Curable compound, curable composition, and method for producing curable compound

Abstract

Provided is a curable compound which can be cured at a low temperature in the presence of oxygen.　The present disclosure provides a curable compound represented by formula (1). [In the formula, R1 denotes a curable functional group having a cyclic imide structure, and R2 denotes a functional group which has a succinimide structure and promotes curing of the curable functional group. D1 and D2 may be the same as, or different from, each other, and are each a single bond or a linking group. L denotes a divalent group having a repeating unit that contains a structure represented by formula (I) and a structure represented by formula (II).]

Description

Curable compound, curable composition, and method for producing curable compound

[0001] The present disclosure relates to a curable compound, a curable composition, and a method for producing the curable compound. More specifically, the present disclosure relates to a curable compound, a curable composition containing the curable compound, and a method for producing the curable compound. This application claims priority from Japanese Patent Application No. 2024-030367, filed in Japan on February 29, 2024, the contents of which are incorporated herein by reference.

[0002] Engineering plastics are high-performance materials that combine high heat resistance and mechanical properties, and are used as essential materials for making various parts smaller, lighter, more highly functional, and more reliable. However, polyimide, for example, is a type of engineering plastic, but it is difficult to dissolve in solvents and melt, making it difficult to obtain molded articles suitable for specific applications.

[0003] In particular, polyether ether ketone (PEEK), also known as a super engineering plastic, is a thermoplastic resin with a continuous use temperature of 260°C and excellent heat resistance, flame retardancy, and electrical properties. However, due to its melting point of 343°C, it is particularly difficult to melt and to dissolve in solvents, making it poor in processability and making it difficult to obtain molded articles from it.

[0004] On the other hand, there are known curable compounds that can be molded into cured products having a PEEK skeleton. These curable compounds are easily melted and have excellent solvent solubility, and therefore have good handleability and processability, allowing cured products and molded articles having a PEEK skeleton to be easily obtained (see Patent Documents 1 to 3).

[0005] JP 2021-95542 A JP 2021-95544 A International Publication No. 2019 / 244693

[0006] The above-mentioned curable compounds are sometimes required to be curable at relatively low temperatures. To achieve low-temperature curing, it is conceivable to use peroxides as curing agents. However, since peroxides are deactivated by oxygen, it has been difficult to form cured products of stable quality in systems where oxygen is present, such as in an air atmosphere. When peroxides are used as curing agents, they must be cured in a nitrogen atmosphere.

[0007] Accordingly, an object of the present disclosure is to provide a curable composition that can be cured at low temperatures in the presence of oxygen.

[0008] As a result of intensive research aimed at solving the above problems, the inventors of the present disclosure have found that a specific curable compound can be cured at low temperatures in the presence of oxygen. The present disclosure relates to a product that has been completed based on these findings.

[0009] That is, the present disclosure provides a curable compound represented by the following formula (1): [In the formula, R １ represents a curable functional group having a cyclic imide structure, and R ２ represents a functional group having a succinimide structure and promoting the curing of the curable functional group. １ and D ２ are the same or different and represent a single bond or a linking group. L represents a divalent group having a repeating unit containing a structure represented by the following formula (I) and a structure represented by the following formula (II). (In the formula, Ar １ ~Ar ３ are the same or different and represent a group in which two hydrogen atoms have been removed from the structural formula of an aromatic ring, or a group in which two or more aromatic rings are bonded via a single bond or a linking group and two hydrogen atoms have been removed. X represents -CO-, -S-, or -SO ２ Y may be the same or different and represents -S-, -SO ２ represents -, -O-, -CO-, -COO-, or -CONH-, and n represents an integer of 0 or more.

[0010] The above R ２ preferably represents a group represented by the following formula (r-2). (In the formula, R ７~R １０ are the same or different and represent a hydrocarbon group. ９ and R １０ may be bonded to each other to form a ring. ２ (binds to

[0011] The above R １ preferably represents a group represented by the following formula (r-1). [In the formula, Q represents C or CH. Two Qs in the formula are bonded via a single bond or a double bond. R ３ ~R ６ are the same or different and represent a hydrogen atom or a hydrocarbon group. ３ and R ４ may be bonded to each other to form a ring. n' represents an integer of 0 or more. The bond marked with a wavy line in the formula is D. １ Bind to

[0012] The group represented by the above formula (r-1) is preferably a group selected from the groups represented by the following formulas (r-1-1) to (r-1-6). (The bond extending from the nitrogen atom in the formula is D in formula (1) １ (combined with

[0013] The present disclosure also provides a curable composition containing the curable compound and a compound represented by the following formula (2): [In the formula, R １１ and R １２ are the same or different and represent a curable functional group having a cyclic imide structure. １ and D ２ are the same or different and represent a single bond or a linking group. L represents a divalent group having a repeating unit containing a structure represented by the following formula (I) and a structure represented by the following formula (II). (In the formula, Ar １ ~Ar ３ are the same or different and represent a group in which two hydrogen atoms have been removed from the structural formula of an aromatic ring, or a group in which two or more aromatic rings are bonded via a single bond or a linking group and two hydrogen atoms have been removed. X represents -CO-, -S-, or -SO ２Y may be the same or different and represents -S-, -SO ２ represents -, -O-, -CO-, -COO-, or -CONH-, and n represents an integer of 0 or more.

[0014] In the curable composition, the abundance ratio of the compound represented by formula (1) to the compound represented by formula (2) [compound represented by formula (1) / compound represented by formula (2)] calculated from the area ratio by MS analysis is preferably 0.08 or more.

[0015] The present disclosure also provides a method for producing the curable compound, which comprises reacting a compound represented by the following formula (1′) with a cyclic acid anhydride in the presence of a compound having an acetamide structure to obtain a compound represented by the formula (1): [In the formula, D １ and D ２ are the same or different and represent a single bond or a linking group. L represents a divalent group having a repeating unit containing a structure represented by the following formula (I) and a structure represented by the following formula (II). (In the formula, Ar １ ~Ar ３ are the same or different and represent a group in which two hydrogen atoms have been removed from the structural formula of an aromatic ring, or a group in which two or more aromatic rings are bonded via a single bond or a linking group and two hydrogen atoms have been removed. X represents -CO-, -S-, or -SO ２ Y may be the same or different and represents -S-, -SO ２ represents -, -O-, -CO-, -COO-, or -CONH-, and n represents an integer of 0 or more.

[0016] The curable compound of the present disclosure can be cured at low temperatures in the presence of oxygen, and therefore has a wide range of applications in terms of equipment for curing a curable composition containing the curable compound and productivity, and can be used in any situation.

[0017] [Curable Compound] The curable compound of the present disclosure is a compound represented by the following formula (1) (hereinafter, may be referred to as "compound (1)").

[0018]

[0019] In formula (1), R １ represents a curable functional group having a cyclic imide structure. The nitrogen atom in the cyclic imide structure is D １ Combine with.

[0020] In formula (1), R ２ represents a functional group (curing-accelerating group) that has a succinimide structure and accelerates the curing of the curable functional group. ２ is R １ Here, promoting the curing of the curable functional group means promoting the reaction between curable functional groups or between a curable functional group and another reactive functional group, like a catalyst.

[0021] In formula (1), D １ and D ２ are the same or different and represent a single bond or a linking group.

[0022] In formula (1), L represents a divalent group having a repeating unit containing a structure represented by the following formula (I) and a structure represented by the following formula (II).

[0023] In formula (I) and formula (II), Ar １ ~Ar ３ are the same or different and represent a group in which two hydrogen atoms have been removed from the structural formula of an aromatic ring, or a group in which two or more aromatic rings are bonded via a single bond or a linking group and two hydrogen atoms have been removed. X represents -CO-, -S-, or -SO ２ Y may be the same or different and represents -S-, -SO ２ represents -, -O-, -CO-, -COO-, or -CONH-, and n represents an integer of 0 or more.

[0024] The above R １ is preferably a group represented by the following formula (r-1):

[0025] In formula (r-1), Q represents C or CH. Two Qs in the formula are bonded via a single bond or a double bond. ３ ~R ６ are the same or different and represent a hydrogen atom or a hydrocarbon group. ３ and R４ may be bonded to each other to form a ring. n' represents an integer of 0 or more. The bond marked with a wavy line in formula (r-1) is D １ Combine with.

[0026] In formula (r-1), R ３ ~R ６ Examples of the hydrocarbon group in include saturated or unsaturated aliphatic hydrocarbon groups (preferably alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and alkynyl groups having 2 to 10 carbon atoms), aromatic hydrocarbon groups (preferably aryl groups having 6 to 10 carbon atoms such as phenyl groups and naphthyl groups), and groups in which two or more groups selected from the above-mentioned saturated or unsaturated aliphatic hydrocarbon groups and the above-mentioned aromatic hydrocarbon groups are bonded to one another.

[0027] In formula (r-1), R ３ and R ４ may be bonded to each other to form a ring together with adjacent carbon atoms. Examples of the ring include an alicyclic ring having 3 to 20 carbon atoms and an aromatic ring having 6 to 14 carbon atoms. Examples of the alicyclic ring having 3 to 20 carbon atoms include a cycloalkane ring having about 3 to 20 members (preferably 3 to 15 members, particularly preferably 5 to 8 members) such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, or a cyclohexane ring; a cycloalkene ring having about 3 to 20 members (preferably 3 to 15 members, particularly preferably 5 to 8 members) such as a cyclopentene ring or a cyclohexene ring; a perhydronaphthalene ring, a norbornane ring, a norbornene ring, an adamantane ring, or a tricyclo[5.2.1.0 ２，６ ] decane ring, tetracyclo[4.4.0.1 ２，５ .1 ７，１０ Examples of the aromatic ring having 6 to 14 carbon atoms include a benzene ring and a naphthalene ring.

[0028] In formula (r-1), n' is an integer of 0 or more, for example, an integer of 0 to 3, and preferably 0 or 1.

[0029] As the group represented by the above formula (r-1), a group selected from the groups represented by the following formulas (r-1-1) to (r-1-6) is preferred. (The bond extending from the nitrogen atom in the formula is D in formula (1) １ (combined with

[0030] The groups represented by the formulae (r-1-1) to (r-1-6) may have one or more substituents bonded thereto, such as hydrocarbon groups (e.g., hydrocarbon groups having 1 to 14 carbon atoms), alkoxy groups having 1 to 6 carbon atoms, and halogen atoms.

[0031] The group represented by the above formula (r-1) is preferably a group selected from the groups represented by the above formulas (r-1-1) to (r-1-5), and particularly preferably a group represented by the above formula (r-1-1) or (r-1-5).

[0032] Of the groups represented by the above formula (r-1), groups represented by the following formula (r-1') are preferred. (In the formula, Q, R ３ , and R ４ (same as above)

[0033] The above R ２ is preferably a group represented by the following formula (r-2):

[0034] In formula (r-2), R ７ and R ８ are the same or different and represent a hydrogen atom or a hydrocarbon group. ９ and R １０ are the same or different and represent a hydrocarbon group. ９ and R １０ may be bonded to each other to form a ring. ２ Combine with.

[0035] In formula (r-2), R ７ and R ８Examples of the hydrocarbon group in include saturated or unsaturated aliphatic hydrocarbon groups (preferably alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and alkynyl groups having 2 to 10 carbon atoms), aromatic hydrocarbon groups (preferably aryl groups having 6 to 10 carbon atoms such as phenyl groups and naphthyl groups), and groups in which two or more groups selected from the above-mentioned saturated or unsaturated aliphatic hydrocarbon groups and the above-mentioned aromatic hydrocarbon groups are bonded to one another.

[0036] In formula (r-2), R ９ and R １０ Examples of the hydrocarbon group in R include saturated or unsaturated aliphatic hydrocarbon groups (preferably alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and alkynyl groups having 2 to 10 carbon atoms), aromatic hydrocarbon groups (preferably aryl groups having 6 to 10 carbon atoms such as phenyl groups and naphthyl groups), and groups in which two or more groups selected from the above-mentioned saturated or unsaturated aliphatic hydrocarbon groups and aromatic hydrocarbon groups are bonded together. ９ and R １０ As the hydrocarbon group in the formula (I), a saturated or unsaturated aliphatic hydrocarbon group having 1 to 6 carbon atoms (preferably an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkynyl group having 2 to 6 carbon atoms) is preferred, and a saturated or unsaturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (preferably an alkyl group having 1 to 4 carbon atoms) is preferred.

[0037] In formula (r-2), R ９ and R １０ may be bonded to each other to form a ring together with the adjacent nitrogen atom. ３ and R ４ Examples of rings that can be formed include those exemplified and explained above.

[0038] Of the groups represented by the above formula (r-2), groups represented by the following formula (r-2') are preferred.

[0039]

[0040] In formula (r-2'), R ９’ and R １０’are the same or different and represent a saturated or unsaturated aliphatic hydrocarbon group having 1 to 6 carbon atoms (preferably an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkynyl group having 2 to 6 carbon atoms), preferably a saturated or unsaturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.

[0041] In formula (1), D １ and D ２ are the same or different and represent a single bond or a linking group. Examples of the linking group include a divalent hydrocarbon group, a divalent heterocyclic group, a carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, an imide bond, and groups in which a plurality of these are linked together.

[0042] D １ and D ２ Among these, groups containing a divalent aromatic hydrocarbon group are preferred, as they give cured products with particularly excellent heat resistance, and arylene groups having 6 to 14 carbon atoms such as 1,4-phenylene group, 1,3-phenylene group, 4,4'-biphenylene group, 3,3'-biphenylene group, 2,6-naphthalenediyl group, 2,7-naphthalenediyl group, 1,8-naphthalenediyl group, and anthracenediyl group are particularly preferred.

[0043] D １ and D ２ is preferably a group selected from groups represented by the following formulae (d-1) to (d-4), particularly preferably a group represented by the following formula (d-1) (1,2-phenylene group, 1,3-phenylene group, or 1,4-phenylene group), more preferably a 1,4-phenylene group. Note that there are no particular restrictions on the attachment position of the bond in the following formulae.

[0044] Also, D １ and D ２ is preferably a group in which at least one group selected from the group consisting of a carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, and an imide bond is linked to the divalent aromatic hydrocarbon group, and particularly preferably a group in which an ether bond is linked to the divalent aromatic hydrocarbon group.

[0045] Therefore, R in formula (1) １ -D １ The - group is preferably a group represented by the following formula (rd-1'-1) or (rd-1'-2): The bonding position in the following formula is not particularly limited. (In the formula, Q, R ３ , and R ４ (same as above)

[0046] Furthermore, R in formula (1) ２ -D ２ The - group is preferably a group represented by the following formula (rd-2'-1) or (rd-2'-2): The bonding position in the following formula is not particularly limited. (In the formula, R ９’ and R １０’ (same as above)

[0047] Ar １ ~Ar ３ are the same or different and represent a group in which two hydrogen atoms have been removed from the structural formula of an aromatic ring, or a group in which two hydrogen atoms have been removed from a structural formula in which two or more aromatic rings are bonded via a single bond or a linking group.

[0048] Examples of the aromatic ring include aromatic rings having 6 to 14 carbon atoms such as benzene, naphthalene, anthracene, and phenanthrene. Of these, aromatic hydrocarbon rings such as aromatic rings having 6 to 10 carbon atoms such as benzene and naphthalene are preferred.

[0049] Examples of the linking group include a divalent hydrocarbon group having 1 to 5 carbon atoms and a divalent hydrocarbon group having 1 to 5 carbon atoms in which one or more hydrogen atoms have been substituted with a halogen atom.

[0050] Therefore, Ar １ ~Ar ３ The groups may be the same or different and are preferably groups in which two hydrogen atoms have been removed from a structural formula of an aromatic ring having 6 to 14 carbon atoms, or groups in which two or more aromatic rings having 6 to 14 carbon atoms are bonded via a single bond, a linear or branched chain alkylene group having 1 to 5 carbon atoms, or a group in which one or more hydrogen atoms of a linear or branched chain alkylene group having 1 to 5 carbon atoms have been substituted with a halogen atom.

[0051] Ar １ ~Ar ３ Among these, groups selected from the groups represented by the following formulae (a-1) to (a-5), which may be the same or different, are preferred. The bonding positions in the following formulae are not particularly limited.

[0052] Ar in formula (I) １ and Ar ２ Among these, groups in which two hydrogen atoms have been removed from the structural formula of an aromatic ring having 6 to 14 carbon atoms are preferred, and groups represented by the above formula (a-1) or (a-2) are particularly preferred.

[0053] In formula (I), X is —CO—, —S—, or —SO ２ X is, among others, -CO- or -SO ２ - is preferred.

[0054] Ar in formula (II) ３ Among these, groups selected from the groups represented by the above formulae (a-1), (a-4), and (a-5) are preferred.

[0055] In formula (II), Y may be the same or different and may be —S—, —SO ２ Y represents, among others, -S-, -O-, or -SO ２ - is preferred.

[0056] In formula (II), n represents an integer of 0 or more, for example, an integer of 0 to 5, preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3.

[0057] L in formula (1) is preferably a divalent group represented by the following formula (L-1-1) or (L-1-2).

[0058] In the above formula, m1 and m2 are the number of repeating units shown in parentheses contained in the molecular chain (= the divalent group represented by the above formula (L-1-1) or (L-1-2)), i.e., the average degree of polymerization, and are, for example, 2 to 50, preferably 3 to 40, more preferably 4 to 30, even more preferably 5 to 20, and particularly preferably 5 to 10. The values ​​of m1 and m2 can be determined by GPC measurement or NMR spectrum analysis.

[0059] The number of moles of the group represented by formula (r-1) per gram of compound (1) (hereinafter, sometimes referred to as "functional group concentration (r-1)") is, for example, 2 × 10 －５ ~10 x 10 －４ The upper limit of the functional group concentration is preferably 7.5×10 －４ mol / g, particularly preferably 5×10 －４ The lower limit of the functional group concentration is preferably 5×10 －５ mol / g, particularly preferably 7×10 －５ When the functional group concentration (r-1) is within the above range, a cured product having excellent solvent solubility, toughness, and heat resistance can be formed.

[0060] The number of moles of the group represented by formula (r-2) per gram of compound (1) (hereinafter, sometimes referred to as "functional group concentration (r-2)") is, for example, 2 × 10 －５ ~10 x 10 －４ The upper limit of the functional group concentration is preferably 7.5×10 －４ mol / g, particularly preferably 5×10 －４ The lower limit of the functional group concentration is preferably 5×10 －５ mol / g, particularly preferably 7×10 －５ When the functional group concentration (r-2) is within the above range, a cured product having excellent solvent solubility, toughness, and heat resistance can be formed.

[0061] The functional group concentration (r-1) of the compound (1) １The functional group concentration (r-2) can be obtained by determining the area of ​​each peak from the H-NMR spectrum and inputting the determined value into the following formula. The functional group concentration (r-1) can be determined in the same manner. Functional group concentration (r-1) = [peak area of ​​the group represented by formula (r-1) / number of protons of the group represented by formula (r-1)] / Σ [(area of ​​each peak / number of protons of the group to which each peak belongs) × chemical formula weight corresponding to each peak]

[0062] The ring closure rate of compound (1) is preferably 97 mol% or more, more preferably 98 mol% or more, even more preferably 98.5 mol% or more, and particularly preferably 99 mol% or more. When the ring closure rate is within the above range, the compound has excellent solvent solubility. The ring closure rate is calculated as the total ratio of the group represented by the following formula (r-3) and the group represented by the following formula (r-5) to the total of the groups represented by the following formulas (r-3) to (r-6). The number of moles of each group is 1 The ring closure rate can be determined by calculation from the peak area corresponding to each group in the H-NMR spectrum. Ring closure rate [mol %] = [(number of moles of groups represented by formula (r-3) below + number of moles of groups represented by formula (r-5) below) / (number of moles of groups represented by formula (r-3) below + number of moles of groups represented by formula (r-4) below + number of moles of groups represented by formula (r-5) below + number of moles of groups represented by formula (r-6) below)] × 100

[0063]

[0064] The number average molecular weight (Mn; standard polystyrene equivalent) of compound (1) is, for example, 1,000 to 15,000, preferably 1,500 to 12,000, more preferably 2,000 to 10,000, still more preferably 2,200 to 8,000, and particularly preferably 2,500 to 7,500.

[0065] The weight average molecular weight (Mw; standard polystyrene equivalent) of compound (1) is, for example, 1,000 to 45,000. The lower limit of the weight average molecular weight (Mw) is preferably 1,500, more preferably 2,500, even more preferably 3,000, and particularly preferably 4,000. The upper limit of the weight average molecular weight (Mw) is preferably 40,000, more preferably 35,000, and even more preferably 25,000.

[0066] The Mn and Mw are determined by gel permeation chromatography (GPC) measurement (solvent: chloroform, standard polystyrene equivalent). When compound (1) has the above molecular weight, it has excellent solvent solubility.

[0067] Compound (1) has excellent solvent solubility, and the solubility is preferably 1 g or more, more preferably 5 g or more, and particularly preferably 10 g or more, per 100 g of solvent at 23°C.

[0068] Compound (1) has excellent solvent solubility, and the solubility at 23° C. is 1 g or more, preferably 5 g or more, and particularly preferably 10 g or more, per 100 g of solvent.

[0069] [Method for Producing Compound (1)] Compound (1) can be produced, for example, by reacting a compound represented by the following formula (1′): (In the formula, D １ , D ２ and L is the same as above) with a cyclic acid anhydride in the presence of a compound having an acetamide structure.

[0070] Among the compounds represented by formula (1') above, for example, a compound represented by formula (1'-1) below can be produced through the following steps [1-1] and [1-2]. Step [1-1]: A compound represented by formula (1a) below is reacted with a compound represented by formula (1b) below in the presence of a base to obtain a compound represented by formula (1c) below. Step [1-2]: An amino alcohol (a compound represented by formula (1d) below) is reacted with the compound represented by formula (1c) below.

[0071]

[0072] In the above formula, Ar １ ~Ar ３ , X, Y, and n are the same as those in the formula (I) and the formula (II). D represents a linking group; １ and D ２ Examples of the linking group are the same as those in the above. m is the average degree of polymerization of the repeating units, and is, for example, 3 to 50, preferably 4 to 30, and particularly preferably 5 to 20. Z represents a halogen atom.

[0073] (Step [1-1]) Examples of the compound represented by the above formula (1a) include halides of bisaryl compounds such as benzophenone and 2-naphthylphenylketo, and derivatives thereof.

[0074] Examples of the compound represented by the formula (1b) include hydroquinone, resorcinol, and bisphenol A.

[0075] Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate; and organic bases such as pyridine and triethylamine. The amount of the base used can be adjusted appropriately depending on the type of base. For example, the amount of a diacid base such as calcium hydroxide used is about 1.0 to 2.0 moles per mole of the compound represented by formula (1b).

[0076] This reaction can be carried out in the presence of a solvent, such as an organic solvent such as N-methyl-2-pyrrolidone, dimethylformamide, or dimethyl sulfoxide, or a mixed solvent of two or more of these.

[0077] The reaction atmosphere is not particularly limited as long as it does not inhibit the reaction, and may be, for example, a nitrogen atmosphere, an argon atmosphere, etc. The reaction temperature is, for example, about 100 to 200°C.

[0078] (Step [1-2]) Examples of the compound represented by the above formula (1d) include 4-aminophenol, 2-amino-6-hydroxynaphthalene, and positional isomers and derivatives thereof.

[0079] This reaction can be carried out in the presence of a solvent, such as the solvent used in step [1-1]. The reaction temperature is, for example, about 100 to 200°C.

[0080] The cyclic acid anhydride is preferably a compound represented by the following formula (a): ３ and R ４It is particularly preferred to include compounds in which is a hydrogen atom (i.e., maleic anhydride). (Wherein, Q and R ３ ~R ６ is the same as in the above formula (r-1)

[0081] The compound having an acetamide structure is preferably a compound represented by the following formula (b): (In the formula, R ９ and R １０ is the same as in the above formula (r-2))

[0082] R ９ and R １０ is R in the above formula (r-2) ９ and R １０ It corresponds to, among others, R ９ and R １０ is a methyl group (ie, N,N-dimethylacetamide).

[0083] When the compound represented by formula (1') is reacted with the cyclic acid anhydride in the presence of the compound having the acetamide structure, the compound (1) is obtained via an amic acid-forming reaction, a ring-closing reaction, and a cure-accelerating group-forming reaction. The following describes the reaction when the compound represented by formula (a) (sometimes referred to as "compound (a)") is used as the cyclic acid anhydride and the compound represented by formula (b) (sometimes referred to as "compound (b)") is used as the compound having the acetamide structure. Only one type of compound (a) and two or more types of compound (b) may be used.

[0084] In the amic acid forming reaction, the terminal group of the compound represented by the above formula (1') is NH ２The compound (a) reacts with the group to produce a group represented by the formula (r-4) above (maleamic acid in this example). Then, in the ring-closing reaction, the group represented by the formula (r-4) above undergoes dehydration and is converted into a group represented by the formula (r-3) above (maleimide ring in this example) in which at least some of Q-Q are double bonds through a ring-closing reaction. Thereafter, a portion of the compound (b) is hydrolyzed by water present in the system, for example by being produced by dehydration in the ring-closing reaction, to produce acetic acid and an amine, and the amine bonds to one of the carbon atoms constituting the double bond in the group represented by the formula (r-3), thereby producing a succinimide group to which the amino group is bonded.

[0085] The amic acid-forming reaction, ring-closing reaction, and curing-accelerating group-forming reaction can be carried out via two-stage reactions. The first stage is a reaction carried out at room temperature, and the second stage is a reaction carried out under heating and / or in a state where the amount of catalyst is greater than in the first stage. The amic acid-forming reaction mainly proceeds in the first stage, and the ring-closing reaction mainly proceeds in the second stage. The ring-closing reaction may proceed in the first stage, or the amic acid-forming reaction may proceed in the second stage. The curing-accelerating group-forming reaction proceeds in both the first stage and the second stage.

[0086] In the first step, the compound represented by formula (1'), compound (a), and compound (b) are reacted. The first step can be carried out at room temperature (1 to 40°C). The reaction time is, for example, about 1 to 30 hours. This reaction can be carried out by any method, such as a batch method, semi-batch method, or continuous method.

[0087] The amount of compound (a) used in the first step is, for example, about 2.0 to 4.0 moles per mole of the compound represented by formula (1').

[0088] The amount of compound (b) used in the first step is, for example, about 2.0 to 4.0 moles per mole of the compound represented by formula (1').

[0089] The reaction can be carried out in the presence of a solvent. Examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; amides such as formamide, acetamide, N-methyl-2-pyrrolidone (NMP), and N,N-dimethylformamide; halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, bromobenzene, dichlorobenzene, benzotrifluoride, and hexafluoro-2-propanol; sulfoxides such as dimethyl sulfoxide (DMSO), diethyl sulfoxide, and benzyl phenyl sulfoxide; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran (THF), dioxane, 1,2-dimethoxyethane, and cyclopentyl methyl ether; esters such as ethyl acetate; nitriles such as acetonitrile and benzonitrile; and aromatic hydrocarbons such as benzene, toluene, and xylene. These solvents may be used singly or in combination.

[0090] As the solvent, from the viewpoint of sufficiently proceeding the reaction with the compound having the acetamide structure at one end of the compound represented by formula (1'), a solvent having a boiling point higher than that of water is preferred, more preferably an aromatic hydrocarbon, and particularly preferably benzene, toluene, or xylene.

[0091] A catalyst may be added in the first-stage reaction. Adding a catalyst in the first-stage reaction can accelerate the ring-closing reaction and dehydration, generating water in the system during the first-stage reaction and accelerating the curing-accelerating group-forming reaction. Examples of the catalyst include those exemplified and explained as catalysts that can be used in the second-stage reaction described below. Only one type of catalyst may be used, or two or more types may be used.

[0092] The amount of the acid catalyst used in the first step is, for example, 0.02 to 1.0 mol, preferably 0.05 to 0.5 mol, and particularly preferably 0.1 to 0.4 mol, per mole of the compound represented by formula (1').

[0093] The amount of the base catalyst used in the first step is, for example, 0.02 to 1.0 mol, preferably 0.02 to 0.5 mol, and particularly preferably 0.05 to 0.4 mol, per 1 mol of the compound represented by formula (1').

[0094] The catalyst concentration in the reaction system in the first stage is, for example, 0.003 to 0.10 mmol / g, preferably 0.005 to 0.07 mmol / g, and particularly preferably 0.007 to 0.04 mmol / g.

[0095] The second stage can be promoted by heating at a temperature of 200° C. or higher or by adding a catalyst.

[0096] Among these, adding a catalyst is preferred in that it can promote the ring-closure reaction while suppressing the progress of the curing reaction, thereby obtaining a curable compound with a high ring-closure rate and excellent storage stability in solution. Examples of the catalyst include base catalysts and acid catalysts. Of these, acid catalysts are preferred in terms of being able to further suppress side reactions. Only one type of catalyst may be used, or two or more types may be used.

[0097] Examples of the base catalyst include amine compounds and sodium acetate. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, hydrogen bromide, hydrogen iodide, sulfuric acid, sulfuric anhydride, nitric acid, phosphoric acid, phosphorous acid, phosphotungstic acid, and phosphomolybdic acid; sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid; carboxylic acids such as acetic acid and oxalic acid; halogenated carboxylic acids such as chloroacetic acid, dichloroacetic acid, trichloroacetic acid, fluoroacetic acid, difluoroacetic acid, and trifluoroacetic acid; solid acids such as silica, alumina, and activated clay; and cationic ion exchange resins. Among these, at least one acid catalyst selected from the group consisting of p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, and phosphoric acid is preferred.

[0098] The amount of the acid catalyst used in the second step is, for example, 0.02 to 1.0 mol, preferably 0.05 to 0.5 mol, and particularly preferably 0.1 to 0.4 mol, per 1 mol of the compound represented by formula (1').

[0099] The amount of the base catalyst used in the second step is, for example, 0.02 to 1.0 mol, preferably 0.02 to 0.5 mol, and particularly preferably 0.05 to 0.4 mol, per 1 mol of the compound represented by formula (1').

[0100] The catalyst concentration in the reaction system in the second stage is, for example, 0.003 to 0.10 mmol / g, preferably 0.005 to 0.07 mmol / g, and particularly preferably 0.007 to 0.04 mmol / g. When the catalyst concentration is 0.003 mmol or more, the ring closure rate of the curable compound becomes higher, and the storage stability of the solution tends to be improved.

[0101] When a catalyst is added in the first stage, an additional catalyst may or may not be added in the second stage. Taking into consideration that a portion of the catalyst added in the first stage is deactivated, the catalyst may be added in the amount or concentration described above.

[0102] In the second step, compound (b) may be added. The amount of compound (b) used in the second step is, for example, about 2.0 to 30.0 moles per mole of the compound represented by formula (1').

[0103] In the second stage, it is preferable to quickly remove water produced as a by-product of the reaction from the reaction system in order to further promote the progress of the ring-closure reaction. Methods for removing the by-product water include, for example, using a dehydrating agent such as a carboxylic acid anhydride or using a solvent that forms an azeotrope with water. In this case, the removal efficiency may vary depending on the shape and volume of the reaction vessel, the piping layout, and the heat retention state.

[0104] The reaction is preferably terminated after confirming that the reaction has progressed sufficiently by sampling to check the ring closure rate, etc. After completion of the reaction, the resulting reaction product can be separated and purified by common methods such as precipitation, washing, and filtration.

[0105] [Curable composition] A curable composition can be obtained using the compound (1). The present disclosure provides a curable composition containing the compound (1). The curable composition may contain only one type of compound (1), or may contain two or more types of compound (1).

[0106] The curable composition preferably contains a compound represented by the following formula (2) (sometimes referred to as "compound (2)"). Curable compositions containing compound (1) and compound (2) tend to have better solvent solubility and be curable at low temperatures in the presence of oxygen.

[0107] [In the formula, R １１ and R １２ are the same or different and represent a curable functional group having a cyclic imide structure. １ and D ２ are the same or different and represent a single bond or a linking group. L represents a divalent group having a repeating unit containing a structure represented by formula (I) above and a structure represented by formula (II) above.

[0108] In formula (2), R １１ and R １２ may be the same or different and represent a curable functional group having a cyclic imide structure. １１ The nitrogen atom in the cyclic imide structure is D １ and bonded to R １２ The nitrogen atom in the cyclic imide structure is D ２ Binds to R １１ and R １２ The curable functional group having a cyclic imide structure in the formula (1) includes R １ The examples and preferred embodiments of the curable functional group having a cyclic imide structure in the above formula (I) are the same as those exemplified and explained above.

[0109] In formula (2), D １ and D２ are the same or different and represent a single bond or a linking group, and a preferred embodiment is １ and D ２ is the same as

[0110] In formula (2), L represents a divalent group having a repeating unit containing the structure represented by formula (I) above and the structure represented by formula (II) above, and preferred embodiments are the same as those of L in formula (1).

[0111] Compound (2) can be obtained as a mixture with compound (1) by producing compound (1) by the method for producing compound (1). That is, a mixture of compound (1) and compound (2) can be produced by the method for producing compound (1). Compound (2) produced by a known or conventional method may also be used.

[0112] In the curable composition, the abundance ratio of compound (1) to compound (2) [compound (1) / compound (2)] calculated from the area ratio by MS analysis is preferably 0.08 or more, more preferably 0.1 or more, and even more preferably 0.13 or more. When the abundance ratio is 0.08 or more, the curing initiation temperature tends to be lower. The abundance ratio is, for example, less than 1.

[0113] The content of compound (1) in the curable composition is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, relative to the total amount (100% by mass) of the curable composition. Furthermore, the content is, for example, 99% by mass or less, preferably 60% by mass or less, and more preferably 50% by mass or less. Furthermore, when the curable composition contains compound (1) and compound (2), it is preferable that the total content of compound (1) and compound (2) is within the above range.

[0114] The content of compound (1) in the curable composition is preferably 40% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, relative to 100% by mass of the total amount of solids in the curable composition (for example, the total amount of each component excluding the solvent). When the curable composition contains compound (1) and compound (2), it is preferable that the total content of compound (1) and compound (2) is within the above range.

[0115] The curable composition may contain a solvent. Known or commonly used organic solvents can be used as the solvent, and are not particularly limited. Examples of the solvent include chain ketones such as methyl ethyl ketone and methyl isobutyl ketone; cyclic ketones such as cyclopentanone and cyclohexanone; amides such as formamide, acetamide, N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide, and N,N-dimethylacetamide (DMAc); halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, bromobenzene, dichlorobenzene, benzotrifluoride, and hexafluoro-2-propanol; sulfoxides such as dimethyl sulfoxide (DMSO), diethyl sulfoxide, and benzylphenyl sulfoxide; tetrahydrofuran (THF); aromatic hydrocarbons such as benzene, toluene, and xylene; and ethers such as anisole. One or more of the solvents may be used.

[0116] Among these, the solvent is preferably one having a large difference between the heat generation initiation temperature of the compound (1) and the compound (2) and the boiling point of the solvent (= boiling point under normal pressure), since this makes it possible to easily volatilize the solvent while suppressing the progress of the curing reaction of the compound (1) and the compound (2).

[0117] As the solvent, aromatic hydrocarbons and ethers are preferred, more preferably toluene and anisole, and even more preferably toluene, from the viewpoint of excellent solubility of compound (1) and compound (2).

[0118] The curable composition may contain other components in addition to the above-mentioned components. These other components may be known or commonly used additives, such as curable compounds other than Compound (1) and Compound (2), curing agents, curing accelerators, catalysts, fillers, organic resins (such as silicone resins, epoxy resins, and fluororesins), stabilizers (such as antioxidants, UV absorbers, light stabilizers, and heat stabilizers), flame retardants (such as phosphorus-based flame retardants, halogen-based flame retardants, and inorganic flame retardants), flame retardant aids, reinforcing materials, nucleating agents, coupling agents, lubricants, waxes, plasticizers, release agents, impact modifiers, color modifiers, flow improvers, colorants (such as dyes and pigments), dispersants, antifoaming agents, defoaming agents, antibacterial agents, preservatives, viscosity modifiers, thickeners, and crosslinking agents. These other components may be used singly or in combination of two or more.

[0119] The curable composition can initiate curing at low temperatures in the presence of oxygen without the use of a curing agent and a curing accelerator. Therefore, the content of the curing agent and / or curing accelerator in the curable composition is preferably less than 1 mass%, more preferably less than 0.1 mass%, even more preferably less than 0.07 mass%, and particularly preferably less than 0.01 mass%, relative to 100 mass% of the total amount of the curable composition. Furthermore, the content of the curing agent and / or curing accelerator is preferably less than 0.1 parts by mass, more preferably less than 0.08 parts by mass, and even more preferably less than 0.03 parts by mass, relative to 100 parts by mass of the total amount of the compound (1) (or compound (1) and compound (2)).

[0120] The polymerization initiator may be a radical polymerization initiator. The radical polymerization initiator may be a photoradical polymerization initiator or a thermal radical polymerization initiator. One or more of the polymerization initiators may be used.

[0121] Examples of the photoradical polymerization initiator include 2-amino-2-benzoates such as benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyl disulfite, methyl orthobenzoylbenzoate, ethyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2-methyl-1-[4-(methyl)phenyl]-2-morpholinopropanone-1,1-hydroxycyclohexyl phenyl ketone, and 2-dimethylamino-2-(4-morpholino)benzoyl-1-phenylpropane. Examples of the compound include phenyl-1-phenylalkane compounds, aminobenzene derivatives such as tetra(t-butylperoxycarbonyl)benzophenone, benzil, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 4,4'-bis(diethylamino)benzophenone, imidazole compounds such as 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole, halomethylated triazine compounds such as 2,6-bis(trichloromethyl)-4-(4-methoxynaphthalen-1-yl)-1,3,5-triazine, and halomethyloxadiazole compounds such as 2-trichloromethyl-5-(2-benzofuran-2-yl-ethenyl)-1,3,4-oxadiazole. If necessary, a photosensitizer can be added.

[0122] Examples of the thermal radical polymerization initiator include azo compounds such as azobisisobutyronitrile, and organic peroxides. Examples of the organic peroxides include hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, peroxydicarbonates, peroxyketals, and ketone peroxides (specifically, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexanoyl)peroxyhexane, t-butylperoxybenzoate, t-butyl peroxide, and cumene hydride). dropomer, 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, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, and the like.

[0123] The curable composition can be cured at low temperatures even without using a polymerization initiator. Therefore, the content of the polymerization initiator in the curable composition may be 2 parts by mass or less, 1 part by mass or less, 0.5 parts by mass or less, 0.1 parts by mass or less, or 0.02 parts by mass or less, relative to 100 parts by mass of the total amount of the compound (1) (or the compound (1) and the compound (2)).

[0124] The curable composition preferably does not produce any precipitate or insoluble matter at 60° C. Furthermore, it is particularly preferable that the curable composition does not produce any precipitate or insoluble matter at room temperature (for example, 25° C.).

[0125] The curable composition is preferably capable of initiating curing in the presence of oxygen at 320° C. or lower (preferably 300° C. or lower, more preferably 240° C. or lower, and even more preferably 230° C. or lower). In other words, the exotherm initiation temperature is preferably within the above range.

[0126] The curable composition can be cured at low temperatures in the presence of oxygen. Therefore, the curable composition has a wide range of applications in terms of equipment for curing the composition and productivity, and can be used under any circumstances. Furthermore, even when the curable composition is cured in contact with a metal substrate such as copper, the quality of the cured product (dielectric constant, glass transition temperature, flexibility, adhesion, etc.) is unlikely to become unstable. Therefore, the curable composition can be applied to a variety of substrates without being limited by the type of substrate to which it is applied.

[0127] The curable composition can be prepared by mixing the above-mentioned components and heating and stirring them at a temperature of, for example, 80°C or less, preferably room temperature (about 25°C to 80°C), particularly preferably 50 to 70°C.

[0128] [Cured Product] The curable composition is cured by a heat treatment, whereby compounds (1) react with each other to form a cured product. When the curable composition contains compounds (1) and (2), the curable composition may be cured by a reaction between compounds (1) with each other, between compounds (1) and (2), and / or between compounds (2). A drying step for volatilizing the solvent may be performed before the heat treatment. The heat treatment may be performed under normal pressure, or under reduced pressure or pressure. The heat treatment may be performed under an inert gas atmosphere such as nitrogen or argon. However, since the curing of the curable composition proceeds sufficiently even in the presence of oxygen, it is preferable to perform the heat treatment in an air atmosphere, such as in the presence of oxygen.

[0129] The heat treatment temperature is not particularly limited, but from the viewpoint that the curable composition can be cured at a low temperature, it is preferably 320°C or lower (e.g., 60 to 320°C), more preferably 300°C or lower (e.g., 80 to 300°C), even more preferably 240°C or lower (e.g., 100 to 240°C), and particularly preferably 230°C or lower (e.g., 120 to 230°C). Heating may be carried out while maintaining a constant temperature, or may be carried out by changing the temperature stepwise. The heating temperature can be adjusted appropriately depending on the heating time. The heating means is not particularly limited, and known or commonly used means can be used.

[0130] Furthermore, the curing reaction of the curable composition can be stopped midway to form a semi-cured product (B-stage). The semi-cured product temporarily exhibits fluidity when heated, allowing it to conform to the unevenness of a substrate. Furthermore, by further heat treatment, a cured product with ultra-heat resistance, flame retardancy, and good dielectric properties can be formed.

[0131] The degree of cure of the semi-cured product is, for example, 85% or less (for example, 10 to 85%, particularly preferably 15 to 75%, and further preferably 20 to 70%).

[0132] The degree of cure of the semi-cured product can be calculated by measuring the calorific value of the curable composition before curing (uncured) and the calorific value of the semi-cured product by DSC, and then using the following formula: Degree of cure (%) = [1 - (calorific value of semi-cured product / calorific value of uncured curable composition)] x 100

[0133] The glass transition temperature (Tg) of the cured product is preferably 150° C. or higher, more preferably 160° C. or higher, and even more preferably 170° C. or higher. When the glass transition temperature is 150° C. or higher, the cured product has better heat resistance. The glass transition temperature can be measured by DSC measurement.

[0134] The cured product of the curable composition has excellent heat resistance, and has a 5% weight loss temperature (T ｄ５ ) is, for example, 300°C or higher, preferably 400°C or higher, more preferably 430°C or higher, and even more preferably 450°C or higher. ｄ５ The upper limit of the temperature at which the 5% weight loss occurs is, for example, 600° C., preferably 550° C., and particularly preferably 530° C. The 5% weight loss temperature can be measured by TG / DTA (differential thermal / thermogravimetric simultaneous analysis).

[0135] Therefore, the curable composition can be molded by a well-known, conventional molding method, and then subjected to a heat treatment (after drying, if necessary), to produce a molded article made of a cured or semi-cured product of the curable composition.

[0136] The curable composition can be preferably used as a molding material for composites (fiber reinforced plastics, prepregs, etc.) used under severe environmental temperature conditions in, for example, electronic information devices, home appliances, automobiles, precision machinery, aircraft, space industry equipment, energy fields (oil field drilling pipes / tubes, fuel containers), etc., as well as functional materials such as shielding materials, conductive materials (for example, heat conductive materials, etc.), insulating materials, adhesives (for example, heat-resistant adhesives, etc.). Other examples of the material that can be preferably used include sealants, paints, inks, sealants, resists, shaping materials, and forming materials [automotive parts such as thrust washers, oil filters, seals, bearings, gears, cylinder head covers, bearing retainers, intake manifolds, and pedals; semiconductor and liquid crystal manufacturing equipment parts such as substrates, electrical insulating materials (insulating films, etc.), laminates, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, silicon wafer carriers, IC chip trays, electrolytic capacitor trays, and insulating films; optical components such as lenses; compressor parts such as pumps, valves, and seals; aircraft cabin interior parts; medical equipment parts such as sterilization instruments, columns, and piping, and food and beverage manufacturing equipment parts; and forming materials for electrical and electronic equipment parts such as housings used in personal computers, mobile phones, and keyboard supports that support the keyboard inside a personal computer].

[0137] [Molded Article] By molding the curable composition and drying it as necessary, the solidified product of the curable composition can be given a desired shape, and a molded article made of the solidified product can be obtained. The molded product made of the solidified product temporarily exhibits fluidity or adhesiveness when heated, making it possible to perform secondary molding or adhere it to other members. Furthermore, by subjecting the solidified product given a desired shape to a heat treatment, a molded product made of a cured or semi-cured product of the curable composition can be obtained. The shape of the molded product is not particularly limited, and a shape can be appropriately selected depending on the application.

[0138] Each aspect disclosed in this specification can be combined with any other feature disclosed in this specification. Each configuration and combination thereof in each embodiment is an example, and addition, omission, substitution, and other modifications of configurations are possible as appropriate within the scope of the present disclosure. Furthermore, each invention according to this disclosure is not limited by the embodiments or the following examples, but is limited only by the scope of the claims.

[0139] Hereinafter, one embodiment of the present disclosure will be described in more detail based on examples, but the present disclosure is not limited to these examples.

[0140] Example 1 [Preparation of Curable Composition] (Step 1-1) Into a reactor equipped with a stirrer, a nitrogen inlet tube, and a Dean-Stark apparatus, 40.3 g of 4,4'-difluorobenzophenone (DFBP), 35.1 g of bisphenol A (BisA), anhydrous potassium carbonate (K ２ CO ３ 41.2 g of toluene (Tol), 187.2 g of N,N-dimethylacetamide (DMAc), and 18.7 g of toluene (Tol) were added, and the mixture was heated with stirring under a nitrogen atmosphere. The toluene was continuously refluxed at 140 to 150° C. for 10 hours, and then the mixture was returned to room temperature.

[0141] (Step 1-2) Then, 7.4 g of 4-aminophenol (4-AP) was added to the reactor containing the reaction product, and the mixture was again heated with stirring under a nitrogen atmosphere. Toluene reflux was continued at 140-150°C for 10 hours, and then the temperature was returned to room temperature. Subsequently, 18.7 g of N,N-dimethylacetamide (DMAc) and 56.2 g of toluene (Tol) were added to the crude reaction liquid obtained by filtration, thereby obtaining a diamine liquid (Diamine-1, a liquid containing a compound represented by the following formula). Here, m is the average degree of polymerization of the repeating units.

[0142]

[0143] (Step 2) 320.5 g of the diamine solution obtained in step 1-2, 10.4 g of maleic anhydride (MAH), and 118.5 g of N,N-dimethylacetamide (DMAc) were placed in a reactor equipped with a stirrer, a nitrogen inlet tube, and a Dean-Stark apparatus, and the mixture was stirred at room temperature under a nitrogen atmosphere for 1 hour. The mixture was then heated to 140-150°C, at which point toluene refluxed, and the mixture was brought into a toluene reflux state. Subsequently, p-toluenesulfonic acid monohydrate (pTSA.1H) was added as a catalyst. ２ A mixed solution of 1.3 g of dimethylacetamide (DMAc), 11.3 g of N,N-dimethylacetamide (DMAc), and 4.0 g of toluene (Tol) was added over 1 hour, and stirring was continued for 10 hours. The toluene was refluxed to remove water. The reaction solution was returned to room temperature, and then added to 3000 mL of methanol to obtain a powdery solid. This powdery solid was repeatedly washed with methanol and water and then dried under reduced pressure at 80°C overnight to obtain 65.2 g of a mixture (curable composition) of compound (1-1) (including a compound represented by formula (1-1) below and a compound represented by formula (2-1) below) and compound (2-1) (including a compound represented by formula (2-1) below). Note that m in formulas (1-1) and (2-1) below represents the average degree of polymerization of the repeating units.

[0144]

[0145] Example 2 [Preparation of Curable Composition] A reactor equipped with a stirrer, a nitrogen inlet tube, and a Dean-Stark apparatus was charged with 319.2 g of the diamine liquid obtained in step 1-2 in Example 1, 10.4 g of maleic anhydride (MAH), 21.6 g of N,N-dimethylacetamide (DMAc), 3.9 g of toluene (Tol), and p-toluenesulfonic acid monohydrate (pTSA.1H) as a catalyst. ２ 1.3 g of (O) was added and stirred at room temperature for 3 hours under a nitrogen atmosphere. Thereafter, the temperature was raised to 130-140°C to reflux the toluene, and stirring was continued for 10 hours to remove water. After returning the reaction solution to room temperature, the reaction solution was added to 3000 mL of methanol to obtain a powdery solid. This powdery solid was repeatedly washed with methanol and water and then dried under reduced pressure at 80°C overnight to obtain 62.8 g of a mixture (curable composition) of the above compound (1-1) and the above compound (2-1).

[0146] Example 3 [Preparation of Curable Composition] A reactor equipped with a stirrer, a nitrogen inlet tube, and a Dean-Stark apparatus was charged with 322.2 g of the diamine liquid obtained in step 1-2 in Example 1, 10.4 g of maleic anhydride (MAH), 129.8 g of N,N-dimethylacetamide (DMAc), 4.0 g of toluene (Tol), and p-toluenesulfonic acid monohydrate (pTSA·1H) as a catalyst. ２ 1.3 g of O) was added and stirred at room temperature under a nitrogen atmosphere for 3 hours. Thereafter, the temperature was raised to 140-150°C to reflux the toluene, and stirring was continued for 10 hours to remove water. After returning the reaction solution to room temperature, the reaction solution was added to 3,000 mL of methanol to obtain a powdery solid. This powdery solid was repeatedly washed with methanol and water and then dried under reduced pressure at 80°C overnight to obtain 63.4 g of a mixture (curable composition) of the above compound (1-1) and the above compound (2-1).

[0147] Example 4 [Preparation of Curable Composition] 49.70 g of the diamine liquid obtained in step 1-2 in Example 1, 10.4 g of maleic anhydride (MAH), and 10.4 g of N,N-dimethylacetamide (DMAc) were placed in a reactor equipped with a stirrer, a nitrogen inlet tube, and a Dean-Stark apparatus, and the mixture was stirred at room temperature under a nitrogen atmosphere for 1 hour. The mixture was then heated to 130 to 140°C, at which point toluene refluxed, and the toluene was refluxed. Thereafter, p-toluenesulfonic acid monohydrate (pTSA.1H) was added as a catalyst. ２ A mixed solution of 1.3 g of 1-methyl-2-propanol (O), 11.3 g of N,N-dimethylacetamide (DMAc), and 4.0 g of toluene (Tol) was added over 1 hour, and stirring was continued for 10 hours, and the toluene was refluxed to remove water. After returning the reaction solution to room temperature, the reaction solution was added to 3000 mL of methanol to obtain a powdery solid. This powdery solid was repeatedly washed with methanol and water and then dried under reduced pressure at 80°C overnight to obtain 64.4 g of a mixture (curable composition) of compound (1-1) (containing the compound represented by formula (1-1) above and the compound represented by formula (2-1) below) and compound (2-1) (containing the compound represented by formula (2-1) above).

[0148] 5.0 g of the above curable composition, 5.0 g of toluene as a solvent, and 0.05 g of Percumyl D (trade name "Percumyl D", manufactured by NOF Corporation), a radical generator used as a curing accelerator, were mixed and allowed to stand at room temperature under atmospheric pressure for 8 hours to obtain a homogeneous solution. The resulting solution was applied to a glass plate to a thickness of 0.10 mm and then heated and dried at 120°C for 0.5 hours to obtain a curable composition.

[0149] Example 5 [Preparation of Curable Composition] 5.0 g of the curable composition obtained in Example 4, 5.0 g of anisole as a solvent, and 0.05 g of 1B2PZ (1-benzyl-2-phenylimidazole, manufactured by Shikoku Chemical Industry Co., Ltd.), an organic nucleophilic agent serving as a curing accelerator, were mixed and allowed to stand at room temperature for 8 hours under atmospheric pressure to obtain a homogeneous solution. The obtained solution was applied to a glass plate to a thickness of 0.10 mm and then heated and dried at 150°C for 0.5 hours to obtain a curable composition.

[0150] Example 6 [Preparation of Curable Composition] A curable composition was obtained in the same manner as in Example 5, except that an organic nucleophilic agent, 2E4MZ (2-ethyl-4-methylimidazole, manufactured by Shikoku Chemicals Corporation), was used as the curing accelerator.

[0151] Comparative Example 1 [Preparation of Curable Composition] (Step 1-1) Into a reactor equipped with a stirrer, a nitrogen inlet tube, and a Dean-Stark apparatus, 37.25 g of 4,4′-difluorobenzophenone (DFBP), 32.48 g of bisphenol A (BisA), anhydrous potassium carbonate (K ２ CO ３ 29.50 g of toluene (Tol), 214.4 g of N-methylpyrrolidone (NMP), and 90.4 g of toluene (Tol) were added and heated with stirring under a nitrogen atmosphere, and the toluene was refluxed at 130-140°C for 4 hours. The mixture was then further heated to 170-180°C, and the toluene was distilled off. Stirring was continued at 170-180°C for another 10 hours, and the mixture was then returned to room temperature.

[0152] (Step 1-2) Then, 6.520 g of 4-aminophenol (4-AP) and anhydrous potassium carbonate (K ２ CO ３8.260 g of toluene (Tol), 27.9 g of N-methylpyrrolidone (NMP), and 117.4 g of toluene (Tol) were added, and the mixture was again heated with stirring under a nitrogen atmosphere, and the toluene was refluxed at 130-140°C for 3 hours. The mixture was then heated to 170-180°C to distill off the toluene, and stirring was continued for another 4 hours while maintaining the temperature. The mixture was then cooled to room temperature, and the reaction solution was added to 3000 mL of methanol and filtered to obtain a powdery solid. This powdery solid was repeatedly washed with methanol and water and then dried under reduced pressure at 80°C overnight to obtain a powdery solid, diamine-1 (Diamine-1, the compound represented by the above formula).

[0153] (Step 2) A reactor equipped with a stirrer, a nitrogen inlet tube, and a Dean-Stark apparatus was charged with 49.70 g of the diamine-1 obtained in step 1, 6.03 g of maleic anhydride (MAH), 316.0 g of N-methylpyrrolidone (NMP), and 178.3 g of toluene (Tol), and stirred for 5 hours at room temperature under a nitrogen atmosphere. Then, 1.1 g of p-toluenesulfonic acid (pTSA) was added as a catalyst, and the mixture was heated to 140 ° C. and stirred for 8 hours. The toluene was refluxed to remove water. After returning the reaction solution to room temperature, the reaction solution was added to 3000 mL of methanol to obtain a powdery solid. This powdery solid was repeatedly washed with methanol and water, and then dried under reduced pressure at 80 ° C. overnight to obtain 48.8 g of a curable composition containing the compound represented by the formula (1-1).

[0154] Example 7 [Preparation of Cured Product] The curable compositions obtained in Examples 1 to 6 were mixed with an equal weight of anisole and allowed to stand at room temperature under atmospheric pressure for 8 hours to obtain a homogeneous solution. The resulting solution was applied to a substrate to a thickness of 0.10 mm and then heated at 250°C for 2 hours to dry and cure, obtaining a cured product. When a radical generator was used as the curing accelerator, the 2-hour heating at 250°C was carried out in a nitrogen atmosphere. When an organic nucleophile was used as the curing accelerator, or when no curing accelerator was used, the 2-hour heating at 250°C was carried out under atmospheric pressure. The substrates used were glass plates (commercially available float glass, 4 mm thick), aluminum foil (trade name "Aluminum Tough Sheet," 200mm square, manufactured by AS ONE Corporation), or copper plates (commercially available oxygen-free copper, 1 mm thick).

[0155] <Evaluation> The curable compositions prepared in the examples and comparative examples were evaluated as follows.

[0156] (1) Ring Closure Rate For the curable composition, １ The ring closure rate was calculated from the integrated intensity of the H-NMR spectrum signal using the above formula.

[0157] The NMR measurements were carried out under the following conditions: <NMR Measurement> Measurement apparatus: JEOL ECA500 or BRUKER AVANCE 600 MHz Measurement solvent: deuterated DMSO, deuterated chloroform, or a mixture of deuterated chloroform / pentafluorophenol = 2 / 1 (wt / wt) Chemical shift: TMS was used as the reference

[0158] (2) Heat-Generation Initiation Temperature, Glass Transition Temperature DSC measurement was performed on the curable composition. The intersection of the baseline of the temperature-thermal history curve obtained by the DSC measurement and the tangent at the inflection point of the exothermic peak was taken as the heat-generating initiation temperature. In addition, the cured product cured during the first temperature rise in the DSC measurement was subjected to DSC measurement again, and the temperature-thermal history curve obtained during the second temperature rise was taken as the glass transition temperature. The inflection point below the heat-generating initiation temperature on the temperature-thermal history curve obtained during the second temperature rise, or if no heat-generating peak was observed, the inflection point within the measurement temperature range was taken as the glass transition temperature.

[0159] The measurements were carried out under the following conditions: <DSC Measurement> Apparatus: Q2000 (manufactured by TA Instruments) Heating rate: 20°C / min Atmosphere: Nitrogen atmosphere Measurement temperature range: 30 to 450°C

[0160] (3) Liquid Chromatography / Mass Spectrometry The curable composition was subjected to liquid chromatography / mass spectrometry (LC / MS) to determine the area ratio [area value of Peak A / area value of Peak B] of Peak A (HPLC elution time: 15.5 min, MS detected mass-to-charge ratio: 1008 m / z) and Peak B (HPLC elution time: 17.7 min, MS detected mass-to-charge ratio: 963 m / z). Peak A is the peak of compound (1-1), and Peak B is the peak of compound (2-1).

[0161] The measurement was carried out under the following conditions: <LC / MS Measurement> Apparatus: Waters UPLC H-Class Plus / Xevo G2-X2 Qtof Column: Intersil ODS-3 (4.6 x 250 x 5) Eluent: (A) H ２ (B) ACN / THF = 40 / 60 v / v ((A) / (B) = 30 / 70 v / v during steady state, (B) only during separation) Flow rate: 0.4 mL / min Temperature: 40°C Detector: PDA (210-400 nm), MS (m / z 150-3000) Sample concentration: 1 mg / mL

[0162]

[0163] As shown in Table 1, it was confirmed that the curable compositions of the Examples had lower heat generation initiation temperatures in the presence of oxygen than the curable composition of Comparative Example 1, and that the glass transition temperatures of the cured products were equivalent to those of the cured product of the curable composition of Comparative Example 1.

[0164] Variations of the invention according to the present disclosure are described below. [Appendix 1] A curable compound represented by the following formula (1): [In the formula, R １ represents a curable functional group having a cyclic imide structure, and R ２ represents a functional group having a succinimide structure and promoting the curing of the curable functional group. １ and D ２ are the same or different and represent a single bond or a linking group. L represents a divalent group having a repeating unit containing a structure represented by the following formula (I) and a structure represented by the following formula (II). (In the formula, Ar １ ~Ar ３ are the same or different and represent a group in which two hydrogen atoms have been removed from the structural formula of an aromatic ring, or a group in which two or more aromatic rings are bonded via a single bond or a linking group and two hydrogen atoms have been removed. X represents -CO-, -S-, or -SO ２ Y may be the same or different and represents -S-, -SO ２ -, -O-, -CO-, -COO-, or -CONH-. n represents an integer of 0 or more. [Appendix 2] The R ２represents a group represented by the following formula (r-2): (In the formula, R ７ ~R １０ are the same or different and represent a hydrocarbon group. ９ and R １０ may be bonded to each other to form a ring. ２ [Appendix 3] The curable compound according to appendix 2, wherein the group represented by formula (r-2) is a group represented by formula (r-2'): (In the formula, R ９’ and R １０’ are the same or different and represent a saturated or unsaturated aliphatic hydrocarbon group having 1 to 6 carbon atoms. １ represents a group represented by the following formula (r-1): [In the formula, Q represents C or CH. Two Qs in the formula are bonded via a single bond or a double bond. R ３ ~R ６ are the same or different and represent a hydrogen atom or a hydrocarbon group. ３ and R ４ may be bonded to each other to form a ring. n' represents an integer of 0 or more. The bond marked with a wavy line in the formula is D. １ [Additional Note 5] In the formula (r-1), R ３ and R ４ and R are bonded to each other to form an alicyclic ring having 3 to 20 carbon atoms together with adjacent carbon atoms. ３ and R ４ and (r-1-1) to (r-1-6) are each a group selected from the groups represented by the following formulas: (The bond extending from the nitrogen atom in the formula is D in formula (1) １ [Supplementary Note 8] In the formula (1), D １ and D ２The curable compound according to any one of Appendices 1 to 7, wherein D is a group containing a divalent aromatic hydrocarbon group. １ and D ２ are the same or different and are selected from groups represented by the following formulas (d-1) to (d-4): [Supplementary Note 10] R in the formula (1) １ -D １ The curable compound according to any one of Appendices 1 to 9, wherein the - group is a group represented by the following formula (rd-1'-1) or (rd-1'-2): (In the formula, Q, R ３ , and R ４ represents, together with the adjacent carbon atom, an alicyclic ring having 3 to 20 carbon atoms or an aromatic ring having 6 to 14 carbon atoms. [Appendix 11] R in the formula (1) ２ -D ２ The curable compound according to any one of Appendices 1 to 10, wherein the - group is a group represented by the following formula (rd-2'-1) or (rd-2'-2): (In the formula, R ９’ and R １０’ are the same or different and represent a saturated or unsaturated aliphatic hydrocarbon group having 1 to 6 carbon atoms. [Appendix 12] Ar １ ~Ar ３ and each independently represent a group selected from the groups represented by the following formulas (a-1) to (a-5): [Appendix 13] The curable compound according to any one of Appendices 1 to 12, wherein L in formula (1) is a divalent group represented by the following formula (L-1-1) or (L-1-2): (In the above formula, m1 and m2 represent a range of 2 to 50.) [Appendix 14] The curable compound according to any one of Appendices 1 to 13, wherein the number-average molecular weight of compound (1) is 1,000 to 15,000. [Appendix 15] The curable compound according to any one of Appendices 1 to 14, wherein the weight-average molecular weight of compound (1) is 1,000 to 45,000. [Appendix 16] The curable compound according to any one of Appendices 1 to 15, wherein the solubility of compound (1) is 1 g or more per 100 g of solvent at 23°C. [Appendix 17] A curable composition comprising the curable compound according to any one of Appendices 1 to 16 and a compound represented by the following formula (2): [In the formula, R １１ and R １２ are the same or different and represent a curable functional group having a cyclic imide structure. １ and D ２ are the same or different and represent a single bond or a linking group. L represents a divalent group having a repeating unit containing a structure represented by the following formula (I) and a structure represented by the following formula (II). (In the formula, Ar １ ~Ar ３ are the same or different and represent a group in which two hydrogen atoms have been removed from the structural formula of an aromatic ring, or a group in which two or more aromatic rings are bonded via a single bond or a linking group and two hydrogen atoms have been removed. X represents -CO-, -S-, or -SO ２ Y may be the same or different and represents -S-, -SO ２(n) represents -, -O-, -CO-, -COO-, or -CONH-. n represents an integer of 0 or greater.) [Appendix 18] The curable composition according to Appendix 17, wherein the abundance ratio [compound represented by formula (1) / compound represented by formula (2)] calculated from the area ratio by MS analysis of the compound represented by formula (1) and the compound represented by formula (2) is 0.08 or greater. [Appendix 19] The curable composition according to Appendix 17 or 18, wherein the content of compound (1) is 10% by mass or greater, relative to 100% by mass of the total amount of the curable composition. [Appendix 20] The curable composition according to any one of Appendices 17 to 19, wherein the content of compound (1) is 40% by mass or greater, relative to 100% by mass of the total amount of solids in the curable composition. [Appendix 21] The curable composition according to any one of Appendices 17 to 20, further comprising a solvent. [Appendix 22] The curable composition according to Appendix 21, wherein the solvent is toluene. [Appendix 23] A method for producing the curable compound according to any one of Appendices 1 to 16, comprising reacting a compound represented by the following formula (1') with a cyclic acid anhydride in the presence of a compound having an acetamide structure to obtain the compound represented by the formula (1): [In the formula, D １ and D ２ are the same or different and represent a single bond or a linking group. L represents a divalent group having a repeating unit containing a structure represented by the following formula (I) and a structure represented by the following formula (II). (In the formula, Ar １ ~Ar ３ are the same or different and represent a group in which two hydrogen atoms have been removed from the structural formula of an aromatic ring, or a group in which two or more aromatic rings are bonded via a single bond or a linking group and two hydrogen atoms have been removed. X represents -CO-, -S-, or -SO ２ Y may be the same or different and represents -S-, -SO ２ represents -, -O-, -CO-, -COO-, or -CONH-, and n represents an integer of 0 or more.

Claims

1. A curable compound represented by the following formula (1): [In the formula, R １ represents a curable functional group having a cyclic imide structure, and R ２ represents a functional group having a succinimide structure and promoting the curing of the curable functional group. １ and D ２ are the same or different and represent a single bond or a linking group. L represents a divalent group having a repeating unit containing a structure represented by the following formula (I) and a structure represented by the following formula (II). (In the formula, Ar １ ~Ar ３ are the same or different and represent a group in which two hydrogen atoms have been removed from the structural formula of an aromatic ring, or a group in which two or more aromatic rings are bonded via a single bond or a linking group and two hydrogen atoms have been removed. X represents -CO-, -S-, or -SO ２ Y may be the same or different and represents -S-, -SO ２ represents -, -O-, -CO-, -COO-, or -CONH-, and n represents an integer of 0 or more.

2. The above R ２ The curable compound according to claim 1, wherein represents a group represented by the following formula (r-2): (In the formula, R ７ ~R １０ are the same or different and represent a hydrocarbon group. ９ and R １０ may be bonded to each other to form a ring. ２ (binds to 3. The above R １ The curable compound according to claim 1, wherein represents a group represented by the following formula (r-1): [In the formula, Q represents C or CH. Two Qs in the formula are bonded via a single bond or a double bond. R ３ ~R ６ are the same or different and represent a hydrogen atom or a hydrocarbon group. ３ and R ４ may be bonded to each other to form a ring. n' represents an integer of 0 or more. The bond marked with a wavy line in the formula is D. １ Bind to 4. The curable compound according to claim 3, wherein the group represented by formula (r-1) is a group selected from groups represented by the following formulas (r-1-1) to (r-1-6): (The bond extending from the nitrogen atom in the formula is D in formula (1) １ (combined with 5. A curable composition comprising the curable compound according to any one of claims 1 to 4 and a compound represented by the following formula (2): [In the formula, R １１ and R １２ are the same or different and represent a curable functional group having a cyclic imide structure. １ and D ２ are the same or different and represent a single bond or a linking group. L represents a divalent group having a repeating unit containing a structure represented by the following formula (I) and a structure represented by the following formula (II). (In the formula, Ar １ ~Ar ３ are the same or different and represent a group in which two hydrogen atoms have been removed from the structural formula of an aromatic ring, or a group in which two or more aromatic rings are bonded via a single bond or a linking group and two hydrogen atoms have been removed. X represents -CO-, -S-, or -SO ２ Y may be the same or different and represents -S-, -SO ２ represents -, -O-, -CO-, -COO-, or -CONH-, and n represents an integer of 0 or more.

6. The curable composition according to claim 5, wherein the abundance ratio [compound represented by formula (1) / compound represented by formula (2)] calculated from the area ratio by MS analysis of the compound represented by formula (1) and the compound represented by formula (2) is 0.08 or more.

7. A method for producing a curable compound according to any one of claims 1 to 4, comprising reacting a compound represented by the following formula (1') with a cyclic acid anhydride in the presence of a compound having an acetamide structure to obtain the compound represented by the formula (1): [In the formula, D １ and D ２ are the same or different and represent a single bond or a linking group. L represents a divalent group having a repeating unit containing a structure represented by the following formula (I) and a structure represented by the following formula (II). (In the formula, Ar １ ~Ar ３ are the same or different and represent a group in which two hydrogen atoms have been removed from the structural formula of an aromatic ring, or a group in which two or more aromatic rings are bonded via a single bond or a linking group and two hydrogen atoms have been removed. X represents -CO-, -S-, or -SO ２ Y may be the same or different and represents -S-, -SO ２ represents -, -O-, -CO-, -COO-, or -CONH-, and n represents an integer of 0 or more.

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