazabicyclo[5.4.0]unde-7-cene, and 1,8-diazobicyclo[2.2.2]octane.

[0138] The base initiator may be latent by any method. The latent base initiator (latent base initiator) is not particularly limited, but examples include thermal base initiators and photobase initiators. A thermal base initiator is particularly preferred. As a thermal base initiator, known or conventional thermal base initiators, photobase initiators, and curing accelerators can be used, and are not particularly limited, but include, for example, 1,8-diazabicyclo[5.4.0]undecene-7(DBU) salts (e.g., phenol salts, octylates, p-toluenesulfonates, formates, tetraphenylborate salts); salts of 1,5-diazabicyclo[4.3.0]nonene-5(DBN) (e.g., phenol salts, octylates, p-toluenesulfonates, formates, tetraphenylborate salts); tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and N,N-dimethylcyclohexylamine; imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; phosphines such as phosphate esters and salts of triphenylphosphine (TPP) (e.g., tetrafluoroborate salts, triphenylborane salts). Phosphonium compounds such as tetraphenylphosphonium tetraphenylborate and tetraphenylphosphonium tetra(p-tolyl)borate; organometallic salts such as tin octoate and zinc octoate; metal chelates, carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, amineimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, acyloxyimino compounds, compounds disclosed in Japanese Patent Application Publication No. 2024-160873, compounds disclosed in WO2023 / 189126, etc. can be used. These can be used individually or in combination of two or more.

[0139] As photobase initiators, known or conventional photobase initiators and curing accelerators can be used and are not particularly limited, but examples include cobaltamine complexes, o-acyl oximes, carbamic acid derivatives, formamide derivatives, sulfonamides, quaternary ammonium salts, tosylamines, carbamates, amineimide compounds, compounds having an amidine structure, α-aminoacetophenone, compounds disclosed in WO2014 / 014037, heterocyclic photobase generators, nitrobenzylcyclohexylcarbamate, [[(dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(nitrobenzyl)oxy]carbonyl]hexanediamine, triphenylmethanol, carbamoylhydroxylamide, carbamoyl oxime, hexaamminecobalt(III)tris(triphenyl Methyl borate, dicyclohexyltetramethyl diguanidine butyltriphenyl borate, {[bis(dimethylamino)methylidene]amino}cyclohexyl(cyclohexylamino)methaneiminiumtetrakis(fluorophenyl) borate, diisopropyl[bis(dimethylamino)methylene]guanidium(benzoylphenyl)propionate, anthrylmethyldiethylcarbamate, piperidino(hydroxyphenyl)propionone, imidazole carboxylic acid (anthraquinoneyl)ethyl, nitrophenylmethyl methacryloylpiperidine carboxylate, guanidium(benzoylphenyl)propionate, cyclohexylammonium 2-(3-benzoylphenyl)propionate, dicyclohexylammonium 2-(3-benzoylphenyl)propionate, (methacryloyloxy)piperidine carboxylic acid (nitrophenyl)methyl, hydroxypiperidine carboxylic acid (nitrophenyl)methylExamples include cyclohexylcarbamate (anthraquinone-yl)ethyl, diethylcarbamate anthrylmethyl, piperidine carboxylate anthrylmethyl, dicyclohexylcarbamate (anthraquinone-yl)ethyl, imidazole carboxylate (anthraquinone-yl)ethyl, cyclohexyl(hydroxyphenyl)acrylamide, {[bis(dimethylamino)methylidene]amino}cyclohexyl(cyclohexylamino)methaneiminiumtetrakis(fluorophenyl)borate, dicyclohexyltetramethylbiguanidium butyltriphenylborate, and diisopropyl[bis(dimethylamino)methylene]guanidium(benzoylphenyl)propionate. These can be used individually or in combination of two or more.

[0140] Potential base initiators include ionic base initiators and nonionic base initiators, but nonionic base initiators are particularly preferred. Nonionic base initiators are preferred because they have excellent stability over time.

[0141] (Acid initiator) The acid initiator is not particularly limited, and it does not need to be latent, or it may be latent by any method. An acid initiator that has been latent by any method is preferable to an acid initiator that has not been latent, because it can generate the target acid initiator with light, heat, etc., and is particularly preferable to a thermal acid initiator that can generate the target acid initiator with heat.

[0142] The acid initiator is not particularly limited, but examples include organic acids, their salts or esters, inorganic acids, ammonium salts, phosphonium salts, sulfonium salts, iodonium salts, Lewis acids, cationic polymerization catalysts, aryldiazonium salts, aryliodonium salts, arylsulfonium salts, allene-ion complexes, chelate compounds of metals such as aluminum and titanium with acetoacetic acid or diketones, silanols such as triphenylsilanol, compounds or resins having alkoxysilane groups, silanol groups and acyloxysilane groups, or aluminum. Examples include chelate compounds of metals such as titanium and titanium with acetoacetic acid or diketones and compounds of phenols such as bisphenol S, diazonium salts, iodonium salts, sulfonium salts, phosphonium salts, selenium salts, metallocene complexes, oxathiazole derivatives, triazine derivatives, imide compounds, oximesulfonates, diazonaphthoquinones, sulfonic acid esters, Lewis salts, hexafluoroantimonate salts, pentafluorohydroxyantimonate salts, hexafluorophosphate salts, and hexafluoroalzenate salts. These can be used individually or in combination of two or more.

[0143] The organic acids, their salts, or their esters are not particularly limited, but examples include sulfonic acids, carboxylic acids and their esters, and their methyl and ethyl esters.

[0144] While not particularly limited, preferred acid initiators include Lewis acids, chelate compounds of metals such as aluminum and titanium with acetoacetic acid or diketones, or resins with silanols such as triphenylsilanol, compounds or resins having an alkoxysilane group, a silanol group and an asyloxysilane group, sulfonium salts, iodonium salts, and ammonium salts.

[0145] Inorganic acids are not particularly limited, but examples include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and carbonic acid.

[0146] Phosphonium salts are not particularly limited, but examples include tetramethylphosphonium chloride, tetramethylphosphonium bromide, tetraethylphosphonium chloride, tetraethylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, tetrahexylphosphonium bromide, tetraoctylphosphonium bromide, methyltriphenylphosphonium bromide, methyltriphenylphosphonium iodide, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, butyltriphenylphosphonium bromide, and butyltriphenylphosphonium bromide. Examples include ium-iodide, hexyltriphenylphosphonium bromide, octyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, tetrakisshydroxymethylphosphonium chloride, tetrakisshydroxymethylphosphonium bromide, tetrakisshydroxyethylphosphonium chloride, tetrakisshydroxybutylphosphonium chloride, tri-p-tolylsulfonium hexafluorophosphate, (cumene)cyclopentadienyl iron(II) hexafluorophosphate, (thiodi-4,1-phenylene)bis(diphenylsulfonium)bis(hexafluorophosphate), and triphenylsulfonium hexafluorophosphate.

[0147] The sulfonium salts are not particularly limited, but examples include trimethylsulfonium bromide, triethylsulfonium bromide, tributylsulfonium chloride, tributylsulfonium bromide, tributylsulfonium iodide, tributylsulfonium tetrafluoroborate, trihexylsulfonium bromide, trioctylsulfonium bromide, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenylsulfonium iodide, dimethylphenacylsulfonium tetrafluoroborate, triphenylsulfonium tetrafluoroborate, tri-p-tolylsulfonium trifluoromethanesulfonate, nonafluoro- Examples include 1-butanesulfonate triphenylsulfonium, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimonic acid, hexafluoroantimonic acid triphenylsulfonium, 10-camphorsulfonate triphenylsulfonium, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, triphenylsulfonium trifluoromethanesulfonate, (4-hydroxyphenyl)dimethylsulfonium hexafluorophosphate, triphenylsulfonium bromide, triphenylmethylsulfonium chloride, and benzyl(4-hydroxyphenyl)(methyl)sulfonium trifluorotris(perfluoroethyl)phosphate.

[0148] Iodonium salts are not particularly limited, but examples include diphenyliodonium chloride, diphenyliodonium bromide, diphenyliodonium iodide, diphenyliodonium hexafluoroarsenate, bis(4-tert-butylphenyl)iodonium tetrafluoroborate, diphenyliodonium trifluoromethanesulfonic acid, bis(4-tert-butylphenyl)iodonium nonafluoro-1-butanesulfonic acid, (4-isobutylphenyl)(p-tolyl)iodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, [4-[ Examples include (2-hydroxytetradecyl)oxy]phenyl]phenyliodonium hexafluoroantimonate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, bis[4-(tert-butyl)phenyl]iodonium tetra(nonafluoro-tert-butoxy)aluminate, 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl) bolate, diphenyliodonium hexafluorophosphate, and p-isopropylphenyl-p-tolylliodonium trifluorotris(perfluoroethyl) phosphate.

[0149] Lewis acids are not particularly limited, but examples include boron trifluoride, boron trifluoride etherate, tetrafluoroboric acid, dibutyltin dichloride, and dibutyltin dilauric acid.

[0150] Triazine derivatives are not particularly limited, but examples include 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(1,3-benzodioxol-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine.

[0151] The diazonium salt is not particularly limited, but examples include 4-nitrobenzenediazonium tetrafluoroborate.

[0152] As a latent acid initiator, there are no particular limitations, but a latent acid initiator that generates tetrafluoroboric acid, tetrakis(pentafluorophenyl) borate, hexafluorophosphate, fluoroantimonic acid, tetrakis(pentafluorophenyl) borate, trifluorotris(perfluoroethyl) phosphate, pentafluoro(perfluoroalkyl) phosphate, trifluorotri(perfluoroalkyl) phosphate, difluorotetra(perfluoroalkyl) phosphate, fluorohexa(perfluoroalkyl) phosphate, trifluoromethanesulfonic acid, hexafluoroantimonic acid, tetrakis(pentafluorophenyl) gallium, etc. upon exposure to light or heat is preferred.

[0153] The latent acid initiator is not particularly limited, but examples include thermal acid initiators and photoacid initiators. A thermal acid initiator is particularly preferred. Examples of thermal acid initiators include benzyl(4-hydroxyphenyl)(methyl)sulfonium trifluorotris(perfluoroethyl)phosphate(V) salt.

[0154] (Radical initiator) While not particularly limited, thermal radical initiators and photoradical initiators can be used as radical initiators. These may be used alone or in combination of two or more types. Thermal radical initiators are preferred.

[0155] While not particularly limited, azo initiators and organic peroxides can be used as thermal radical initiators. These may be used individually or in combination of two or more.

[0156] Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane1-carbonnitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(-imidazolin-2-yl)propane] disulfate dihydrate, and dimethyl1,1'-azobi Examples include 2,2'-azobis(1-cyclohexane carbonate), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-hydroxymethylpropionitrile), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]n hydrate, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(isobutyrate)dimethyl.

[0157] The organic peroxide is not particularly limited, but examples include hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, peroxydicarbonates, peroxyketals, ketone peroxides, alkyl peroxyesters, and monoperoxycarbonates. These may be used individually or in combination of two or more.

[0158] Organic peroxides are not particularly limited, but examples include benzoyl peroxide, t-butyl peroxy-2-ethylhexaate, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide, benzoyl peroxide, t-butyl peroxy-2-ethylhexanoate, 2,5-dimethyl Examples include tyl-2,5-di(2-ethylhexanoyl)peroxyhexane, t-butylperoxybenzoate, t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-dibutylperoxyhexane, 2,4-dichlorobenzoyl peroxide, 1,4-di(2-t-butylperoxyisopropyl)benzene, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, methyl ethyl ketone peroxide, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate. These may be used individually or in combination of two or more.

[0159] While not particularly limited, examples of photoradical initiators include acetophenones, benzophenones, thioxanthones, diazonium salts, metallocenes, oxime esters, thioxanthones, acetophenones, benzoins, benzophenones, triazines, borates, carbazoles, imidazoles, acylphosphine oxides, phosphines, quinones, borates, carbazoles, and titanocene compounds. Amines and phosphines can also be used in combination as accelerators.

[0160] The photoradical polymerization initiator is not particularly limited, but examples include benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyl disulfite, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy- Acetophenone compounds such as 2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Tel, benzyldimethyl ketal, methyl benzoyl benzoate, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, ethyl 4-dimethylaminobenzoate, thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthio Xanthones, 2-methyl-1-[4-(methyl)phenyl]-2-morpholinopropanone-1-one, 1-hydroxycyclohexylphenyl ketone, 2-dimethylamino-2-(4-morpholino)benzoyl-1-phenylpropane, tetra(t-butylperoxycarbonyl)benzophenone, benzyl, 2-hydroxy-2-methyl-1-phenyl-propanone-1-one, 4,4-bisdiethylaminobenzophenone, 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole, 2,6-bis(trichloromethyl)-4-(4-methoxynaphthalene-1-yl)-1,3,5-triazine, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-tri Examples of photoradical initiators that can be used include lorromethyl-(piperonyl)-6-triazine, 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine, 2-trichloromethyl-5-(2-benzofuran-2-ylethenyl)-1,3,4-oxadiazole, 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], or O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxynaphthyl)ethylidene)hydroxylamine, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, or 2,4,6-trimethylbenzoyldiphenylphosphine oxide, quinone compounds such as 9,10-phenanthylenequinone, camphorquinone, and ethylanthraquinone. These photoradical initiators may be used individually or in any ratio of two or more. Additionally, a photosensitizer can be added as needed.

[0161] Other initiators, though not limited to those mentioned above, include phosphines and onium salts.

[0162] Phosphines are not particularly limited, but examples include trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-n-butylphosphine, tri-n-cyclohexylphosphine, tri-n-octylphosphine, tricyclohexylphosphine, triphenylphosphine, tripenzylphosphine, tris(2-methylphenyl)phosphine, tris(3-methylphenyl)phosphine, tris(4-methylphenyl)phosphine, tris(diethylamino)phosphine, dimethylphenylphosphine, diethylphenylphosphine, dicyclohexylphenylphosphine, diethylphenylphosphine, dicyclohexylphenylphosphine, ethyldiphenylphosphine, diphenylcyclohexylphosphine, and chlorodiphenylphosphine.

[0163] Examples of onium salts include, but are not limited to, ammonium salts and pyridium salts. Examples of ammonium salts and pyridium salts include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium acetate, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium acetate, tetra-n-butylammonium fluoride, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium iodide, tetra-n-butylammonium acetate, tetra-n-butylammonium borohydride, tetra-n-butylammonium hexafluorophosphite, tetra-n-butylammonium hydrogen sulfite, tetra-n-butylammonium tetrafluoroborate, tetra-n-butylammonium tetraphenylborate, tetra-n-butylammonium p-toluenesulfonate, tetra-n-hexylammonium chloride, tetra-n-hexylammonium bromide, and tetra-n-hexylammonium acetate. , tetra-n-octylammonium chloride, tetra-n-octylammonium bromide, tetra-n-octylammonium acetate, trimethyl-n-octylammonium chloride, trimethylbenzylammonium chloride, trimethylbenzylammonium bromide, triethyl-n-octylammonium chloride, triethylbenzylammonium chloride, triethylbenzylammonium bromide, tri-n-butyl-n-octylammonium chloride, tri-n-butylbenzylammonium fluoride, tri-n-butylbenzylammonium chloride, tri-n-butylbenzylammonium bromide, tri-n-butylbenzylammonium iodide, methyltriphenylammonium chloride, methyltriphenylammonium bromide, ethyltriphenylammonium chloride, ethyltriphenylammonium bromide, n-butyltriphenylammonium chloride, n-butyltriphenylammonium bromide, 1-methylpyridinium bromide,Examples include 1-ethylpyridinium bromide, 1-n-butylpyridinium bromide, 1-n-hexylpyridinium bromide, 1-n-octylpyridinium bromide, 1-n-dodecylpyridinium bromide, 1-n-phenylpyridinium bromide, 1-methylpicolinium bromide, 1-ethylpicolinium bromide, 1-n-butylpicolinium bromide, 1-n-hexylpicolinium bromide, 1-n-octylpicolinium bromide, 1-n-dodecylpicolinium bromide, and 1-n-phenylpicolinium bromide.

[0164] [Other ingredients] The curable resin composition may contain other components besides those mentioned above. These other components are not particularly limited, but examples include solvents, resins, curing components, leveling agents, defoaming agents, sensitizers, coloring components, silane coupling agents, acid components, curing accelerators, curing catalysts, chain transfer agents, polymerization inhibitors, ultraviolet absorbers, near-infrared absorbers, and other additives. The content of these other components can be appropriately set within a range that solves the problems of the present invention.

[0165] (solvent) As the solvent, the solvents mentioned in the section on the method for producing episulfide resins when explaining the episulfidation reaction can be used. Among these, ester-based solvents, ketone-based solvents, and alcohol-based solvents are preferred.

[0166] (resin) Examples of resins include alkyd resins, polyester resins, polyvinyl chloride, poly(meth)acrylic acid ester resins, polyepoxy resins, polyurethane resins, cellulose derivatives, vinyl chloride vinyl acetate copolymers, polyamide resins, polyvinyl acetal resins, diallyl phthalate resins, silicone resins, butadiene-acrylonitrile copolymers, polyamide resins, polyformaldehyde resins, polycarbonate resins, polystyrene resins, polyvinyl ether resins, polyvinyl ester resins, polyvinylamide resins, novolac resins, and phenolic resins. These resins may be used individually or in combination of two or more types.

[0167] (hardening component) As the curing component, polymerizable monomers, polymerizable resins, etc., can be used. These may be used individually or in combination of two or more. The curing component may contain any of the functional groups. It is not particularly limited, but for example, it may contain a carboxyl group, epoxy group, (meth)acrylate group, vinyl group, thiol group, allyl group, hydroxyl group, blocked isocyanate group, acid anhydride unit, episulfide, phenol group, oxetane group, or oxazoline group. Preferably, it is any of a carboxyl group, epoxy group, episulfide, (meth)acrylate group, vinyl group, blocked isocyanate group, thiol group, oxetane group, or oxazoline group. More preferably, it is any of an epoxy group, thiol group, (meth)acrylate group, or episulfide group. Even more preferably, it is any of a thiol group, (meth)acrylate group, or episulfide group. Multiple of these functional groups may be present in the same compound.

[0168] The curing component containing a (meth)acrylate group is not particularly limited, but examples include (meth)acrylate oligomers, polyfunctional (meth)acrylates, (meth)acrylic monomers, and (meth)acrylate-containing resins. These may be used individually or in combination of two or more.

[0169] Examples of (meth)acrylate oligomers include epoxy (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, and acrylic (meth)acrylate. These may be used individually or in combination of two or more types.

[0170] In addition, as curing components containing (meth)acrylate groups, you can use highly hydrophobic polybutadiene (meth)acrylate oligomers having (meth)acrylate groups in the side chains of polybutadiene oligomers, silicone (meth)acrylate oligomers having polysiloxane bonds in the main chain, aminoplast resin (meth)acrylate oligomers obtained by modifying aminoplast resins that have many reactive groups in a small molecule, or oligomers having cationic polymerizable functional groups in the molecules of novolac-type epoxy resins, bisphenol-type epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers, etc.

[0171] The (meth)acrylate oligomer is not particularly limited, but (meth)acrylic monomers and polyfunctional (meth)acrylates can be used, with polyfunctional (meth)acrylates being preferred.

[0172] The polyfunctional (meth)acrylate is not particularly limited, but is a (meth)acrylate having two or more ethylenically unsaturated bonds in its molecule, for example, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphate di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, Examples include dipentaerythritol tri(meth)acrylate, propionic acid-modified pentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol di(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl) isocyanurate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and ethylene oxide-modified bisphenol A diacrylate.

[0173] The (meth)acrylate-containing resin is not particularly limited, but examples include resins having (meth)acrylate moieties manufactured by known methods. The (meth)acrylate-containing resin may or may not have functional groups other than (meth)acrylate groups, such as carboxyl groups, epoxy groups, and blocked isocyanate groups.

[0174] The amount of curing component containing (meth)acrylate groups is not particularly limited, but preferably it is added in an amount of 1 to 500 parts per 100 parts of episulfide resin.

[0175] The curing components containing thiol groups are not particularly limited, but examples include thiophenols, mercaptos, mercapto alcohols, mercapto organic acids, and mercaptoamines. These can be used individually or in combination of two or more.

[0176] As the curing component containing a thiol group, a latent thiol that generates thiols by heat, light, base, acid, radical, oxidation-reduction reaction, etc. may be used. The conditions for generating thiols may be one of the above conditions or two or more. Preferably, it is a latent thiol that generates thiols by heat, light, base, and radical; more preferably, it is a latent thiol that generates thiols by heat, light, and base; and even more preferably, it is a latent thiol that generates thiols by heat, base, and heat and base. Preferably, the curing components containing thiol groups are mercaptos, thiophenols, and latent thiols. Mercaptos and thiophenols are particularly preferred from the viewpoint of low-temperature curability, and latent thiols are particularly preferred from the viewpoint of long-term stability.

[0177] Thiophenols are not particularly limited, but examples include thiophenol, tert-butylthiophenol, methylthiophenol, benzenedithiol, trimercaptobenzene, thiobisbenzenethiol, hydroxybenzenethiol, methoxybenzenethiol, propylbenzenethiol, mercaptobenzoic acid, naphthalenedithiol, and the like.

[0178] Mercaptos are not particularly limited, but examples include methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, n-butyl mercaptan, allyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, n-decyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-hexadecyl mercaptan, n-octadecyl mercaptan, cyclohexyl mercaptan, isopropyl mercaptan, tert-butyl mercaptan, tert-nonyl mercaptan, and tert-dodecyl mercaptan. , benzyl mercaptan, 4-chlorobenzyl mercaptan, methyl thioglycolate, ethyl thioglycolate, n-butyl thioglycolate, n-octyl thioglycolate, methyl (3-mercaptopropionate), ethyl (3-mercaptopropionate), 3-methoxybutyl (3-mercaptopropionate), n-butyl (3-mercaptopropionate), 2-ethylhexyl (3-mercaptopropionate), n-octyl (3-mercaptopropionate), methyl thioglycolate, octyl thioglycolate, thioglycolate Monomercapto compounds such as methoxybutyl mercapate, methyl mercaptopropionate, octyl mercaptopropionate, methoxybutyl mercaptopropionate, tridecyl mercaptopropionate, methanedithiol, 1,2-dimercaptoethane, 2,2-dimercaptopropane, 1,3-dimercaptopropane, 1,2,3-trimercaptopropane, 1,4-dimercaptobutane, 1,6-dimercaptohexane, bis(2-mercaptoethyl)sulfide, 1,2-bis(2-mercaptoethylthio)ethane, 1,5-dimercapto-3-oxapene Methane, 1,8-dimercapto-3,6-dioxaoctane, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-mercaptomethyl-1,3-dimercaptopropane, 2-mercaptomethyl-1,4-dimercaptopropane, 2-(2-mercaptoethylthio)-1,3-dimercaptopropane, 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, 1,1,1-tris(mercaptomethyl)propane, tetrakis(mercaptomethyl)methane, 4,8-dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 5,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 1,1,3,3-Tetrakis(mercaptomethylthio)propane, Ethylene glycol bis(2-mercaptoacetate), Ethylene glycol bis(3-mercaptopropionate), 1,4-Butanediol 1,1-Dimercaptocyclohexane, 1,2-Dimercaptocyclohexane Xane, 1,3-dimercaptocyclohexane, 1,4-dimercaptocyclohexane, 1,3-bis(mercaptomethyl)cyclohexane, 1,4-bis(mercaptomethyl)cyclohexane, 2,5-bis(mercaptomethyl)-1,4-dithiane, 2,5-bis(mercaptoethyl)-1,4-dithiane, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, Bis(4-mercaptophenyl) sulfide, bis(4-mercaptophenyl) ether, 2,2-bis(4-mercaptophenyl)propane, bis(4-mercaptomethylphenyl) sulfide, bis(4-mercaptomethylphenyl) ether, 2,2-bis(4-mercaptomethylphenyl)propane, dithiothreitol, hexanedithiol, propanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-Butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis(3-mercaptobutyrate) Trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(4-mercaptobutyrate), trimethylolpropane tris(4-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(2-(3-sulfanylbutanoyloxy)ethyl)-1,3,5-triazinan-2,4,6-trione, pentaerythritol tetrakis(3-mercaptopropionate), Trimethylolpropanetris(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), dipentaerythritol hexakis(2-mercaptopropionate), dipentaerythritol hexakis(3-mercaptobutyrate), dipentaerythritol hexakis(4-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), tris-[(3-mercaptopropionate] [Oxy)-ethyl]-isocyanurate, tetraethylene glycol bis(3-mercaptopropionate), trimethylolpropanedipropanthol, pentaerythritol tripropanthol, pentaerythritol tetrapropanthol, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-Dimercapto-s-triazine, diallylaminotriazinedithiol, (vinylbenzylpropyl)aminotriazinedithiol, (diisopropylamino)triazinedithiol, (diisobutylamino)triazinedithiol, di(ethylhexyl)aminotriazinedithiol, (allylamino)triazinedithiol, (butylamino)triazinedithiol, bis(2-mercaptoethyl)sulfide, pentaerythritol tetrakis(2-mercaptoacetate), 2,5-bis(mercaptomethyl)-1,4-dithiane, 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, 4,8-dimercaptomethyl-1,11-di Mercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, bis(mercaptomethyl)benzene, pentaerythritol tetramercaptoacetate, trimethylolpropane trimercaptoacetate, glycolpropane dimercaptoacetate, pentaerythritol tetra(mercaptopropionate), trimethylolpropane tris(mercaptopropionate), glycol di(mercaptopropionate) , polysulfide polymers, polyoxyalkylene polythiols, polyether polythiols, polyoxyalkylenedithiols, polyoxyalkylenthiliols, polyether thiols, polyoxyalkylenthiols, mercapto-terminated polymers such as polysulfide polymers and thiocarboxylic acid polyesters, Examples include polyvalent mercaptos such as resins manufactured by any method that contains mercapto groups. These may be used individually or in combination of two or more. Polyvalent mercaptos are particularly preferred.

[0179] Among the polyvalent mercaptos, the preferred ones are 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, diallylaminotriazinedithiol, (vinylbenzylpropyl)aminotriazinedithiol, (diisopropylamino)triazinedithiol, (diisobutylamino)triazinedithiol, di(ethylhexyl)aminotriazinedithiol, (allylamino)triazinedithiol, (butylamino)triazinedithiol, trimethylolpropanetris (mercaptopropionate), dipentaerythritol hexakis (mercaptopropionate), pentaerythritol tetrakis (mercaptopropionate), pentaerythritol tetrakis (mercaptobutyrate), and trimethylolpropanetris (mercaptobutyrate).

[0180] Mercapto alcohols are not particularly limited, but examples include mercaptomethanol, mercaptoethanol, mercaptopropanol, mercaptobutanol, hydroxypropyl mercaptan, phenylmercaptoethanol, phenylhydroxyethyl mercaptan, mercaptobutanol, mercaptobutanediol, mercaptobutanetriol, thioglycerol, mercaptopropanediol, mercaptopropanediol, dimercaptopropanol, dimercaptopropanol, dimethylpropanediol, and glyceryl dithioglycolate.

[0181] Mercapto organic acids are not particularly limited, but examples include mercaptocarboxylic acids such as thioglycolic acid, mercaptopropionic acid, mercaptobenzoic acid, dimercaptopropionic acid, thiolactic acid, thiomalic acid, thiocoumaric acid, mercaptobutanoic acid, and mercaptoundecanoic acid.

[0182] The amount of curing component containing thiol groups is not particularly limited, but it is preferably 1 to 150 parts per 100 parts of episulfide resin, more preferably 1 to 100 parts, and even more preferably 1 to 50 parts.

[0183] When using a curing component containing a thiol group, it is preferable to use a base initiator among the curing initiators described above.

[0184] The curing component containing epoxy groups is not particularly limited, but known compounds can be used. Examples include bisphenol epoxy compounds, phenol epoxy compounds, alcohol epoxy compounds, glycidyl ester epoxy compounds, glycidyl ether epoxy compounds, amine epoxy compounds, glycidylamine epoxy resins, alicyclic epoxy compounds, compounds having an alicyclic skeleton and epoxy groups in the same molecule, urethane epoxy compounds, naphthalene skeleton-containing epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, urethane resins containing epoxy groups, (meth)acrylic resins containing epoxy groups, ester resins containing epoxy groups, ether resins containing epoxy groups, and epoxy resins that are precursors to the episulfide resin developed in this study. These may be used individually or mixed in any ratio of two or more as needed. Preferably, the compounds have two or more epoxy groups in one molecule.

[0185] The curing component containing epoxy groups is not particularly limited, but it may or may not contain functional groups such as (meth)acrylate groups, carboxyl groups, epoxy groups, or blocked isocyanate groups in addition to epoxy groups.

[0186] The amount of the curing component containing epoxy groups is not particularly limited, but it is preferable to add 1 to 500 parts per 100 parts of the episulfide resin.

[0187] The curing component containing the episulfide group is not particularly limited, but examples include compounds obtained by converting the above-mentioned epoxy group-containing curing component to episulfide. Preferably, it is a compound having two or more episulfide skeletons in one molecule.

[0188] The curing component containing an episulfide group is not particularly limited, but it may or may not contain other functional groups such as (meth)acrylate groups, carboxyl groups, epoxy groups, blocked isocyanate groups, etc.

[0189] The curing component containing an oxetane group is not particularly limited, but known compounds can be used. For example, (3-ethyloxetane-3-yl)methyl acrylate, (3-ethyloxetane-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyl oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl-3-{[3-(trie Toxysilyl)propoxy]methyl}oxetane, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)] Methyl ether 3-ethyl-3-hydroxymethyl oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycosidine bis(3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-Bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol Examples include lithritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, and resins containing oxetane groups obtained by any method. These may be used individually or mixed in any ratio of two or more as needed.

[0190] The curing component containing acid anhydride units can be any known or conventional acid anhydride, and is not particularly limited, but examples include acid anhydrides that are liquid at 25°C, such as methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, and methylendomethylenetetrahydrophthalic anhydride; acid anhydrides such as succinic anhydride, hydrogenated pyromellitic anhydride, hydrogenated biphenyl dianhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylcyclohexenedicarboxylic acid anhydride; and resins containing acid anhydride units obtained by any method.

[0191] The curing component containing a phenol group is not particularly limited, but examples include phenol, naphthol, hydroquinone, catechol, resorcinol, bisphenol A, bisphenol F, bisphenol sulfone, bisphenol ether, bisphenol sulfide, halogenated bisphenol A, novolac resin, and resins containing a phenol group obtained by any method.

[0192] The curing component containing a blocked isocyanate group is not particularly limited, but in addition to the blocked isocyanate group, the (meth)acrylate-containing resin may also have functional groups such as carboxyl groups, epoxy groups, and blocked isocyanate groups. The curing component containing a blocked isocyanate group is not particularly limited, but for example, a compound obtained by reacting a compound having an isocyanate group with a blocking agent can be mentioned.

[0193] Compounds having an isocyanate group are not particularly limited, but include, for example, aliphatic compounds such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate; alicyclic compounds such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanate methyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanate methyl)cyclohexane; and 1,5-naphthylene diiso Examples of compounds having aromatic structures include cyanates, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyliisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, 2,4-toluenediisocyanate, 2,6-toluenediisocyanate, xylylenediisocyanate, m-tetramethylxylylenediisocyanate, 4,4-diphenylmethane diisocyanate, tolylenediisocyanate, bischloromethyldiphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanatemethyl)benzene. Examples of these compounds include biuret, isocyanurate, adduct, and allophanate forms.

[0194] Examples of blocking agents, though not particularly limited, include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, imide compounds, urea compounds, imine compounds, and bisulfite compounds.

[0195] Examples of oxime compounds include formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, and benzophenone oxime. Examples of lactam compounds include ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam. Examples of phenolic compounds include phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, p-tert-butylphenol, nonylphenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, p-naphthol, and p-nitrophenol. Examples of alcohol compounds include methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, and furfuryl alcohol. Examples of amine compounds include diphenylamine, phenylnaphthylamine, aniline, and carbazole. Examples of active methylene compounds include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone. Among these, diethyl malonate is preferred. Examples of pyrazole compounds include pyrazole, methylpyrazole, and 3,5-dimethylpyrazole. Examples of mercaptan compounds include butyl mercaptan, thiophenol, and tert-dodecyl mercaptan. Examples of imidazole compounds include imidazole, 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole. Examples of imide compounds include succinimide, maleimide, maleimide, and phthalimide. Examples of urea compounds include urea, thiourea, and ethyleneurea. Examples of imine compounds include ethyleneimine and polyethyleneimine. Examples of bisulfite compounds include sodium bisulfite and potassium bisulfite. These blocking agents can be used individually or in combination of two or more types.

[0196] The blocking agent is preferably at least one selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds, and is preferably at least one selected from the group consisting of oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds from the viewpoint of protective reactions, deprotection reactions, and transesterification reactions.

[0197] (acid, acid anhydride) The curable resin composition is not particularly limited, but acids or acid anhydrides may be added to improve stability over time or other physical properties.

[0198] The curing components containing acids or acid anhydrides are not particularly limited, but include, for example, nitric acid, hydrochloric acid, sulfuric acid, fuming sulfuric acid, boric acid, carbonic acid, arsenic acid, phosphoric acid, hydrocyanic acid, formic acid, acetic acid, peracetic acid, thioacetic acid, oxalic acid, tartaric acid, propionic acid, butyric acid, succinic acid, maleic acid, benzoic acid, nitric anhydride, sulfuric acid anhydride, boron oxide, arsenic pentoxide, phosphorus pentoxide, chromic anhydride, acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, silica gel, silica alumina, aluminum chloride, fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, bromoacetic acid, Examples include dibromoacetic acid, tribromoacetic acid, iodoacetic acid, cyanoacetic acid, nitroacetic acid, phenoxyacetic acid, thioacetic acid, pyruvate, 2-chloropropionic acid, 2,2-dichloropropionic acid, 2-bromopropionic acid, 2,2-dibromopropionic acid, 3-cyanopropionic acid, 3-nitropropionic acid, 2-chlorobutyric acid, 4-cyanobutyric acid, o-chlorobenzoic acid, o-bromobenzoic acid, o-fluorobenzoic acid, o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid, trifluoroacetic anhydride, chloroacetic anhydride, dichloroacetic anhydride, trichloroacetic anhydride, and acid anhydrides of the aforementioned monofunctional organic acids. Two or more of these compounds may be used in combination.

[0199] The curing components containing oxazoline groups are not particularly limited, but include 2,2'-bis(2-oxazoline), 1,2,4-tris-(2-oxazolinyl-2)-benzene, 4-furan-2-ylmethylene-2-phenyl-4H-oxazol-5-one, 1,4-bis(4,5-dihydro-2-oxazolyl)benzene, 1,3-bis(4,5-dihydro-2-oxazolyl)benzene, 2,3-bis(4-isopropenyl-2-oxazoline-2-yl)butane, and 2,2'-bis Examples include su-4-benzyl-2-oxazoline, 2,6-bis(isopropyl-2-oxazoline-2-yl)pyridine, 2,2'-isopropylidenebis(4-tert-butyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2,2'-methylenebis(4-tert-butyl-2-oxazoline), and 2,2'-methylenebis(4-phenyl-2-oxazoline), 2,2'-bis(4-methyl-2-oxazoline), etc. In addition to these, polymers and oligomers containing oxazolyl, such as Epocross (trade name, manufactured by Nippon Shokubai Co., Ltd.), may also be used. Two or more of these compounds may be used in combination.

[0200] (Sensitizer) The curable resin composition may contain a sensitizer for the purpose of further improving sensitivity or improving the film properties after curing. The sensitizer is not particularly limited and may include, for example, p-methoxyphenol, hydroquinone, alkyl-substituted hydroquinone, benzophenone derivatives such as catechol and tert-butylcatechol, chalcone derivatives and unsaturated ketone derivatives such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiadin such as phenothiazine, etc. Examples include ion derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyradinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxaliloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyririum derivatives, thiopyrillium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, and organoruthenium complexes. These may be used individually or in combination of two or more.

[0201] (Leveling agent, defoaming agent) Examples of leveling agents or defoaming agents include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyester-modified hydroxyl-containing polydimethylsiloxane, polyether ester-modified hydroxyl-containing polydimethylsiloxane, acrylic copolymers, methacrylic copolymers, polyether-modified polymethylalkylsiloxane, alkyl acrylate copolymers, alkyl methacrylate copolymers, and lecithin.

[0202] Examples of antifoaming agents include silicone resins, silicone solutions, and copolymers of alkyl vinyl ethers, alkyl acrylates, and alkyl methacrylates.

[0203] (Coloring ingredient) The curable resin composition may contain a coloring component. The coloring component is not particularly limited and may include dyes, organic pigments, inorganic pigments, or conventionally known colorants such as carbon black. These coloring components may be used individually or in combination of two or more in order to obtain the desired color density and hue.

[0204] Examples of dyes include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

[0205] Examples of organic pigments include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, surene pigments, or metal complex pigments.

[0206] Examples of inorganic pigments include titanium dioxide, zinc oxide, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin gray, talc, bentonite, black iron oxide, carbon black, cadmium red, red iron oxide, molybdenum red, molybdate orange, chromium vermilion, lead yellow, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chromium green, Victoria green, ultramarine, dark blue, cobalt blue, cerulean blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, or cobalt violet.

[0207] Examples of carbon black include acetylene black, channel black, and furnace black.

[0208] The curable resin composition may further contain, depending on the purpose, oxygen scavengers and reducing agents such as phosphine, phosphonate, and phosphite, anti-fogging agents, anti-fading agents, anti-halation agents, fluorescent whitening agents, surfactants, bulking agents, plasticizers, flame retardants, antioxidants, pigment precursors, ultraviolet absorbers, foaming agents, antifungal agents, antistatic agents, magnetic materials, storage stabilizers such as silane coupling agents and quaternary ammonium chloride, plasticizers, slipping agents, antiblocking agents, light stabilizers, defoaming agents, infrared absorbers, thixotropic agents, antibacterial agents, fine particles such as silica, and other additives that impart various properties, as well as diluent solvents.

[0209] <Cured film> The cured film of the present invention is formed using the curable resin composition described above, and can be formed using known methods. The cured film can be obtained, for example, by applying the curable resin composition to a substrate, preheating to evaporate the solvent, and then postheating to cure it. The preheating temperature is not particularly limited and may be, for example, 20 to 200°C, preferably 50 to 150°C, and more preferably 50 to 100°C. The postheating temperature is not particularly limited and may be, for example, 40 to 300°C, preferably 50 to 150°C, and more preferably 70 to 100°C. The thickness of the cured film is preferably 0.01 μm to 300 mm.

[0210] The cured film of the present invention may be formed by exposure to active energy rays, or by using photolithography or printing. When forming a cured film using photolithography, for example, the curable resin composition can be applied to a substrate, exposed through a mask, developed to form a pattern, and then heated and fired to produce the cured film. Furthermore, the cured film of the present invention may be formed by methods other than those described above, for example, by molding methods such as vacuum forming, pressure forming, TOM forming, injection molding, in-mold forming, press forming, and stamping forming.

[0211] The curable resin composition of the present invention can be coated onto a variety of substrates. Examples of substrates include metals such as aluminum, iron, chromium, zinc, magnesium, titanium, and steel; thermoplastic polymers such as polyethylene, polypropylene, polyurethane, polyacrylate, polycarbonate, and their copolymers; thermosetting polymers such as vulcanized rubber; and metal films and organic films such as urea-formaldehyde foam, melamine resin, wood, carbon fiber reinforced plastics, glass fiber reinforced plastics, and other fiber-reinforced plastics, paper, glass, silicon wafers, ITO, and molybdenum.

[0212] The curable resin composition of the present invention does not require high-temperature heating; for example, a cured film with excellent properties can be obtained even with low-temperature firing at 100°C or below. Therefore, even when a plastic film substrate with low heat resistance is used as the substrate, it is possible to obtain an excellent cured film without damaging the substrate.

[0213] As described above, the curable composition of the present invention exhibits excellent curability at low temperatures and stability over time, and can be applied to various substrates. It is suitably used in various inks, overcoat varnishes, various printing plate materials, photoresists, color resists, electrophotographs, optical fibers, holographic materials and other photosensitive materials, various recording media such as microcapsules, as well as optical materials, adhesives, sealants, release coatings, encapsulants, and various coatings. [Examples]

[0214] The present invention will be described in more detail below with reference to examples and comparative examples. In the examples and comparative examples, "parts" and "%" refer to "parts by mass" and "% by mass" respectively, unless otherwise specified.

[0215] <Gel Permeation Chromatography (GPC)> The weight-average molecular weight (Mw) was determined as a polystyrene equivalent value by GPC (gel permeation chromatography) measurement under the following conditions. Specifically, the resin was dissolved in tetrahydrofuran to prepare a 1% solution, which was then measured using the following apparatus and measurement conditions. Equipment: HLC-8420-GPC system (manufactured by Tosoh Corporation) Columns: TSK-GELGuardColumn, SuperHZ-LTSK-GEL, SUPERHZM-N (2 columns connected in series) Leaching solvent: tetrahydrofuran Standard material: Polystyrene (manufactured by Tosoh Corporation) Flow rate: 0.35 mL / min, Sample solution volume: 10 μL, Column temperature: 40°C

[0216] <Nuclear magnetic resonance analysis (NMR)> Measurement conditions and equipment: BRUKERAVANCE400 Resonance frequency: 400MHz ( 1 (H-NMR) Deuterated solvent: Dimethyl sulfoxide-d6 or deuterated chloroform 1 Tetramethylsilane was used as the internal standard for 1H-NMR, and the chemical shift values ​​were expressed as δ values ​​(ppm). 13 As an internal standard substance for 13C-NMR, chemical shift values were expressed as δ values (ppm) using dimethyl sulfoxide or chloroform contained in a heavy solvent. 1 In 1H-NMR, the quantitative analysis of the composition ratio was performed using the following chemical shift values. Vinyl: around 4.5 - 7.0 ppm Epoxide: around 2.0 - 3.0 ppm Episulfide: around 1.5 - 3.0 ppm 13 In 13C-NMR, the quantitative analysis of the composition ratio was performed using the following chemical shift values. Vinyl: around 100 - 160 ppm Epoxide: around 40 - 70 ppm Episulfide: around 20 - 50 ppm

[0217] <Synthesis of episulfide resin> [Example 1-1] <First step> In a reaction vessel equipped with a gas introduction tube, a stirrer, a thermometer, and a reflux condenser, 27 parts of trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd.), 377 parts of 4-vinylcyclohexene oxide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 110 parts of ethyl acetate were mixed at 50°C. Then, 81 parts of a 10% diethyl ether complex of boron trifluoride in ethyl acetate solution was slowly dropped and stirred. Then, 260 parts of ethyl acetate was added, and the obtained reaction mixture was separated and washed with water, dried with sodium sulfate, and distilled under reduced pressure to obtain a resin containing a structural unit (G2-1) represented by the following chemical formula, which corresponds to the structural unit represented by the general formula (2) of the present disclosure. <​​​​​​​​​​​​​​Thereafter, 300 parts of the obtained solid content were separated, mixed with 300 parts of ethyl acetate, and then 572 parts of an ethyl acetate solution with a peracetic acid concentration of 30% at 50°C were slowly added, followed by stirring. The obtained reaction mixture was washed with water, dried with sodium sulfate, and distilled under reduced pressure to obtain an epoxy resin (Aep-1) containing (G2-1) as a constitutional unit and the following (GS-1) corresponding to other constitutional units of the present disclosure.

[0220] Other constitutional unit (GS-1)

Chemical formula

[0221] ​​​​​​​​​​​​​​​​​​

[0223] [Synthesis of 4-vinylcyclohexene-1,2-episulfide] In a reaction vessel equipped with a gas inlet tube, stirrer, thermometer, and refluxer, 239 parts of 4-vinylcyclohexene-1,2-epoxide, 293 parts of ammonium thiocyanate, and 2290 parts of methanol solvent were charged and stirred at 43°C. After confirming the consumption of the raw materials, the reaction mixture was extracted with dichloromethane and washed with water, and the resulting residue was concentrated and purified by silica gel column chromatography. The obtained purified product was identified as 4-vinylcyclohexene-1,2-episulfide by NMR.

[0224] [ka]

[0225] [Examples 1-2 to 1-18] Epoxy resin (Aep-2~18) and episulfide resin (A-2~18) were obtained by the same method as in Example 1-1, except that the compound composition was changed as shown in Tables 1-1 and 1-2. The mass composition ratio and weight-average molecular weight of the obtained episulfide resins are shown in Tables 1-1 and 1-2.

[0226] [Table 1-1]

[0227] [Table 1-2]

[0228] The abbreviations used in Table 1 are shown below. Karenz BEI: 1,1-(bisacryloyloxymethyl)ethyl isocyanate

[0229] The constituent units contained in the episulfide resin (A-18) of Example 1-18, and the constituent units included in the synthesis process of (A-18) are shown below.

[0230] The structural unit (G1-2) represented by the general formula (1)

Chemical formula

[0231] Structural unit (GS-2)

Chemical formula

[0232] The structural unit (G2-2) represented by the general formula (2)

Chemical formula

[0233] [Examples 1-19] <Modification step> In a reaction vessel equipped with a gas introduction tube, a stirrer, a thermometer, and a reflux condenser, 100 parts of an epoxy resin (Aep-1), 404 parts of butyl acetate, 20 parts of acrylic acid, 0.11 part of 4-methoxyphenol, and 0.83 part of trimethylbenzylammonium chloride were mixed at room temperature. Then, while bubbling dry air, the temperature was raised to 120 °C and stirring was carried out. The resulting reaction mixture was washed three times with brine. Then, the organic layer was dried using magnesium sulfate and distilled off under reduced pressure to obtain an epoxy resin (Aep-19) containing, as structural units, (G2-1), the following (G2-4) corresponding to the structural unit represented by the general formula (2) of the present disclosure, and (GS-1). The mass composition ratio of the obtained epoxy resin (Aep-19) was 1 1H-NMR, 13 The weight average molecular weight was determined by GPC measurement through 13C-NMR measurement.

[0234] The structural unit (G2-4) represented by the general formula (2)

Chemical formula

[0235] <Third step><Proceed to In a reaction vessel equipped with a gas inlet pipe, stirrer, thermometer, and refluxer, 100 parts of the epoxy resin (Aep-19) and 226 parts of butyl acetate were charged and stirred under a dry air atmosphere. Then, while stirring, a mixture of 32 parts of thiourea and 206 parts of methanol was added dropwise, followed by the addition of 0.04 parts of 18-crown-6-ether and 21 parts of molecular sieve 4A, and the reaction was carried out at 50°C while bubbling dry air. After that, the reaction mixture was filtered, the filtrate was removed by vacuum distillation, and the residue was washed three times with saline solution. Subsequently, the organic layer was dried and removed by vacuum distillation using magnesium sulfate to obtain episulfide resin (A-19) containing (G1-1) as a constituent unit represented by general formula (1) and (G2-1) and (G2-4) as constituent units represented by general formula (2). The mass composition ratio of the obtained episulfide resin (A-19) was 1 H-NMR, 13 The weight-average molecular weight was determined by GPC measurement using 1C-NMR.

[0236] [Examples 1-20 to 1-22] Epoxy resins (Aep-20~22) and episulfide resins (A-20~22) were obtained by the same method as in Examples 1-19, except that the compound composition was changed as shown in Table 2. The mass composition ratio and weight-average molecular weight of the obtained episulfide resins are shown in Table 2.

[0237] [Table 2]

[0238] [Examples 1-23] <First step> In a reaction vessel equipped with a gas inlet pipe, a stirrer, a thermometer, and a refluxer, 27 parts of trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd.), 377 parts of 4-vinylcyclohexene oxide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 110 parts of ethyl acetate were mixed at 50°C. Then, 81 parts of a 10% ethyl acetate solution of boron trifluoride diethyl ether complex were slowly added dropwise, and the mixture was stirred. After that, ethyl acetate was added, and the resulting reaction mixture was separated and washed with water, followed by drying with sodium sulfate and distillation under reduced pressure to obtain a resin containing (G2-1) as a constituent unit.

[0239] <Second process> Subsequently, 300 parts of the obtained solids were separated and mixed with 300 parts of ethyl acetate. Then, 1500 parts of ethyl acetate solution with a 30% peracetic acid concentration at 50°C were slowly added and stirred. The resulting reaction mixture was washed with water, dried with sodium sulfate, and removed by vacuum distillation to obtain a resin containing (GS-1) as a constituent unit. The mass composition ratio of the obtained resin was 1 H-NMR, 13 The weight-average molecular weight was determined by GPC measurement using 1C-NMR.

[0240] <Modification process> In a reaction vessel equipped with a gas inlet pipe, a stirrer, a thermometer, and a refluxer, 336 parts of the resin obtained above, 1100 parts of butyl acetate, 6 parts of acrylic acid, 0.04 parts of 4-methoxyphenol, and 0.27 parts of trimethylbenzylammonium chloride were mixed at room temperature. Then, the temperature was raised to 120°C while bubbling dry air, and the mixture was stirred. The resulting reaction mixture was washed three times with saline solution. Subsequently, the organic layer was dried with magnesium sulfate and removed by vacuum distillation to obtain epoxy resin (Aep-23) containing (GS-1) and (G2-4) as constituent units. The mass composition ratio of the obtained epoxy resin (Aep-23) was 1 H-NMR, 13 The weight-average molecular weight was determined by GPC measurement using 1C-NMR.

[0241] <Third process> In a reaction vessel equipped with a gas inlet pipe, stirrer, thermometer, and refluxer, 100 parts of the epoxy resin (Aep-23) and 226 parts of butyl acetate were charged and stirred under a dry air atmosphere. Then, while stirring, a mixture of 65 parts of thiourea and 206 parts of methanol was added dropwise, followed by the addition of 0.04 parts of 18-crown-6-ether and 21 parts of molecular sieve 4A. The reaction was carried out at 50°C while bubbling dry air. The reaction mixture was then filtered, the filtrate was removed by vacuum distillation, and the residue was washed three times with saline solution. The organic layer was then dried with magnesium sulfate and removed by vacuum distillation to obtain episulfide resin (A-23) containing (G1-1) as a constituent unit represented by general formula (1) and (G2-4) as a constituent unit represented by general formula (2). The mass composition ratio of the obtained episulfide resin (A-23) was 1 H-NMR, 13 The weight-average molecular weight was determined by GPC measurement using 1C-NMR.

[0242] [Examples 1-24 to 1-26] Epoxy resins (Aep-24~26) and episulfide resins (A-24~26) were obtained by the same method as in Examples 1-23, except that the compound composition was changed as shown in Table 3. The mass composition ratio and weight-average molecular weight of the obtained episulfide resins are shown in Table 3.

[0243] [Table 3]

[0244] The constituent units represented by general formula (2) contained in the episulfide resins (A-24 to A-26) of Examples 1-24 to 1-26 are shown below.

[0245] The constituent unit represented by general formula (2) (G2-5, G2-6, G2-7) [ka]

[0246] [Examples 1-27] <First modification process> In a reaction vessel equipped with a gas inlet pipe, stirrer, thermometer, and refluxer, 334 parts epoxy resin (Aep-1), 404 parts butyl acetate, 8 parts acrylic acid, 0.05 parts 4-methoxyphenol, and 0.3 parts trimethylbenzylammonium chloride were mixed at room temperature. The mixture was then heated to 120°C while bubbling dry air and stirred. The resulting reaction mixture was washed three times with saline solution. The organic layer was then dried with magnesium sulfate and removed by reduced-pressure distillation to obtain a resin containing (G2-1), (G2-4), and (GS-1) as constituent units. The mass composition ratio of the obtained resin was: 1 H-NMR, 13 The weight-average molecular weight was determined by GPC measurement using 1C-NMR.

[0247] <Second modification process> In a reaction vessel equipped with a gas inlet pipe, a stirrer, a thermometer, and a refluxer, 342 parts of the above resin, 1415 parts of butyl acetate, 12 parts of succinic anhydride, 0.05 parts of methoxyphenol, and 0.5 parts of triethylamine were charged, and the mixture was heated to 120°C while bubbling dry air, and stirred. The resulting reaction mixture was washed with water, the organic layer was dried using magnesium sulfate, and the organic layer was removed by reduced pressure distillation to obtain an epoxy resin (Aep-27) containing (G2-1), (G2-8) and (GS-1), which correspond to the constituent units represented by general formula (2) in this disclosure, as constituent units. The mass composition ratio of the obtained epoxy resin (Aep-27) is 1 H-NMR, 13 The weight-average molecular weight was determined by GPC measurement using 1C-NMR.

[0248] The constituent unit (G2-8) is represented by general formula (2). [ka]

[0249] <Third process> In a reaction vessel equipped with a gas inlet pipe, a stirrer, a thermometer, and a refluxer, 100 parts of the epoxy resin (Aep-27) and 226 parts of butyl acetate were charged and stirred under a dry air atmosphere. Then, while stirring, a mixture of 58 parts of thiourea and 206 parts of methanol was added dropwise, followed by the addition of 0.07 parts of 18-crown-6-ether and 38 parts of molecular sieve 4A. The reaction was carried out at 50°C while bubbling dry air. After that, the reaction mixture was filtered, the filtrate was removed by vacuum distillation, the residue was washed with water, and the organic layer was dried with magnesium sulfate and removed by vacuum distillation to obtain episulfide resin (A-27) containing (G1-1) as a constituent unit represented by general formula (1), and (G2-1) and (G2-8) as constituent units represented by general formula (2). The mass composition ratio of the obtained episulfide resin (A-27) was 1 H-NMR, 13 The weight-average molecular weight was determined by GPC measurement using 1C-NMR.

[0250] [Examples 1-28 to 1-30] Epoxy resin (Aep-28~30) and episulfide resin (A-28~30) were obtained by the same method as in Example 1-27, except that the compound composition was changed as shown in Table 4. The mass composition ratio and weight-average molecular weight of the obtained episulfide resins are shown in Table 4.

[0251] The constituent units represented by general formula (2) contained in the episulfide resins (A-28 to A-30) of Examples 1-28 to 1-30 are shown below.

[0252] The constituent unit represented by general formula (2) (G2-9, G2-10, G2-11) [ka]

[0253] [Examples 1-31] <First modification process> In a reaction vessel equipped with a gas inlet pipe, stirrer, thermometer, and refluxer, 334 parts epoxy resin (Aep-1), 404 parts butyl acetate, 6 parts acrylic acid, 0.03 parts 4-methoxyphenol, and 0.2 parts trimethylbenzylammonium chloride were mixed at room temperature. The mixture was then heated to 120°C while bubbling dry air and stirred. The resulting reaction mixture was washed three times with saline solution. The organic layer was then dried using magnesium sulfate and removed by reduced-pressure distillation to obtain a resin containing (G2-1), (G2-4), and (GS-1) as constituent units. The mass composition ratio of the obtained resin was: 1 H-NMR, 13 The weight-average molecular weight was determined by GPC measurement using 1C-NMR.

[0254] <Second modification process> In a reaction vessel equipped with a gas inlet pipe, a stirrer, a thermometer, and a refluxer, 340 parts of the above resin, 415 parts of dehydrated butyl acetate, 20 parts of 1,1-(bisacryloyloxymethyl)ethyl isocyanate, 0.03 parts of methoxyphenol, and 0.06 parts of dibutyltin dilaurate (DBTDL) were charged, and the mixture was stirred at room temperature while bubbling dry air. Then, the temperature was raised to 70°C and the mixture was stirred. The resulting reaction mixture was washed with water, the organic layer was dried using magnesium sulfate, and the organic layer was removed by vacuum distillation to obtain an epoxy resin (Aep-31) containing (G2-1), (G2-12) and (GS-1), which correspond to the constituent units represented by general formula (2) in this disclosure, as constituent units. The mass composition ratio of the obtained epoxy resin (Aep-31) is 1 H-NMR, 13 The weight-average molecular weight was determined by GPC measurement using 1C-NMR.

[0255] The constituent unit (G2-12) represented by general formula (2) [ka]

[0256] <Third process> In a reaction vessel equipped with a gas inlet pipe, a stirrer, a thermometer, and a refluxer, 100 parts of the epoxy resin (Aep-31) and 226 parts of butyl acetate were charged and stirred under a dry air atmosphere. Then, while stirring, a mixture of 58 parts of thiourea and 206 parts of methanol was added dropwise, followed by the addition of 0.07 parts of 18-crown-6-ether and 38 parts of molecular sieve 4A. The reaction was carried out at 50°C while bubbling dry air. After that, the reaction mixture was filtered, the filtrate was removed by vacuum distillation, the residue was washed with water, and the organic layer was dried with magnesium sulfate and removed by vacuum distillation to obtain episulfide resin (A-31) containing (G1-1) as a constituent unit represented by general formula (1) and (G2-1) and (G2-12) as constituent units represented by general formula (2). The mass composition ratio of the obtained episulfide resin (A-31) was 1 H-NMR, 13 The weight-average molecular weight was determined by GPC measurement using 1C-NMR.

[0257] [Examples 1-32] <First modification process> In a reaction vessel equipped with a gas inlet pipe, stirrer, thermometer, and refluxer, 334 parts epoxy resin (Aep-1), 404 parts butyl acetate, 10 parts acrylic acid, 0.05 parts 4-methoxyphenol, and 0.4 parts trimethylbenzylammonium chloride were mixed at room temperature. The mixture was then heated to 120°C while bubbling dry air and stirred. The resulting reaction mixture was washed three times with saline solution. The organic layer was then dried with magnesium sulfate and removed by reduced-pressure distillation to obtain a resin containing (G2-1), (G2-4), and (GS-1) as constituent units. The mass composition ratio of the obtained resin was: 1 H-NMR, 13 The weight-average molecular weight was determined by GPC measurement using 1C-NMR.

[0258] <Second modification process> In a reaction vessel, 343 parts of the above resin, 1415 parts of dehydrated butyl acetate, 14 parts of triethylamine, and 0.05 parts of methoxyphenol were stirred at 0°C. Then, while stirring at 0°C, 12 parts of acrylic acid chloride were added dropwise, and the mixture was stirred at 0°C. After that, the temperature was raised to room temperature and stirred further, then the temperature was raised to 60°C and stirred while bubbling dry air. The resulting reaction mixture was washed with water, the organic layer was dried with magnesium sulfate, and the organic layer was removed by vacuum distillation to obtain an epoxy resin (Aep-32) containing (G2-1), (G2-13) corresponding to general formula (2) in this disclosure, and (GS-1) as constituent units. The mass composition ratio of the obtained epoxy resin (Aep-32) is 1 H-NMR, 13 The weight-average molecular weight was determined by GPC measurement using 1C-NMR.

[0259] The constituent unit represented by general formula (2) (G2-13) [ka]

[0260] <Third process> In a reaction vessel equipped with a gas inlet pipe, a stirrer, a thermometer, and a refluxer, 100 parts of the epoxy resin (Aep-32) and 226 parts of butyl acetate were charged and stirred under a dry air atmosphere. Then, while stirring, a mixture of 58 parts of thiourea and 206 parts of methanol was added dropwise, followed by the addition of 0.07 parts of 18-crown-6-ether and 38 parts of molecular sieve 4A. The reaction was carried out at 50°C while bubbling dry air. After that, the reaction mixture was filtered, the filtrate was removed by vacuum distillation, the residue was washed with water, and the organic layer was dried with magnesium sulfate and removed by vacuum distillation to obtain episulfide resin (A-32) containing (G1-1) as a constituent unit represented by general formula (1) and (G2-1) and (G2-13) as constituent units represented by general formula (2). The mass composition ratio of the obtained episulfide resin (A-32) was 1 H-NMR, 13 The weight-average molecular weight was determined by GPC measurement using 1C-NMR.

[0261] [Examples 1-33 to 1-36] Epoxy resins (Aep-33~36) and episulfide resins (A-33~36) were obtained by the same method as in Examples 1-32, except that the compound composition was changed as shown in Table 4. The mass composition ratio and weight-average molecular weight of the obtained episulfide resins are shown in Table 4.

[0262] [Table 4]

[0263] The constituent units represented by general formula (2) contained in the episulfide resins (A-33 to A-36) of Examples 1-33 to 1-36 are shown below.

[0264] The constituent unit represented by general formula (2) (G2-14, G2-15, G2-16, G2-17) [ka]

[0265] [Examples 1-37~38] Except for the change in the compound composition shown in Table 5, epoxy resin (Aep-37~38) and episulfide resin (A-37~38) were obtained by the same method as in Examples 1-19. The mass composition ratio and weight-average molecular weight of the obtained episulfide resins are shown in Table 5.

[0266] [Table 5]

[0267] [Examples 1-39] <First step> In a reaction vessel equipped with a gas inlet pipe, a stirrer, a thermometer, and a refluxer, 24 parts trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd.), 321 parts 4-vinylcyclohexene oxide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 110 parts ethyl acetate were mixed at 70°C. After cooling to room temperature, 20 parts 4-epoxycyclohexylmethyl methacrylate and 0.4 parts 4-methoxyphenol were added and stirred. Then, 78 parts of a 10% ethyl acetate solution of boron trifluoride diethyl ether complex were slowly added dropwise and stirred. Subsequently, ethyl acetate was added, and the resulting reaction mixture was subjected to liquid-liquid washing with water, followed by drying with sodium sulfate and distillation under reduced pressure to obtain a resin containing the following (G2-3) as constituent units, which correspond to the constituent units represented by general formula (2) in this disclosure.

[0268] The constituent unit (G2-3) represented by general formula (2) [ka]

[0269] <Second process> Subsequently, 365 parts of the obtained resin and 144 parts of ethyl acetate were mixed, and then 1229 parts of sodium bicarbonate, 2723 parts of acetone, and 2478 parts of water were added and stirred at room temperature. Then, 1746 parts of Oxon (potassium peroxysulfate double salt) were added in four parts at 2-hour intervals. After stirring at room temperature, water was added and extracted with ethyl acetate, washed with water, and dried with magnesium sulfate to obtain epoxy resin (Aep-39) containing (G2-3) and (GS-1) as constituent units. The mass composition ratio of the obtained epoxy resin (Aep-39) was 1 H-NMR, 13 The weight-average molecular weight was determined by GPC measurement using 1C-NMR.

[0270] <Third process> In a reaction vessel equipped with a gas inlet pipe, a stirrer, a thermometer, and a refluxer, 100 parts of the epoxy resin (Aep-39) and 320 parts of toluene were charged and stirred. Then, while stirring, a solution of 66 parts of thiourea and 292 parts of methanol was added dropwise, followed by the addition of 0.08 parts of 18-crown-6-ether and 43 parts of molecular sieve 4A. The reaction was carried out at 50°C while bubbling dry air. After that, the reaction mixture was filtered, the filtrate was removed by vacuum distillation, the residue was washed with water, and the organic layer was dried with magnesium sulfate and removed by vacuum distillation to obtain episulfide resin (A-39) containing (G1-1) as a constituent unit represented by general formula (1) and (G2-3) as a constituent unit represented by general formula (2). The mass composition ratio of the obtained episulfide resin (A-39) was 1 H-NMR, 13 The weight-average molecular weight was determined by GPC measurement using 1C-NMR.

[0271] [Examples 1-40] Except for the change in the compound composition shown in Table 6, epoxy resin (Aep-40) and episulfide resin (A-40) were obtained by the same method as in Examples 1-39. The mass composition ratio and weight-average molecular weight of the obtained episulfide resin are shown in Table 6.

[0272] [Table 6]

[0273] The constituent units included in the synthesis process of the episulfide resin (A-40) in Examples 1-40 are shown below.

[0274] Constituent unit (GS-3) [ka]

[0275] [Synthesis of (2-oxapent-4-enyl)-3,4-epoxycyclohexane] The compound with the structure shown below was synthesized using the method described in U.S. Patent No. US6075155. [ka]

[0276] [Manufacturing Example 1] (Process 1) In a round-bottom flask, 14.0 g of distilled 1,2,3,6-tetrahydrobenzaldehyde, 90.6 g of ethylene glycol monoallyl ether, and 16.24 g of triethylsilane were placed and stirred at 0°C. Then, 45.75 g of concentrated sulfuric acid was added dropwise over 1 hour using a dropping funnel, and the mixture was slowly heated to room temperature while further stirring was performed. Pentane was then added to the reaction mixture, washed with saturated brine, dried over sodium sulfate, and removed by vacuum distillation. The mixture was then purified by column chromatography. The resulting purified product (RM-1p) was obtained as follows: 1 HNMR 13 Based on the results of 1C NMR measurements, the structure was identified as follows.

[0277] (RM-1p) [ka]

[0278] (Process 2) In a reaction vessel equipped with a stirrer, dropping funnel, and thermometer, 32.3 g of 3-chloroperoxybenzoic acid (65% purity) and 300 mL of methylene chloride were placed and cooled to 0-3°C using an ice bath. Then, 150 mL of methylene chloride and 23.9 g of the compound (RM-1p) obtained in step 1 were added dropwise, ensuring the temperature did not exceed 10°C. The reaction mixture was then heated to room temperature and stirred further. The resulting reaction mixture was filtered, the filtrate was washed with saturated sodium bicarbonate water, and the organic layer was dried over sodium sulfate. Subsequently, the residue was removed by vacuum distillation, and the resulting residue was purified by column chromatography. The purified product obtained was 1 HNMR 13 CNMR measurement results It was identified as having the following structure.

[0279] (RM-1) [ka]

[0280] [Manufacturing Examples 2 and 3] Compounds RM-2 and RM-3 were obtained using the same method as for compound RM-1, except that the formulation was changed to the one shown in Table 7.

[0281] RM-2, RM-3 [ka] RM-2: m=5~6 RM-3:m=9

[0282] [Table 7]

[0283] [Examples 1-41] <First step> In a reaction vessel equipped with a gas inlet pipe, a stirrer, a thermometer, and a refluxer, 24 parts of trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd.), 452 parts of (2-oxapent-4-enyl)-3,4-epoxycyclohexane, and 159 parts of ethyl acetate were mixed at 50°C. Then, 78 parts of a 10% ethyl acetate solution of boron trifluoride diethyl ether complex were slowly added dropwise, and the mixture was stirred. After that, ethyl acetate was added, and the resulting reaction mixture was separated and washed with water, then dried with sodium sulfate and diluted under reduced pressure to obtain a resin containing the following (G2-18), which corresponds to the constituent unit represented by general formula (2) in this disclosure.

[0284] The constituent unit represented by general formula (2) (G2-18) [ka]

[0285] <Second process> Subsequently, 476 parts of the obtained resin and 187 parts of ethyl acetate were mixed, and then 1278 parts of sodium bicarbonate, 2833 parts of acetone, and 2577 parts of water were added and stirred at room temperature. Then, 1816 parts of Oxon (potassium peroxysulfate double salt) were added in four parts at 2-hour intervals. After stirring at room temperature, water was added and extracted with ethyl acetate, washed with water, and dried with magnesium sulfate to obtain epoxy resin (Aep-41) containing (G2-18) and (GS-4) below as constituent units. The mass composition ratio of the obtained epoxy resin (Aep-41) is 1 H-NMR, 13 The weight-average molecular weight was determined by GPC measurement using 1C-NMR.

[0286] Constituent unit (GS-4) [ka]

[0287] <Third process> In a reaction vessel equipped with a gas inlet pipe, stirrer, thermometer, and refluxer, 100 parts of the epoxy resin (Aep-41) and 320 parts of butyl acetate were charged and stirred. Then, while stirring, a mixture of 51 parts of thiourea and 206 parts of methanol was added dropwise, followed by the addition of 0.06 parts of 18-crown-6-ether and 33 parts of molecular sieve 4A, and the reaction was carried out at 50°C. After that, the reaction mixture was filtered, the filtrate was removed by vacuum distillation, the residue was washed with water, and the organic layer was dried with magnesium sulfate and removed by vacuum distillation to obtain episulfide resin (A-41) containing the following constituent units represented by general formula (1) (G1-3) and the constituent unit represented by general formula (2) (G2-18). The mass composition ratio of the obtained episulfide resin (A-41) is 1 H-NMR, 13 The weight-average molecular weight was determined by GPC measurement using 1C-NMR.

[0288] Constituent units (G1-3) represented by general formula (1) [ka]

[0289] [Examples 1-42 to 1-44] Except for the change in the compound composition shown in Table 8, epoxy resins (Aep-42~44) and episulfide resins (A-42~44) were obtained by the same method as in Example 1-41. The mass composition ratio and weight-average molecular weight of the obtained episulfide resins are shown in Table 8.

[0290] [Table 8]

[0291] The constituent units represented by general formula (1), the constituent units represented by general formula (2), and the constituent units contained in the resin during the synthesis process of the episulfide resins (A-42 to A-44) of Examples 1-42 to A-44 are shown below.

[0292] The constituent unit represented by general formula (1) (G1-4, G1-5, G1-6) [ka]

[0293] The constituent unit represented by general formula (2) (G2-19, G2-20, G2-21) [ka]

[0294] constituent units (GS-5, GS-6, GS-7) [ka]

[0295] [Comparative Example 1-1] Except for the change in the compound composition shown in Table 9, epoxy resin (HAep-1) and episulfide resin (HA-1) were obtained by the same method as in Example 1-1. The mass composition ratio and weight-average molecular weight of the obtained episulfide resin are shown in Table 9.

[0296] [Table 9]

[0297] [Comparative Example 1-2] In a reaction vessel equipped with a gas inlet pipe, stirrer, thermometer, and refluxer, 27 parts of trimethylolpropane (Tokyo Chemical Co., Ltd.), 377 parts of 4-vinylcyclohexene oxide (Tokyo Chemical Co., Ltd.), and 110 parts of ethyl acetate were added and mixed at 50°C. Then, 81 parts of a 10% ethyl acetate solution of boron trifluoride diethyl ether complex were slowly added dropwise and stirred. Subsequently, 260 parts of ethyl acetate were added, and the resulting reaction mixture was separated and washed with water, then dried with sodium sulfate and evaporated under reduced pressure to obtain resin (HA-2). The mass composition ratio of the obtained resin (HA-2) was 1 H-NMR, 13 The weight-average molecular weight was determined by GPC measurement using 1C-NMR. Table 10 shows the mass composition ratio and weight-average molecular weight.

[0298] [Table 10]

[0299] [Synthesis of curing initiator (K-1)] In a reaction vessel equipped with a gas inlet tube, stirrer, thermometer, and refluxer, 3.0 parts of 4-methoxybenzoyl chloride and 18 parts of anhydrous tetrahydrofuran were added. Then, a mixture of 1.8 parts of 4-(methylamino)pyridine, 3.0 parts of triethylamine, and 27 parts of anhydrous tetrahydrofuran was added dropwise while cooling in an ice bath. After stirring for 1 hour, the mixture was stirred at room temperature for 24 hours. The resulting reaction mixture was purified by silica gel column chromatography to obtain a curing initiator (K-1), which is a thermobase initiator as shown in the formula below.

[0300] Curing initiator (K-1) [ka]

[0301] [Synthesis of other components (S-1)] 272 parts of 6-(dibutylamino)-1,3,5-triazine-2,4-dithiol, 400 g of ethyl vinyl ether, and 1000 mL of acetone were added to a reaction vessel equipped with a gas inlet tube, a stirrer, a thermometer, and a refluxer. The mixture was heated under reflux for 12 hours with stirring, and then the acetone and excess ethyl vinyl ether were removed by vacuum distillation to obtain the other component (S-1), which is a hardened component (latent thiol) containing thiol groups.

[0302] Other ingredients (S-1) [ka]

[0303] <Manufacturing of curable resin compositions> [Example 2-1] A curable resin composition was obtained by stirring and mixing 100 parts of episulfide resin (A-1), 0.21 parts of 4-methylaminopyridine as a curing initiator, and 401 parts of methyl ethyl ketone (MEK) at room temperature.

[0304] [Examples 2-2 to 2-114, Comparative Examples 2-1 to 2-5] Except for the changes in the compound composition shown in Tables 11 to 19, a curable resin composition was obtained by preparing it in the same manner as in Example 2-1.

[0305] <Evaluation of curable resin compositions> The obtained curable resin compositions were evaluated for their low-temperature curability and long-term stability. The evaluation results are shown in Tables 11 to 19.

[0306] [Low temperature curability] The obtained curable resin composition was poured into a pre-weighed metal container and dried at 40°C for 30 minutes. The resulting dried film was heated at 85°C for 30 minutes. The metal container containing the cured film was then wrapped in a 100-mesh stainless steel mesh and immersed overnight in methyl ethyl ketone (MEK) at room temperature. Next, it was removed from the MEK, dried in a vacuum oven at 60°C for 3 hours, and then weighed. The gel fraction was calculated using the following formula (1). Evaluation was performed according to the following criteria. The practical level is S to C. Formula (1): (W3-W1) / (W2-W1)×100[%] W1: Weight of the metal container (g) W2: The sum of the weights of the sample and the metal container after heating at 85°C for 30 minutes. W3: The sum of the weights of the sample and the metal container after immersion in MEK. (Evaluation Criteria) S: Gel fraction is 90% or higher A: Gel fraction is 75% or more, but less than 90%. B: Gel fraction is 60% or more, but less than 75%. C: Gel fraction is 50% or more, but less than 60%. D: Gel fraction less than 50% (unusable)

[0307] [Stability over time] The viscosity of the obtained curable resin composition was measured before storage, and after storage at 25°C for one week and two weeks. Viscosity was measured using an EMS viscometer (manufactured by Kyoto Electronics Manufacturing Co., Ltd.) under the following conditions: measurement temperature 25°C, motor speed 1000 rpm, and spherical probe Al 2 mm. Temporal stability was evaluated by calculating the viscosity increase rate after storage relative to the initial viscosity, according to the following criteria. Practical levels are S to C. (Evaluation Criteria) S: Thickening rate less than 10% A: Thickening rate of 10% or more, but less than 20% B: Thickening rate of 20% or more, but less than 30% C: Thickness ratio of 30% or more, but less than 50% D: Thickening rate of 50% or more, or presence of precipitate or gel (unusable)

[0308] [Transparency] The resulting curable resin composition was poured into a metal container and dried at 40°C for 30 minutes. The resulting dried film was heated at 85°C for 30 minutes. The degree of coloration of the resulting cured film was evaluated according to the following criteria. Practical levels range from S to C. (Evaluation Criteria) S: No coloration, no cloudiness. A: Pale yellow coloration, no cloudiness. B: No coloration, cloudy. C: Pale yellow coloration, cloudy. D: Colored red (unusable)

[0309] [Table 11]

[0310] [Table 12]

[0311] [Table 13]

[0312] [Table 14]

[0313] [Table 15]

[0314] [Table 16]

[0315] [Table 17]

[0316] [Table 18]

[0317] [Table 19]

[0318] The abbreviations used in Tables 11 to 19 are shown below. V-65: 2,2'-Azobis(2,4-dimethylvaleronitrile) PEMP: Pentaerythritol tetrakis(3-mercaptopropionate) DPHA: Dipentaerythritol hexaacrylate MEK: Methyl ethyl ketone TBIS-AHSP: Episulfide resin "TBIS-AHSP" manufactured by Taoka Chemical Co., Ltd. jER152: A curing component containing epoxy groups, manufactured by Mitsubishi Chemical Corporation. Blonate 1227EV: A curing component containing blocked isocyanate groups, manufactured by Daiei Sangyo Co., Ltd. (Blonate Co., Ltd.). OXT-221: A curing component containing oxetane groups, manufactured by Toagosei Co., Ltd. D-230: Huntsman Jeffamine D-230, polyetheramine (basic compound (KA)) D-400: Huntsman's Jeffamine D-400, polyetheramine (basic compound (KA)) D-2000: Huntsman's Jeffamine D-2000, polyetheramine (basic compound (KA)) D-4000: Huntsman's Jeffamine D-4000, polyetheramine (basic compound (KA))

[0319] TBIS-AHSP [ka]

[0320] The curable resin composition of the present invention exhibited good curability at low temperatures such as 85°C, while also showing good stability over time and transparency. In contrast, the comparative example showed inferior results compared to the example in terms of low-temperature curability, stability over time, and transparency.

Claims

1. An episulfide resin characterized by having a constituent unit represented by the following general formula (1) and a constituent unit represented by the following general formula (2). General formula (1) 【Chemistry 1】 [In general formula (1), ring D represents an aliphatic ring having 5 to 10 carbon atoms, A represents a unit having 2 to 30 carbon atoms including a thiirane ring, B represents a direct bond or a divalent linking group, E represents an oxygen atom, a sulfur atom, a divalent linking group containing an oxygen atom, or a divalent linking group containing a sulfur atom, and n represents an integer of 1 or more.] General formula (2) 【Chemistry 2】 [In general formula (2), ring F represents an aliphatic ring having 5 to 10 carbon atoms, J represents a direct bond or a divalent linking group, G represents a direct bond or a divalent linking group, I represents an oxygen atom, a sulfur atom, a divalent linking group containing an oxygen atom, or a divalent linking group containing a sulfur atom, L and K each independently represent a hydrogen atom or a monovalent organic group, Y represents a hydrogen atom or a methyl group, and m represents an integer of 1 or more.]

2. The episulfide resin according to claim 1, wherein the weight-average molecular weight is 1,000 to 1,000,000.

3. The episulfide resin according to claim 1, comprising 50 to 99% by mass of a constituent unit represented by general formula (1) and 1 to 30% by mass of a constituent unit represented by general formula (2).

4. A curable resin composition comprising the episulfide resin according to claim 1 and a curing initiator.

5. The curable resin composition according to claim 4, comprising 0.001 to 100% by mass of a curing initiator based on the mass of the episulfide resin.

6. A cured film formed using the curable resin composition according to claim 4 or 5.

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