Copolymer, film, and method for producing copolymer

Abstract

To provide a new copolymer having both a polyamide skeleton and a polyester skeleton.SOLUTION: (1 is an integer of 1 or more; m1 and m2 are each an integer of 0 or more, and m1 + m2 is 1 or more; R1 and R2 are each a chain alkylene group having 1 to 20 carbon atoms; R3 is a chain alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms; n1 and n2 are each an integer of 1 or more; and are each an integer of 1 to 11; is a chain aliphatic hydrocarbon group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, a heteroarylene group having 4 or 5 carbon atoms, a group represented by the general formula "- unito-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu-Tu- X3 p1 X3 X2 R5 Z1 R4 Z1 R5 p2 R4 Z2 X2 X1 Z2. ). ). [Chemical Formula 1] SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a copolymer, a film, and a method for producing the copolymer. [Background technology]

[0002] Block copolymers having both polyamide and polyester backbones in the main chain can be designed to combine the properties derived from these two backbones. For example, polyamide backbones are advantageous for constructing polymers with high heat resistance and mechanical strength, while polyester backbones are advantageous for constructing polymers with high moldability. Some polyamide and polyester backbones also have the advantage of being highly biodegradable.

[0003] As a method for producing a block copolymer having both a polyamide skeleton and a polyester skeleton, there have been known methods, such as a method for producing a random copolymer in which repeating units derived from ε-caprolactone and repeating units derived from 2-pyrrolidone are randomly arranged by reacting ε-caprolactone with 2-pyrrolidone (see Non-Patent Document 1), a method for producing a block copolymer in which repeating units derived from ε-caprolactone and 2-pyrrolidone are randomly arranged by reacting ε-caprolactone with 2-pyrrolidone, and a method for producing a block copolymer in which a polyamide having a structure in which ε-caprolactone is sequentially reacted and has amino groups at both ends and a polyester having a structure in which ε-caprolactone is sequentially reacted and then diisocyanate is reacted to the hydroxyl groups at both ends and has isocyanate groups at both ends. Known methods include a method of producing a block copolymer having both a polyamide skeleton and a polyester skeleton by reacting an amino group in the polyamide with an isocyanate group in the polyester (see Non-Patent Document 2), and a method of producing a block copolymer having both a polyamide skeleton and a polyester skeleton by using a polyester having a structure in which glycol and dicarboxylic acid are alternately polymerized and having amino groups at both ends, and a polyamide having carboxy groups at both ends, and reacting the amino group in the polyester with the carboxy group in the polyamide (see Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2023 / 238706 [Non-patent literature]

[0005] [Non-Patent Document 1] Atsuyoshi Nakayama, Naoko Yamano, Norioki Kawasaki, Yasuhide Nakayama, Polym. Degrad. Stab. 2013, 98, 1882-1888. [Non-patent document 2] Seda Cakir, Rene Kierkels, Cor Koning, J. Polym. Sci. Part A: Polym. Chem. 2011, 49, 2823-2833. Summary of the Invention [Problem to be solved by the invention]

[0006] A wide variety of polymers having both polyamide and polyester skeletons are expected, but only a very limited number of types have been reported to date. Therefore, the development of new copolymers is desired for the development of new applications such as new films that exhibit excellent properties.

[0007] An object of the present invention is to provide a novel copolymer having both a polyamide skeleton and a polyester skeleton. [Means for solving the problem]

[0008] In order to solve the above problems, the present invention employs the following configuration. [1] The following general formula (1)

[0009] [ka] (wherein l is an integer of 1 or more; m1 and m2 each independently represent an integer of 0 or greater, provided that at least one of m1 and m2 is an integer of 1 or greater, and when l is 2 or greater, l instances of m1 may be the same or different from each other, and l instances of m2 may be the same or different from each other; R 1 and R 2 are each independently a chain alkylene group having 1 to 20 carbon atoms, and when at least one of l and m1 is 2 or more, l×m1 R 1 may be the same or different, and when at least one of l and m2 is 2 or more, l × m2 R 2 may be the same or different from each other; R 3 is a chain alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms, and when l is 2 or more, l R 3 may be the same or different from each other; n1 and n2 each independently represent an integer of 1 or greater, and when l is 2 or greater, l instances of n1 may be the same or different from each other, and l instances of n2 may be the same or different from each other; p1 and p2 each independently represent an integer of 1 to 11, and when at least one of l and n1 is 2 or greater, l×n1 p1s may be the same as or different from one another, and when at least one of l and n2 is 2 or greater, l×n2 p2s may be the same as or different from one another; X 1 represents a chain aliphatic hydrocarbon group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, a heteroarylene group having 4 or 5 carbon atoms, or a group represented by the general formula "-X 2 -Z 1 -X 3 -(in the formula, X 2 and X 3 are each independently an arylene group having 6 to 12 carbon atoms; Z 1 is a heteroatom or a heteroatom-containing group, or a group represented by the general formula "-R 4 -Z 2 -R 5 -(In the formula, R 4 and R 5are each independently a chain aliphatic hydrocarbon group having one or more carbon atoms, provided that the total number of carbon atoms in these aliphatic hydrocarbon groups is 20 or less; Z 2 is a hetero atom or a hetero atom-containing group, and when l is 2 or more, l X 1 may be the same or different.) A copolymer represented by the formula:

[0010] [2] X 1 is the general formula "-X 21 -OX 31 -(in the formula, X 21 and X 31 and each independently represents an arylene group having 6 to 9 carbon atoms. [3] R 1 and R 2 are each independently a chain alkylene group having 3 to 5 carbon atoms. [4] R 3 is a chain alkylene group having 3 to 5 carbon atoms. [5] The copolymer according to any one of [1] to [4], wherein the sum of m1 and m2 is 1 to 120. [6] The copolymer according to any one of [1] to [5], wherein p1 and p2 each independently represent an integer of 1 to 4.

[0011] [7] The copolymer according to any one of [1] to [6], wherein the sum of n1 and n2 is 2 to 240. [8] R 1 and R 2 The copolymer according to any one of [1] to [7], wherein p1 and p2 are the same as each other. [9] A film containing the copolymer according to any one of [1] to [8].

[10] The following general formula (11)

[0012] [ka] (In the formula, m1 and m2 each independently represent an integer of 0 or greater, provided that at least one of m1 and m2 represents an integer of 1 or greater; R 1 and R 2 are each independently a chain alkylene group having 1 to 20 carbon atoms, and when m1 is 2 or more, m1 R 1 may be the same or different, and when m2 is 2 or more, m2 R 2 may be the same or different from each other; R 3 represents a chain alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms; p1 and p2 each independently represent an integer of 1 to 11. and a compound represented by The following general formula (12)

[0013] [ka] (In the formula, n1 and n2 each independently represent an integer of 1 or more; p1 and p2 each independently represent an integer of 1 to 11, and when n1 is 3 or greater, n1-1 instances of p1 may be the same as or different from one another, and when n2 is 3 or greater, n2-1 instances of p2 may be the same as or different from one another; X 1 represents a chain aliphatic hydrocarbon group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, a heteroarylene group having 4 or 5 carbon atoms, or a group represented by the general formula "-X 2 -Z 1 -X 3 -(in the formula, X 2 and X 3 are each independently an arylene group having 6 to 12 carbon atoms; Z 1 is a heteroatom or a heteroatom-containing group, or a group represented by the general formula "-R 4 -Z 2 -R 5 -(In the formula, R 4 and R 5are each independently a chain aliphatic hydrocarbon group having one or more carbon atoms, provided that the total number of carbon atoms in these aliphatic hydrocarbon groups is 20 or less; Z 2 is a heteroatom or a heteroatom-containing group. and a compound represented by By reacting the following general formula (1)

[0014] [ka] (In the formula, m1, m2, R 1 , R 2 , R 3 , n1, n2, p1, p2 and X 1 is the same as above; l is an integer of 1 or more; when l is 2 or more, l m1s may be the same or different from each other, l m2s may be the same or different from each other, l n1s may be the same or different from each other, l n2s may be the same or different from each other, and l R 3 may be the same or different, and l X 1 may be the same or different from each other; when at least one of l and m1 is 2 or more, l × m1 R 1 may be the same or different from each other; when at least one of l and m2 is 2 or more, l × m2 R 2 may be the same or different from each other; when at least one of l and n1 is 2 or more, l×n1 p1s may be the same or different from each other; when at least one of l and n2 is 2 or more, l×n2 p2s may be the same or different from each other. A method for producing a copolymer, wherein the copolymer is obtained by: [Effects of the Invention]

[0015] According to the present invention, there is provided a novel copolymer having both a polyamide skeleton and a polyester skeleton. [Brief explanation of the drawings]

[0016] [Figure 1] 1 shows the results of 1H-NMR analysis of compound (15) obtained in Production Example 1. [Figure 2] 1 shows the results of 1H-NMR analysis of compound (13) obtained in Production Example 4. [Figure 3] 1 shows the results of 1H-NMR analysis of compound (12) obtained in Production Example 7. [Figure 4] 1 shows the results of 1H-NMR analysis of the copolymer (1) obtained in Example 1. [Figure 5] 1 shows imaging data of the films obtained in Examples 10 to 18. [Figure 6] 1 shows imaging data of the film obtained in Comparative Example 1. [Figure 7] 1 shows imaging data of the solid obtained in Comparative Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0017] In this specification, the concentration unit "M" means "mol / L." In this specification, when copolymers and compounds are represented by general formulas or other formulas (non-generalized formulas, sometimes simply referred to as "formulas" in this specification), symbols may be assigned to these general formulas or other formulas. In such cases, the copolymers and compounds may be given names that include the symbols. For example, a copolymer represented by the general formula (1) described below may be referred to as "copolymer (1)" in this specification.

[0018] <<Copolymer>> The copolymer according to one embodiment of the present invention is represented by the following general formula (1):

[0019] [ka] (wherein l is an integer of 1 or more; m1 and m2 each independently represent an integer of 0 or greater, provided that at least one of m1 and m2 is an integer of 1 or greater, and when l is 2 or greater, l instances of m1 may be the same or different from each other, and l instances of m2 may be the same or different from each other; R 1 and R 2 are each independently a chain alkylene group having 1 to 20 carbon atoms, and when at least one of l and m1 is 2 or more, l×m1 R 1 may be the same or different, and when at least one of l and m2 is 2 or more, l × m2 R 2 may be the same or different from each other; R 3 is a chain alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms, and when l is 2 or more, l R 3 may be the same or different from each other; n1 and n2 each independently represent an integer of 1 or greater, and when l is 2 or greater, l instances of n1 may be the same or different from each other, and l instances of n2 may be the same or different from each other; p1 and p2 each independently represent an integer of 1 to 11, and when at least one of l and n1 is 2 or greater, l×n1 p1s may be the same as or different from one another, and when at least one of l and n2 is 2 or greater, l×n2 p2s may be the same as or different from one another; X 1 represents a chain aliphatic hydrocarbon group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, a heteroarylene group having 4 or 5 carbon atoms, or a group represented by the general formula "-X 2 -Z 1 -X 3 -(in the formula, X 2 and X 3 are each independently an arylene group having 6 to 12 carbon atoms; Z 1 is a heteroatom or a heteroatom-containing group, or a group represented by the general formula "-R 4 -Z 2 -R 5 -(In the formula, R 4 and R 5are each independently a chain aliphatic hydrocarbon group having one or more carbon atoms, provided that the total number of carbon atoms in these aliphatic hydrocarbon groups is 20 or less; Z 2 is a hetero atom or a hetero atom-containing group, and when l is 2 or more, l X 1 may be the same or different.) (In this specification, this copolymer may be referred to as "copolymer (1)").

[0020] Copolymer (1) is a novel copolymer having both a polyamide skeleton and a polyester skeleton, and includes a block copolymer, including a multi-block copolymer having a block containing a polyamide skeleton and a block containing a polyester skeleton.

[0021] The heat resistance and mechanical strength of the copolymer (1) can be increased by, for example, adjusting the structure and size of the polyamide skeleton. On the other hand, the processability of the copolymer (1) can be improved by adjusting the structure and size of the polyester skeleton, for example. That is, in the copolymer (1), by adjusting the ratio of the polyamide skeleton and the ratio of the polyester skeleton, it is possible to adjust the balance of the properties derived from these skeletons. Furthermore, both the polyamide backbone and the polyester backbone have biodegradability depending on their structure, and therefore, by adjusting the structure of these backbones, the biodegradability of the copolymer (1) can be improved.

[0022] In the general formula (1), l defines the molecular size of the copolymer (1) and is an integer of 1 or more. On the other hand, the upper limit of 1 is not particularly limited. For example, in terms of facilitating the production of copolymer (1), such as facilitating the purification of copolymer (1), 1 is preferably 100 or less, more preferably 50 or less, and even more preferably 30 or less, and may be, for example, 10 or less.

[0023] In the general formula (1), m1 is a group represented by the general formula "-OR 1 It specifies the number of groups represented by "-C(=O)-" and is an integer of 0 or more. When m1 is 2 or more, the group is a repeating unit in a block containing a polyester skeleton, and m1 is the number of repeats. Similarly, in the general formula (1), m2 represents a group represented by the general formula "-C(=O)-R 2 It defines the number of groups represented by "-O-" and is an integer of 0 or more. When m2 is 2 or more, the group is a repeating unit in a block containing a polyester skeleton, and m2 is the number of repeats.

[0024] m1 is 0 or more, and may be, for example, any one of 1 or more, 2 or more, 5 or more, 8 or more, 11 or more, 15 or more, and 22 or more. On the other hand, the upper limit of m1 is not particularly limited. For example, a copolymer (1) having m1 of 60 or less can be more easily produced. In order to more easily produce a copolymer (1) having good properties, m1 may be, for example, 50 or less, 35 or less, 28 or less, 21 or less, 15 or less, or 8 or less. For example, m1 can be appropriately set within a numerical range that is set by arbitrarily combining any of the above lower limit values ​​with any of the above upper limit values.

[0025] When l is 2 or more, the l instances of m1 may be the same or different from one another. In this specification, not only in the case of m1, but also in the case of objects to be compared that "may be the same or different from one another" means that all may be the same, all may be different, or only some may be the same. When l m1's are different from one another, the combination of l m1's is not particularly limited.

[0026] m2 is 0 or more, and may be, for example, any one of 1 or more, 2 or more, 5 or more, 8 or more, 11 or more, 15 or more, and 22 or more. On the other hand, the upper limit of m2 is not particularly limited. For example, a copolymer (1) having m2 of 60 or less can be more easily produced. In order to more easily produce a copolymer (1) having good properties, m2 may be, for example, 50 or less, 35 or less, 28 or less, 21 or less, 15 or less, or 8 or less. For example, m2 can be appropriately set within a numerical range that is set by arbitrarily combining any of the above lower limit values ​​with any of the above upper limit values.

[0027] When l is 2 or more, l instances of m2 may be the same or different, and the combination of l instances of m2 is not particularly limited.

[0028] However, in general formula (1), neither m1 nor m2 is 0, and at least one of m1 and m2 is an integer of 1 or more.

[0029] m1+m2 (the total value of m1 and m2) is 1 or more, and may be, for example, any one of 2 or more, 4 or more, 10 or more, 16 or more, 22 or more, 30 or more, and 44 or more. On the other hand, the upper limit of m1+m2 is not particularly limited. For example, a copolymer (1) in which m1+m2 is 120 or less can be more easily produced. In order to more easily produce a copolymer (1) with good properties, m1+m2 may be, for example, 100 or less, 70 or less, 56 or less, 42 or less, 30 or less, or 16 or less. m1+m2 can be appropriately set within a numerical range that is set by arbitrarily combining any of the above lower limit values ​​with any of the above upper limit values. For example, in one embodiment, m1+m2 may be any of 1 to 120, 2 to 120, 4 to 120, 10 to 120, 16 to 120, 22 to 120, 30 to 120, and 44 to 120, or any of 1 to 100, 1 to 70, 1 to 56, 1 to 42, 1 to 30, and 1 to 16, or any of 2 to 100, 4 to 70, 10 to 56, 16 to 42, and 22 to 30. However, these are examples of m1+m2, and m1+m2 is not limited to these.

[0030] For example, a copolymer (1) in which m1 and m2 are different from each other can be more easily produced.

[0031] In general formula (1), R 1 and R 2 are each independently a chain alkylene group having 1 to 20 carbon atoms. 1 The alkylene group in R 2 The alkylene groups in R may be the same or different from each other. 1 and R 2 are preferably the same as each other.

[0032] R 1 and R 2 The alkylene group in the formula (I) may be either linear or branched. R 1 and R 2Examples of the alkylene group in the formula (I) include a methylene group, an ethylene group, a propylene group (methylethylene group), a trimethylene group, a tetramethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, a 1,2-dimethylethylene group, a 1,1-dimethylethylene group, an ethylethylene group, a pentamethylene group, a 1-methyltetramethylene group, a 2-methyltetramethylene group, a 1,1-dimethyltrimethylene group, a 1,2-dimethyltrimethylene group, a 1,3 -Dimethyltrimethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, 1-methyl-2-ethylethylene group, n-propylethylene group, hexamethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 1,1-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 1,4-dimethyltetramethylene group, 2,3-dimethyltetramethylene group , 2,2-dimethyltetramethylene group, 1-ethyltetramethylene group, 2-ethyltetramethylene group, 1-methyl-2-ethyltrimethylene group, 1-methyl-3-ethyltrimethylene group, 2-methyl-3-ethyltrimethylene group, 1-methyl-1-ethyltrimethylene group, 2-methyl-2-ethyltrimethylene group, 1,2,3-trimethyltrimethylene group, 1,1,2,2-tetramethylethylene group, heptane-1,7-diyl group, octane-1,8 -diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group, octadecane-1,18-diyl group, nonadecane-1,19-diyl group, and icosane-1,20-diyl group.

[0033] R 1 and R 2 The number of carbon atoms of the alkylene group in the formula (I) may be, for example, any one of 1 to 17, 1 to 14, 1 to 11, 1 to 8, and 1 to 5, any one of 3 to 20, 6 to 20, 9 to 20, 12 to 20, and 15 to 20, or 3 to 5. For example, R 1 and R 2 When m is an alkylene group having 3 to 5 carbon atoms, the polyester skeleton to which m1 and m2 are assigned has high biodegradability, and copolymer (1) has more preferable properties.

[0034] When either or both of l and m1 are 2 or more, l × m1 R 1 may be the same or different from each other. If either or both of l and m2 are 2 or more, l × m2 R 2 may be the same or different from each other.

[0035] In general formula (1), R 3 is a chain alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms. R 3 The alkylene group in the formula (I) may be either linear or branched. R 3Examples of the alkylene group in the formula (I) include an ethylene group, a propylene group (methylethylene group), a trimethylene group, a tetramethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, a 1,2-dimethylethylene group, a 1,1-dimethylethylene group, an ethylethylene group, a pentamethylene group, a 1-methyltetramethylene group, a 2-methyltetramethylene group, a 1,1-dimethyltrimethylene group, a 1,2-dimethyltrimethylene group, a 1,3-dimethyltrimethylene group, a 1-ethyltrimethylene group, a 2-ethyltrimethylene group, a 1-methyl-2-ethylethylene group, an n-propylethylene group, a hexamethylene group, a 1-methylpentamethylene group, a 2-methylpentamethylene group, a 3-methylpentamethylene group, a 1,1-dimethyltetramethylene group, a 1,2- Examples thereof include a dimethyltetramethylene group, a 1,3-dimethyltetramethylene group, a 1,4-dimethyltetramethylene group, a 2,3-dimethyltetramethylene group, a 2,2-dimethyltetramethylene group, a 1-ethyltetramethylene group, a 2-ethyltetramethylene group, a 1-methyl-2-ethyltrimethylene group, a 1-methyl-3-ethyltrimethylene group, a 2-methyl-3-ethyltrimethylene group, a 1-methyl-1-ethyltrimethylene group, a 2-methyl-2-ethyltrimethylene group, a 1,2,3-trimethyltrimethylene group, a 1,1,2,2-tetramethylethylene group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, and a dodecane-1,12-diyl group.

[0036] R 3 The alkylene group in the formula (I) may have, for example, any of 2 to 9, 2 to 7, and 2 to 5 carbon atoms, any of 3 to 12, 6 to 12, and 9 to 12 carbon atoms, or 3 to 9 carbon atoms.

[0037] R 3 The arylene group in the formula (I) is preferably monocyclic. R 3 Examples of the arylene group in the formula (I) include phenylene groups such as a 1,4-phenylene group (benzene-1,4-diyl group), a 1,3-phenylene group, and a 1,2-phenylene group; toluenediyl groups such as toluene-2,6-diyl (2-methylbenzene-1,3-diyl), toluene-2,5-diyl, toluene-2,4-diyl, toluene-2,3-diyl, and toluene-3,5-diyl; xylenediyl groups such as o-xylene-3,4-diyl, o-xylene-3,5-diyl, o-xylene-3,6-diyl, m-xylene-2,4-diyl, m-xylene-2,5-diyl, m-xylene-2,6-diyl, p-xylene-2,3-diyl, p-xylene-2,5-diyl, and p-xylene-2,6-diyl; trimethylbenzene-diyl groups such as 1,2,3-trimethylbenzene-4,5-diyl group, 1,2,3-trimethylbenzene-4,6-diyl group, 1,2,4-trimethylbenzene-3,5-diyl group, 1,2,4-trimethylbenzene-3,6-diyl group, and 1,3,5-trimethylbenzene-2,4-diyl group; Diethylbenzene-diyl groups such as 1,3-diethylbenzene-4,5-diyl group, 1,3-diethylbenzene-4,6-diyl group, 1,3-diethylbenzene-2,4-diyl group, 1,3-diethylbenzene-2,5-diyl group, 1,4-diethylbenzene-2,3-diyl group, 1,4-diethylbenzene-2,5-diyl group, and 1,4-diethylbenzene-2,6-diyl group; dimethylethylbenzene-diyl groups such as 1,3-dimethyl-2-ethylbenzene-4,5-diyl group, 1,3-dimethyl-2-ethylbenzene-4,6-diyl group, 1,2-dimethyl-4-ethylbenzene-3,6-diyl group, 1,2-dimethyl-4-ethylbenzene-3,5-diyl group, and 1,2-dimethyl-4-ethylbenzene-5,6-diyl group; Diethylmethylbenzene-diyl groups such as 1,3-diethyl-5-methylbenzene-2,4-diyl group and 1,3-diethyl-5-methylbenzene-2,6-diyl group: biphenyl-diyl groups such as biphenyl-2,2'-diyl group, biphenyl-3,3'-diyl group, biphenyl-4,4'-diyl group, biphenyl-2,3'-diyl group, biphenyl-2,4'-diyl group, and biphenyl-3,4'-diyl group; etc.

[0038] As used herein, R 3 The term "monocyclic" refers to a ring shape that is not a fused ring, including but not limited to the arylene group in the above. Therefore, for example, a group having a structure in which one or more hydrogen atoms have been removed from biphenyl is defined as monocyclic in this specification.

[0039] R 3 is preferably a chain alkylene group having 2 to 6 carbon atoms, and more preferably a chain alkylene group having 3 to 5 carbon atoms. Such a copolymer (1) not only has good properties but can also be produced more easily.

[0040] If l is 2 or more, l R 3 may be the same or different, and l R 3 The combination is not particularly limited.

[0041] In general formula (1), n1 defines the number of groups represented by the general formula "-C(=O)-(CH2)p1-NH-" and is an integer of 1 or greater. The group is a repeating unit in a block containing a polyamide skeleton, and n1 is the number of repeats. Similarly, in general formula (1), n2 defines the number of groups represented by the general formula "-NH-(CH2)p2-C(=O)-" and is an integer of 1 or greater. The group is a repeating unit in a block containing a polyamide skeleton, and n2 is the number of repeats.

[0042] n1 is 1 or more, and may be, for example, any one of 4 or more, 6 or more, 9 or more, 13 or more, and 16 or more. On the other hand, the upper limit of n1 is not particularly limited. For example, a copolymer (1) having n1 of 120 or less can be more easily produced. In order to more easily produce a copolymer (1) having good properties, n1 may be, for example, any of 60 or less, 45 or less, 35 or less, 25 or less, 15 or less, and 8 or less. For example, n1 can be appropriately set within a numerical range that is set by arbitrarily combining any of the above lower limit values ​​with any of the above upper limit values.

[0043] When l is 2 or more, the l n1s may be the same or different, and the combination of the l n1s is not particularly limited.

[0044] n2 is 1 or more, and may be, for example, any one of 4 or more, 6 or more, 9 or more, 13 or more, and 16 or more. On the other hand, the upper limit of n2 is not particularly limited. For example, a copolymer (1) having n2 of 120 or less can be more easily produced. In order to more easily produce a copolymer (1) having good properties, n2 may be, for example, any of 60 or less, 45 or less, 35 or less, 25 or less, 15 or less, and 8 or less. For example, n2 can be appropriately set within a numerical range that is set by arbitrarily combining any of the lower limit values ​​and any of the upper limit values ​​described above.

[0045] When l is 2 or more, the l n2's may be the same or different, and the combination of the l n2's is not particularly limited.

[0046] In general formula (1), both n1 and n2 may be 1, but it is preferable that at least one of n1 and n2 is an integer of 2 or more.

[0047] n1+n2 (the total value of n1 and n2) is 2 or more, and may be, for example, any one of 8 or more, 12 or more, 18 or more, 26 or more, and 32 or more. On the other hand, the upper limit of n1+n2 is not particularly limited. For example, a copolymer (1) in which n1+n2 is 240 or less can be more easily produced. In terms of more easily producing a copolymer (1) with good properties, n1+n2 may be, for example, 120 or less, 90 or less, 70 or less, 50 or less, 30 or less, or 16 or less. n1+n2 can be appropriately set within a numerical range that is set by arbitrarily combining any of the above lower limit values ​​with any of the above upper limit values. For example, in one embodiment, n1+n2 may be any of 2 to 240, 8 to 240, 12 to 240, 18 to 240, 26 to 240, and 32 to 240, or any of 2 to 120, 2 to 90, 2 to 70, 2 to 50, 2 to 30, and 2 to 16, or any of 8 to 120, 12 to 90, 18 to 70, and 26 to 50. However, these are examples of n1 and n2, and n1 and n2 are not limited to these.

[0048] n1 and n2 may be the same or different from each other. For example, a copolymer (1) in which n1 and n2 are different from each other can be more easily produced.

[0049] In general formula (1), p1 and p2 each represent the number of repeating methylene groups (-CH2-) and are each independently an integer of 1 to 11. That is, p1 and p2 may be the same or different from each other. From the viewpoint of easier production of copolymer (1), it is preferable that p1 and p2 are the same as each other.

[0050] For example, p1 and p2 may each independently be any of 1 to 8, 1 to 6, and 1 to 4, or any of 3 to 11, 5 to 11, and 8 to 11, or may be 3 to 8. For example, in terms of improving the biodegradability of the copolymer (1), it is preferable that p1 and p2 each independently be an integer of 1 to 4.

[0051] When either or both of l and n1 are 2 or more, the l×n1 p1s may be the same or different. When either or both of l and n2 are 2 or greater, l×n2 p2's may be the same or different from each other.

[0052] In the copolymer (1), R 1 and R 2It is more preferable that p1 and p2 are the same as each other, and p1 and p2 are the same as each other. Such a copolymer (1) can be produced more easily.

[0053] In general formula (1), X 1 represents a chain aliphatic hydrocarbon group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, a heteroarylene group having 4 or 5 carbon atoms, or a group represented by the general formula "-X 2 -Z 1 -X 3 -(in the formula, X 2 and X 3 are each independently an arylene group having 6 to 12 carbon atoms; Z 1 is a heteroatom or a heteroatom-containing group, or a group represented by the general formula "-R 4 -Z 2 -R 5 -(In the formula, R 4 and R 5 are each independently a chain aliphatic hydrocarbon group having one or more carbon atoms, provided that the total number of carbon atoms in these aliphatic hydrocarbon groups is 20 or less; Z 2 is a heteroatom or a heteroatom-containing group.

[0054] X 1 The chain aliphatic hydrocarbon group having 1 to 12 carbon atoms in the formula (I) is a divalent group, and may be either a linear or branched chain, and may be either a saturated or unsaturated aliphatic hydrocarbon group.

[0055] X 1 The saturated aliphatic hydrocarbon group in the formula (I) is a chain alkylene group having 1 to 12 carbon atoms, and the alkylene group is the alkylene group selected from the group consisting of the above-mentioned R 1 and R 2 Among the alkylene groups in the above, those having 1 to 12 carbon atoms are exemplified.

[0056] X 1Examples of the unsaturated aliphatic hydrocarbon group in the formula (I) include divalent groups having 2 to 12 carbon atoms, in which one or more single bonds (CC) between carbon atoms in the saturated aliphatic hydrocarbon group (alkylene group) are replaced with a double bond (C=C) or a triple bond (C≡C). The total number of unsaturated bonds (double bonds and triple bonds) in the unsaturated aliphatic hydrocarbon group is not particularly limited, but is preferably 1 to 3, and may be, for example, 1 or 2, or may be 1. The unsaturated aliphatic hydrocarbon group preferably has a double bond as an unsaturated bond but does not have a triple bond, and is more preferably an alkenylene group.

[0057] X 1 The arylene group having 6 to 12 carbon atoms in the formula (I) is preferably monocyclic. X 1 The arylene group in the formula (I) is the same as the above-mentioned R 3 Examples of the arylene group include the same arylene groups having 6 to 12 carbon atoms as those in the above.

[0058] X 1 In the heteroarylene group having 4 or 5 carbon atoms, examples of the heteroatom constituting the aromatic ring skeleton include an oxygen atom, a nitrogen atom, and a sulfur atom. The number of heteroatoms constituting the aromatic ring skeleton in the heteroarylene group may be one or may be two or more, and when there are two or more heteroatoms, the combination thereof is not particularly limited.

[0059] Among the heteroarylene groups, examples of those having an oxygen atom as the heteroatom include furan-diyl groups such as a furan-2,3-diyl group, a furan-2,4-diyl group, a furan-2,5-diyl group, a furan-3,4-diyl group, a furan-2,5-diyl group, and a furan-3,5-diyl group. Among the heteroarylene groups, examples of those having a nitrogen atom as the heteroatom include pyridine-diyl groups such as pyridine-2,3-diyl group, pyridine-2,4-diyl group, pyridine-2,5-diyl group, pyridine-2,6-diyl group, pyridine-3,4-diyl group, and pyridine-3,5-diyl group; and pyrrole-diyl groups such as pyrrole-2,3-diyl group, pyrrole-2,4-diyl group, pyrrole-2,5-diyl group, and pyrrole-3,4-diyl group. Among the heteroarylene groups, examples of those having a sulfur atom as the heteroatom include thiophene-diyl groups such as a thiophene-2,3-diyl group, a thiophene-2,4-diyl group, a thiophene-2,5-diyl group, and a thiophene-3,4-diyl group.

[0060] X 1 In the general formula "-X 2 -Z 1 -X 3 X in the group represented by "-" 2 is bonded to a carbon atom in one of the carbonyl groups in the general formula (1), and X 3 is bonded to the carbon atom in the other carbonyl group in the general formula (1). General formula “-X 2 -Z 1 -X 3 -” Medium, X 2 and X 3 are each independently an arylene group having 6 to 12 carbon atoms. 2 the arylene group in X 3 The arylene groups in X may be the same or different from each other. 2 and X 3 are preferably the same as each other.

[0061] X 2 and X 3 The arylene group having 6 to 12 carbon atoms in the formula (I) is the same as the above-mentioned X 1 Examples of the arylene group include the same arylene groups having 6 to 12 carbon atoms as those mentioned above.

[0062] X 2 and X 3 The arylene group in the formula (I) preferably has 6 to 9 carbon atoms.

[0063] General formula “-X 2 -Z 1 -X 3 -” Medium, Z 1 is a heteroatom or a heteroatom-containing group. Z 1 Among these, preferred examples of the heteroatom include an oxygen atom (O) and a sulfur atom (S). Z 1 Among these, the heteroatom-containing group is a divalent group having a heteroatom, and is preferably a divalent group having a nitrogen atom (N), a silicon atom (Si), or a phosphorus atom (P).

[0064] Among the heteroatom-containing groups, examples of divalent groups having a nitrogen atom (nitrogen atom-containing groups) include imino groups (—NH—). Among the heteroatom-containing groups, examples of divalent groups having a silicon atom (silicon atom-containing groups) include dialkylsilylene groups such as a dimethylsilylene group (-Si(CH3)2-). Among the heteroatom-containing groups, examples of divalent groups having a phosphorus atom (phosphorus atom-containing groups) include arylphosphanylene groups such as a phenylphosphanylene group (-P(C6H5)-).

[0065] General formula “-X 2 -Z 1 -X 3 Among the groups represented by "-", X 2 and X 3 When is a phenylene group, preferred examples of the group include divalent groups having a diaryl ether skeleton, diarylamine skeleton, diaryl sulfide skeleton, diaryl phosphine skeleton, or diaryl silane skeleton, as represented by the following formula: 2 -Z 1 -X 3The group represented by "-" is not limited to these.

[0066] [ka] (In the formula, one of the bonds marked with a symbol "*" is formed with a carbon atom in one carbonyl group in the general formula (1), and the other is formed with a carbon atom in the other carbonyl group in the general formula (1).)

[0067] X 1 In the general formula "-R 4 -Z 2 -R 5 -" 4 is bonded to a carbon atom in one of the carbonyl groups in the general formula (1), and R 5 is bonded to the carbon atom in the other carbonyl group in the general formula (1). General formula “-R 4 -Z 2 -R 5 -” Medium, R 4 and R 5 are each independently a chain aliphatic hydrocarbon group having one or more carbon atoms. 4 the aliphatic hydrocarbon group in R 5 The aliphatic hydrocarbon groups in R may be the same or different from each other. 4 and R 5 are preferably the same as each other. However, R 4 The number of carbon atoms in the aliphatic hydrocarbon group and R 5 The total number of carbon atoms in the aliphatic hydrocarbon group in R is 20 or less. 4 The number of carbon atoms in the aliphatic hydrocarbon group and R 5 The aliphatic hydrocarbon groups in each of the above groups independently have 1 to 19 carbon atoms.

[0068] R 4 and R 5The aliphatic hydrocarbon group in the formula (I) is a divalent group, and may be either a linear or branched chain group, and may be either a saturated or unsaturated aliphatic hydrocarbon group.

[0069] R 4 and R 5 The saturated aliphatic hydrocarbon group in the formula (I) is a chain alkylene group having 1 to 19 carbon atoms, and the alkylene group is the alkylene group selected from the group consisting of the above-mentioned R 1 and R 2 Among the alkylene groups in the above, those having 1 to 19 carbon atoms are exemplified.

[0070] R 4 and R 5 Examples of the unsaturated aliphatic hydrocarbon group in the formula (I) include divalent groups having 2 to 19 carbon atoms, in which one or more single bonds (CC) between carbon atoms in the saturated aliphatic hydrocarbon group (alkylene group) are replaced with a double bond (C=C) or a triple bond (C≡C). The total number of unsaturated bonds (double bonds and triple bonds) in the unsaturated aliphatic hydrocarbon group is not particularly limited, but is preferably 1 to 3, and may be, for example, 1 or 2, or may be 1. The unsaturated aliphatic hydrocarbon group preferably has a double bond as an unsaturated bond but does not have a triple bond, and is more preferably an alkenylene group.

[0071] R 4 and R 5 The number of carbon atoms of the unsaturated aliphatic hydrocarbon group in the formula (I) may be, for example, any one of 2 to 16, 2 to 13, 2 to 10, 2 to 7, and 2 to 4; any one of 3 to 19, 6 to 19, 9 to 19, 12 to 19, and 15 to 19; or any one of 3 to 16 and 6 to 13.

[0072] General formula “-R 4 -Z 2 -R 5 -” Medium, Z 2 is a heteroatom or a heteroatom-containing group. Z 2Among these, preferred examples of the heteroatom include an oxygen atom and a sulfur atom. Z 2 Among these, the heteroatom-containing group is a divalent group having a heteroatom, and is preferably a divalent group having a nitrogen atom, a silicon atom, or a phosphorus atom.

[0073] Among the heteroatom-containing groups, examples of divalent groups having a nitrogen atom (nitrogen atom-containing groups) include imino groups (—NH—). Among the heteroatom-containing groups, examples of divalent groups having a silicon atom (silicon atom-containing groups) include a silylene group (-SiH2-). Among the heteroatom-containing groups, examples of divalent groups having a phosphorus atom (phosphorus atom-containing groups) include a phosphanylene group (-PH-) group.

[0074] X 1 is the general formula "-X 2 -Z 1 -X 3 It is preferable that the group is a group represented by "-".

[0075] General formula “-R 4 -Z 2 -R 5 Among the groups represented by "-", R 4 and R 5 However, when the alkylene group has 1 to 3 carbon atoms, preferred examples of the group include divalent groups having a dialkyl ether skeleton, a dialkylamine skeleton, a dialkyl sulfide skeleton, a dialkyl phosphine skeleton, or a dialkyl silane skeleton, as represented by the following formula: -CH2-O-CH2- -(CH2)2-O-(CH2)2- -(CH2)3-O-(CH2)3- -CH2-S-CH2- -(CH2)2-S-(CH2)2- -(CH2)3-S-(CH2)3- -CH2-NH-CH2- -(CH2)2-NH-(CH2)2- -(CH2)3-NH-(CH2)3- -CH2-SiH2-CH2- -(CH2)2-SiH2-(CH2)2- -(CH2)3-SiH2-(CH2)3- -CH2-PH-CH2- -(CH2)2-PH-(CH2)2- -(CH2)3-PH-(CH2)3-

[0076] If l is 2 or more, l X 1 may be the same or different, and l X 1 The combination is not particularly limited.

[0077] X 1 is the general formula "-X 21 -Z 11 -X 31 -(in the formula, X 21 and X 31 are each independently an arylene group having 6 to 9 carbon atoms; Z 11 is an oxygen atom, a sulfur atom, a silicon atom-containing group, a phosphorus atom-containing group, or a nitrogen atom-containing group. Such a copolymer (1) not only has good properties but can also be produced more easily.

[0078] The general formula “-X 21 -Z 11 -X 31 X in the group represented by "-" 21 is bonded to a carbon atom in one of the carbonyl groups in the general formula (1), and X 31 is bonded to the carbon atom in the other carbonyl group in the general formula (1). General formula “-X 21 -Z 11 -X 31 -” Medium, X 21 and X 31 are each independently an arylene group having 6 to 9 carbon atoms. 21 the arylene group in X 31The arylene groups in X may be the same or different from each other. 21 and X 31 are preferably the same as each other.

[0079] X 21 and X 31 The arylene group having 6 to 9 carbon atoms in the formula (I) is the same as the above-mentioned X 1 Among the arylene groups in the above, the same arylene groups having 6 to 9 carbon atoms can be mentioned. X 21 and X 31 More specifically, the arylene group in the formula (I) includes phenylene groups such as a 1,4-phenylene group (a benzene-1,4-diyl group), a 1,3-phenylene group, and a 1,2-phenylene group; toluenediyl groups such as toluene-2,6-diyl (2-methylbenzene-1,3-diyl), toluene-2,5-diyl, toluene-2,4-diyl, toluene-2,3-diyl, and toluene-3,5-diyl; xylenediyl groups such as o-xylene-3,4-diyl, o-xylene-3,5-diyl, o-xylene-3,6-diyl, m-xylene-2,4-diyl, m-xylene-2,5-diyl, m-xylene-2,6-diyl, p-xylene-2,3-diyl, p-xylene-2,5-diyl, and p-xylene-2,6-diyl; trimethylbenzene-diyl groups such as 1,2,3-trimethylbenzene-4,5-diyl group, 1,2,3-trimethylbenzene-4,6-diyl group, 1,2,4-trimethylbenzene-3,5-diyl group, 1,2,4-trimethylbenzene-3,6-diyl group, and 1,3,5-trimethylbenzene-2,4-diyl group; etc.

[0080] The general formula “-X 21 -Z 11 -X 31 Z in the group represented by "-" 11 is an oxygen atom, a sulfur atom, a silicon atom-containing group, a phosphorus atom-containing group, or a nitrogen atom-containing group. Z 11 The silicon atom-containing group, the phosphorus atom-containing group, and the nitrogen atom-containing group in 1 These are the same as the silicon atom-containing group, phosphorus atom-containing group and nitrogen atom-containing group in the above formula.

[0081] X 1 is the general formula "-X 21 -OX 31 -(in the formula, X 21 and X 31 are each independently an arylene group having 6 to 9 carbon atoms. It is more preferable that the group is a group represented by the formula: ##STR1## Such a copolymer (1) has better properties and can be produced more easily.

[0082] The number average molecular weight (Mn) of the copolymer (1) is preferably 5,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 8,000 to 40,000. The weight average molecular weight (Mw) of the copolymer (1) is preferably 10,000 to 300,000, more preferably 10,000 to 150,000, and even more preferably 12,000 to 120,000. When the number-average molecular weight or weight-average molecular weight of the copolymer (1) is equal to or greater than the lower limit, the strength of the copolymer (1) and a film containing the copolymer (1) described below will be increased. When the number-average molecular weight or weight-average molecular weight of the copolymer (1) is equal to or less than the upper limit, the formability of the copolymer (1) and a film containing the copolymer (1) described below will be increased.

[0083] In this specification, unless otherwise specified, the "average molecular weight" is a value calculated as polymethyl methacrylate measured by gel permeation chromatography (GPC).

[0084] In copolymer (1), when the polyester skeleton side is the terminal of copolymer (1), the terminal may be an amino group (-NH2) bonded to a methylene group marked with symbol p1 or p2, or may be a salt formed by the amino group and an acid. Examples of the acid that forms a salt with the amino group include hydrogen halides such as hydrogen chloride, hydrogen bromide, and hydrogen iodide; sulfonic acids, etc. In the copolymer (1), when the polyamide skeleton side is the terminal part of the copolymer (1), the terminal part may be a carboxy group (-C(=O)-OH) bonded to a methylene group marked with symbol p1 or p2, or an anion (-C(=O)-OH) dissociated from the carboxy group. - ) and a cation. Examples of the cation that forms the salt include metal ions, ammonium ions (NH4 + ) and other inorganic cations; protons (H + ) and other organic cations such as ammonium ions having a structure in which the cation is added.

[0085] <<Copolymer manufacturing method>> A method for producing a copolymer according to one embodiment of the present invention comprises:

[0086] [ka] (In the formula, m1 and m2 each independently represent an integer of 0 or greater, provided that at least one of m1 and m2 represents an integer of 1 or greater; R 1 and R 2 are each independently a chain alkylene group having 1 to 20 carbon atoms, and when m1 is 2 or more, m1 R 1 may be the same or different, and when m2 is 2 or more, m2 R 2 may be the same or different from each other; R 3 represents a chain alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms; p1 and p2 each independently represent an integer of 1 to 11. (Herein, this specification may be referred to as "compound (11)") represented by the following formula: The following general formula (12)

[0087] [ka] (In the formula, n1 and n2 each independently represent an integer of 1 or more; p1 and p2 each independently represent an integer of 1 to 11, and when n1 is 3 or greater, n1-1 instances of p1 may be the same as or different from one another, and when n2 is 3 or greater, n2-1 instances of p2 may be the same as or different from one another; X 1 represents a chain aliphatic hydrocarbon group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, a heteroarylene group having 4 or 5 carbon atoms, or a group represented by the general formula "-X 2 -Z 1 -X 3 -(in the formula, X 2 and X 3 are each independently an arylene group having 6 to 12 carbon atoms; Z 1 is a heteroatom or a heteroatom-containing group, or a group represented by the general formula "-R 4 -Z 2 -R 5 -(In the formula, R 4 and R 5 are each independently a chain aliphatic hydrocarbon group having one or more carbon atoms, provided that the total number of carbon atoms in these aliphatic hydrocarbon groups is 20 or less; Z 2 is a heteroatom or a heteroatom-containing group. (Herein, this specification may be referred to as "compound (12)") represented by the following formula: By reacting the following general formula (1)

[0088] [ka] (In the formula, m1, m2, R 1 , R 2 , R3 , n1, n2, p1, p2 and X 1 is the same as above; l is an integer of 1 or more; when l is 2 or more, l m1s may be the same or different from each other, l m2s may be the same or different from each other, l n1s may be the same or different from each other, l n2s may be the same or different from each other, and l R 3 may be the same or different, and l X 1 may be the same or different from each other; when at least one of l and m1 is 2 or more, l × m1 R 1 may be the same or different from each other; when at least one of l and m2 is 2 or more, l × m2 R 2 may be the same or different from each other; when at least one of l and n1 is 2 or more, l×n1 p1s may be the same or different from each other; when at least one of l and n2 is 2 or more, l×n2 p2s may be the same or different from each other. The present invention provides a method for producing a copolymer, which produces a copolymer represented by the following formula (i.e., copolymer (1)):

[0089] The production method of this embodiment is a method for producing the above-mentioned copolymer (1). First, the raw material compounds used in the production method of this embodiment will be described.

[0090] <Compound (11)> The compound (11) is represented by the general formula (11). The compound (11) is a raw material compound for forming the polyester skeleton and a part of the polyamide skeleton in the copolymer (1).

[0091] m1 and m in general formula (11) 2、 R 1 , R 2 , R 3 , p1 and p2 are respectively m1 and m 2、 R 1 , R 2 , R 3, p1 and p2, and the preferred embodiments thereof are also the same as those in the case of the general formula (1). Therefore, further explanation of these symbols will be omitted here.

[0092] The compound (11) may be one in which the amino group forms a salt. Examples of salts of compound (11) include salts formed by reaction with inorganic acids, such as hydrochlorides, sulfates, and nitrates.

[0093] <Compound (12)> The compound (12) is represented by the general formula (12). The compound (12) is a raw material compound for forming the polyamide skeleton in the copolymer (1).

[0094] n1, n2, p1, p2 and X in the general formula (12) 1 respectively represent n1, n2, p1, p2 and X in the general formula (1). 1 is the same as n1-1 is 0 or more, and when n1-1 is 2 or more (n1 is 3 or more), the n1-1 p1s may be the same or different, and the combination of the n1-1 p1s is not particularly limited. n2-1 is 0 or more, and when n2-1 is 2 or more (n2 is 3 or more), the n2-1 p2s may be the same or different, and the combination of the n2-1 p2s is not particularly limited. n1, n2, p1, p2 and X in the general formula (12) 1 The preferred embodiments of are the same as those of the general formula (1). Therefore, further explanation of these symbols will be omitted hereinafter. Next, various conditions in the manufacturing method of this embodiment will be described.

[0095] <Manufacturing conditions> In the production method of this embodiment, copolymer (1) is obtained by reacting compound (11) with compound (12). This reaction is an amidation reaction that forms an amide bond between compound (11) and compound (12).

[0096] The compound (11) and the compound (12) used in the reaction may each be one kind or two or more kinds. When two or more kinds are used, the combination and ratio thereof can be arbitrarily selected depending on the purpose. From the viewpoint of easy adjustment of the properties of the copolymer (1), it is preferable to use a compound (11) containing R 1 , R 2 , R 3 , p1 and p2 are the same, and as compound (12), p1, p2 and X 1 It is preferable to use compounds in which p1 and p2 are the same, and it is more preferable to use compounds (11) and (12) in which p1 and p2 are the same.

[0097] During the reaction, the molar ratio of [amount (mol) of compound (11)]:[amount (mol) of compound (12)] is preferably 60:40 to 40:60, more preferably 55:45 to 45:55, and particularly preferably 50:50. The closer the molar ratio is to 50:50, the more efficiently and in higher yield the copolymer (1) can be obtained.

[0098] The reaction is preferably carried out in the presence of a solvent. The solvent is preferably one that can dissolve both compound (11) and compound (12), and examples of such solvents include amides such as N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), and N,N-dimethylacetamide (DMAc). The solvent used in the reaction may be one type only, or two or more types. When two or more types are used, the combination and ratio thereof can be selected arbitrarily depending on the purpose.

[0099] When the reaction is carried out in the presence of a solvent, it is preferable to carry out the reaction using a salt in order to improve the solubility of compound (12) in the reaction solution, thereby improving the reaction rate. The salt is preferably an inorganic salt. Examples of the inorganic salt include lithium salts (more specifically, lithium halides) such as lithium chloride (LiCl), lithium bromide (LiBr), and lithium iodide (LiI); and calcium salts such as calcium chloride. The salt used in the reaction may be one type only, or two or more types. When two or more types are used, the combination and ratio thereof can be selected arbitrarily depending on the purpose. The amount of salt used is preferably an amount such that the concentration of salt relative to the solvent ([amount of salt used (g)] / [amount of solvent used (L)]) is 10 to 200 g / L.

[0100] When reacting the compound (11) with the compound (12), it is preferable to use a condensing agent, since this improves the reaction rate. The condensing agent may be a known one, and specific examples thereof include carbodiimide compounds (compounds having a carbodiimide skeleton (-N=C=N-)), compounds other than carbodiimide compounds that can activate a carboxy group (-C(=O)-OH), and the like.

[0101] Examples of the carbodiimide compounds include N,N'-dicyclohexylcarbodiimide (DCC), N,N'-diisopropylcarbodiimide (DIPC), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (EDC) and its hydrochloride (EDC·HCl). Examples of compounds capable of activating a carboxy group other than the carbodiimide compounds include carbonyldiimidazole (CDI), N-hydroxysuccinimide (HOSu), 1-hydroxybenzotriazole (HOBt), 1-hydroxy-7-azabenzotriazole (HOAt), ethyl 2-cyano-2-(hydroxyimino)acetate (Oxyma), 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (HATU), and 1-[bis(dimethylamino)methylene]-1H-benzotriazolium 3-oxide hexafluorophosphate (HATU). hexafluorophosphate (HBTU), 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide tetrafluoroborate (TATU), 1-[bis(dimethylamino)methylene]-1H-benzotriazolium 3-oxide tetrafluoroborate (TBTU), (1-cyano-2-ethoxy-2-oxoethylideneaminooxy)dimethylaminomorpholinocarbenium hexafluorophosphate (COMU), 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM), and the like.

[0102] The condensing agent used in the reaction may be one type only, or two or more types may be used. When two or more types are used, the combination and ratio thereof can be selected arbitrarily depending on the purpose.

[0103] The amount of the condensing agent used is preferably 1 to 5 times, and may be, for example, 1.5 to 4 times, the molar amount of the carboxy groups in the compound (12).

[0104] When one or more of the carbodiimide compounds are used in the reaction, it is preferable to use one or more compounds other than the carbodiimide compounds that can activate carboxy groups in combination. The use of these condensing agents in combination further improves the reaction rate. When these condensing agents are used in combination, the amount of the compound capable of activating a carboxy group other than the carbodiimide-based compound is preferably 0.2 to 1.5 times by mole, and may be, for example, 0.4 to 1.0 times by mole, relative to the amount of the carbodiimide-based compound used.

[0105] The reaction temperature during the reaction of compound (11) with compound (12) is preferably 0 to 150°C, more preferably 40 to 80°C. The reaction time of the compound (11) and the compound (12) is preferably 5 to 36 hours, more preferably 10 to 24 hours.

[0106] Compound (11) may be produced from a compound represented by the following general formula (13) (sometimes referred to herein as "compound (13)") in which the amino group is protected with a protecting group. In this case, for example, compound (11) is obtained by deprotecting compound (13), and the reaction mixture is then post-treated as necessary. Thereafter, compound (11) may be isolated from the reaction mixture or the post-treatment product and subjected to a reaction with compound (12), or compound (11) may be directly subjected to a reaction with compound (12). When compound (11) is isolated, it can be isolated by a known method.

[0107] [ka] (In the formula, G 1 and G 2 are each independently a protecting group; m1, m2, R 1 , R 2 , R 3 , p1 and p2 are the same as above.)

[0108] In general formula (13), G 1 and G 2 are each independently a protecting group. 1 and the protecting group in G 2The protecting groups in may be the same or different from each other. In terms of easier production of compound (13), 1 and G 2 are preferably the same as each other.

[0109] G 1 and G 2 The protecting group in the formula (I) may be a known protecting group, and specific examples thereof include groups that can be removed under acidic conditions, such as a tert-butoxycarbonyl group (Boc group).

[0110] The compound (13) can be deprotected (protective group removed) by a known method. For example, deprotection under acidic conditions can be carried out by adding an acid (strong acid) dissolved in an organic solvent such as hydrogen chloride dissolved in ethyl acetate, hydrogen chloride dissolved in 1,4-dioxane, or trifluoroacetic acid dissolved in dichloromethane to compound (13). The reaction temperature during the deprotection may be, for example, 10 to 35°C, or may be room temperature. The reaction temperature during the deprotection may be, for example, 0.5 to 10 hours, or may be 0.5 to 5 hours.

[0111] In this specification, "room temperature" means a temperature that is neither particularly cold nor hot, that is, an ordinary temperature, and examples thereof include temperatures of 15 to 25°C.

[0112] After the deprotection reaction under acidic conditions, the amino group in compound (11) usually forms a salt with an acid. Therefore, for example, the salt is treated with an aqueous base or directly with a base to form an amino group, thereby obtaining compound (11).

[0113] Whether or not the base is used as an aqueous solution, the base may be either an inorganic base or an organic base. Examples of the inorganic base include sodium hydrogen carbonate. Examples of the organic base include aliphatic amines such as triethylamine and N,N-diisopropylethylamine; and aromatic amines such as pyridine, 2,6-lutidine (also known as 2,6-dimethylpyridine), 2,4,6-collidine (also known as 2,4,6-trimethylpyridine), and 4-dimethylaminopyridine (DMAP). Regardless of whether the base is used as an aqueous solution or not, the base is preferably an organic base in that it has high solubility in the reaction liquid. The base used in the reaction may be one type only, or two or more types. When two or more types are used, the combination and ratio thereof can be selected arbitrarily depending on the purpose.

[0114] The amount of base used is preferably 0.5 to 5 times the molar amount of the acid to be treated, and may be, for example, 0.5 to 2 times the molar amount.

[0115] After the reaction of compound (11) with compound (12), for example, water is added to the reaction solution, or the reaction solution is added to water, and then, if necessary, a salt such as potassium carbonate (K2CO3) or sodium sulfate (Na2SO4) is added to the resulting mixture. The addition of the salt promotes the precipitation of the target product (copolymer (1)). Next, the insoluble matter (precipitate) is recovered, and the recovered insoluble matter is further washed with water and, if necessary, dried. This process is repeated once or twice or more times, and the final washed product is dried to obtain copolymer (1).

[0116] The washed objects may be dried under normal pressure or under reduced pressure (vacuum drying). The washed objects may be dried at room temperature or by heating (heat drying). The temperature during heat drying may be, for example, 40 to 80°C. The pressure and temperature during drying of the washed objects may be combined as desired depending on the purpose. The resulting copolymer (1) may be further purified by repeatedly washing with water and drying at least once.

[0117] The structure of the copolymer (1) can be confirmed by known techniques such as nuclear magnetic resonance (NMR) spectroscopy, mass spectroscopy (MS), and infrared spectroscopy (IR).

[0118] Compound (13) can be produced by reacting a compound represented by the following general formula (15) (sometimes referred to herein as "compound (15)"), a compound represented by the following general formula (16a1) (sometimes referred to herein as "compound (16a1)"), and a compound represented by the following general formula (16a2) (sometimes referred to herein as "compound (16a2)").

[0119] [ka] (In the formula, m1, m2, R 1 , R 2 , R 3 , p1, p2, G 1 and G 2 is the same as above.)

[0120] Compound (16a1) and compound (16a2) may be the same as or different from each other.

[0121] The above reactions, i.e., the esterification reaction between compound (15) and compound (16a1) and the esterification reaction between compound (15) and compound (16a2), can be carried out by known methods. For example, compound (13) can be obtained by dehydration condensation of these compounds using a condensing agent. Examples of the condensing agent used in this reaction include the same condensing agents as those used in the reaction between compound (11) and compound (12) described above.

[0122] Compound (15) can be produced by reacting a compound represented by the following general formula (17) (sometimes referred to herein as "compound (17)") with either or both of a compound represented by the following general formula (1811) (sometimes referred to herein as "compound (1811)") or a compound represented by the following general formula (1812) (sometimes referred to herein as "compound (1812)") and a compound represented by the following general formula (1821) (sometimes referred to herein as "compound (1821)") or a compound represented by the following general formula (1822) (sometimes referred to herein as "compound (1822)"). When neither compound (1811) nor compound (1812) is used, m1 is 0, and when neither compound (1821) nor compound (1822) is used, m2 is 0.

[0123] [ka] (In the formula, R 1 , R 2 , R 3 , m1 and m2 are the same as above.)

[0124] The compound (1811) and the compound (1821) may be the same as or different from each other. Similarly, compound (1812) and compound (1822) may be the same as or different from each other.

[0125] The above reactions, i.e., the esterification reaction between compound (17) and compound (1811) or compound (1812), and the esterification reaction between compound (17) and compound (1821) or compound (1822), can be carried out by known methods. For example, compound (15) can be obtained by dehydration condensation of these compounds in the presence of a catalyst. Examples of catalysts used in this reaction include known catalysts such as tin(II) 2-ethylhexanoate and tin(II) octoate.

[0126] Compound (12) can be produced by using a compound represented by the following general formula (19) (sometimes referred to herein as "compound (19)"), activating the carboxy group (-C(=O)-OH) therein, and then reacting this activated compound with either or both of a compound represented by the following general formula (16b1) (sometimes referred to herein as "compound (16b1)") and a compound represented by the following general formula (16b2) (sometimes referred to herein as "compound (16b2)"). When compound (16b1) is not used, n1 is 1, and when compound (16b2) is not used, n2 is 1.

[0127] [ka] (In the formula, X 1 , n1, n2, p1, and p2 are the same as above.)

[0128] Compound (16b1) and compound (16b2) may be the same as or different from each other.

[0129] Examples of compounds obtained by activating the above-mentioned compound (19) include carboxylic acid chlorides having a structure in which the carboxy group in compound (19) is converted to a chlorocarbonyl group (—C(═O)—Cl). The carboxylic acid chloride of compound (12) can be obtained by a known method, for example, by reacting compound (12) with thionyl chloride (SOCl2).

[0130] The above-mentioned reactions, i.e., the amidation reaction between the activated compound (19) and compound (16b1), and the amidation reaction between the activated compound (19) and compound (16b2), can be carried out by known methods. The reactions proceed via a compound represented by the following general formula (14) (sometimes referred to as "compound (14)" in this specification) as a reaction product.

[0131] [ka] (In the formula, X 1 , p1 and p2 are the same as above.)

[0132] <<Film>> A film according to one embodiment of the present invention contains the copolymer according to one embodiment of the present invention described above. The film of this embodiment contains copolymer (1), which gives it high mechanical strength and excellent film properties. Furthermore, by adjusting the type of copolymer (1), the film of this embodiment can have high transparency and moldability. The film of this embodiment can be molded to obtain a molded article.

[0133] The mechanical strength of the film of this embodiment can be evaluated, for example, by preparing a dumbbell-shaped No. 7 test piece described in JIS K 6251:2017 using the film having a thickness of 90 to 110 μm, and conducting a tensile test using the test piece in accordance with JIS K 6251:2017 at a temperature of 23°C and a tensile speed of 10 mm / min, based on the measured values ​​of maximum stress (MPa) and elongation at break (%).

[0134] In the film of this embodiment, the maximum stress can be, for example, any one of 10 MPa or more, 15 MPa or more, 20 MPa or more, 25 MPa or more, and 30 MPa or more. On the other hand, the film having a maximum stress of 50 MPa or less can be more easily achieved.

[0135] In the film of this embodiment, the breaking elongation can be, for example, any one of 3% or more, 30% or more, 120% or more, 210% or more, and 300% or more. On the other hand, the film having a breaking elongation of 400% or less can be more easily achieved.

[0136] The film of the present embodiment is suitable as, for example, a protective film, a packaging film, etc. Furthermore, a molded article obtained by molding the film of the present embodiment is suitable as a packaging material having a storage section for storing an object to be packaged.

[0137] The film of this embodiment can be produced using a composition containing copolymer (1). For example, the film can be formed by applying a liquid composition containing the copolymer (1) and a solvent to the surface of an object to be formed into a film, and then drying (removing the solvent).

[0138] Examples of the solvent contained in the composition include amides such as N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), and N,N-dimethylacetamide (DMAc); organic acids that are liquid at room temperature such as formic acid; and fluoroalcohols such as 1,1,1,3,3,3-hexafluoro-2-propanol.

[0139] The film and composition may or may not contain other components other than the above-mentioned solvents, in addition to the copolymer (1). Examples of the other components include various additives known in the field of films, such as antioxidants, antistatic agents, and antiblocking agents.

[0140] The copolymer (1) and the other components contained in the film may each be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof can be selected arbitrarily depending on the purpose. The copolymer (1), the solvent, and the other components contained in the composition may each be one kind or two or more kinds. When two or more kinds are contained, the combination and ratio thereof can be selected arbitrarily depending on the purpose.

[0141] In the film, the ratio of the content of copolymer (1) to the total mass of the film ([content of copolymer (1) in film (parts by mass)] / [total mass of film (parts by mass)]×100) is preferably 60% by mass or more, more preferably 80% by mass or more, and may be, for example, any one of 90% by mass or more, 95% by mass or more, and 98% by mass or more. The higher the ratio, the greater the effect obtained by containing copolymer (1) in the film. On the other hand, the proportion is 100% by mass or less. The ratio is usually the same as the ratio of the content (parts by mass) of copolymer (1) to the total content (parts by mass) of components in the composition that do not vaporize at room temperature ([content (parts by mass) of copolymer (1) in the composition)] / [total content (parts by mass) of components in the composition that do not vaporize at room temperature]×100).

[0142] When the composition contains a solvent, the content of the solvent in the composition is preferably 0.5 to 10 L per 1 kg of the content of the copolymer (1).

[0143] The composition can be applied, for example, by pouring and spreading it on the surface of the object to form a film; or by using various coaters such as a spin coater, air knife coater, curtain coater, die coater, blade coater, roll coater, gate roll coater, or bar coater.

[0144] The drying conditions for the composition are not particularly limited, but when the composition contains the solvent, it is preferable to heat-dry the composition. The composition containing the solvent is preferably heat-dried under conditions of, for example, 50 to 80°C and 1 to 180 minutes.

[0145] The composition is obtained by blending the copolymer (1), the solvent as required, and the other components as required. The temperature and time for adding and mixing each component are not particularly limited as long as the components do not deteriorate, and may be adjusted appropriately. The temperature is preferably 15 to 35°C, and may be room temperature. [Example]

[0146] The present invention will be described in more detail below with reference to specific examples, although the present invention is not limited to the examples shown below.

[0147] In the following Preparation Examples and Examples, 1 H-NMR was measured using a nuclear magnetic resonance spectrometer "Avance III HD 600 spectrometer" manufactured by Bruker. In the production of compound (15) in Production Examples 1 to 3, in the production of compound (13) in Production Examples 4 to 6, and in the production of compound (14) in Production Example 7, 1 When measuring H-NMR, a sample of the target substance (10 mg) was dissolved in deuterated chloroform (CDCl3, manufactured by Kanto Chemical Co., Ltd., deuteration rate 99.8% or more, containing 0.03 vol% tetramethylsilane) (1 mL) to prepare a measurement sample. 1 When measuring H-NMR, a measurement sample was prepared by dissolving a target sample (10 mg) in deuterated methanol (CD3OD, manufactured by Kanto Chemical Co., Ltd., deuteration rate 99.8%) (1 mL) containing calcium chloride at a concentration of 10 wt / v% (mass / volume%). 1 When measuring H-NMR, a measurement sample was prepared by dissolving a target sample (10 mg) in deuterated trifluoroacetic acid (CF3COOD, manufactured by Kanto Chemical Co., Inc., deuteration rate 99.8%) (1 mL).

[0148] In the following examples, gel permeation chromatography (GPC) measurements were carried out by the following method. Specifically, 1,1,1,3,3,3-hexafluoro-2-propanol with triethylamine added to a concentration of 0.05 M was used as the eluent. A Flom FG-32 degasser was used, and dissolved gases in the eluent were removed under reduced pressure (23.0 kPa). A JASCO PU-4185 pump was used, and the eluent flow rate was set to 0.15 mL / min. A JASCO AS-4150 autosampler was used, with a sample loop capacity of 20 μL. The sample concentration was 1 mg / mL. A JASCO CO-4060 column oven was used, and the heating temperature was set to 40°C. A JASCO RI-4035 detector was used. Showa Denko LF-404 and LF-G columns were used for GPC. The molecular weight of the sample was calculated from a calibration curve prepared using polymethyl methacrylate standard samples (manufactured by Showa Denko KK, molecular weights: 7290, 20100, 72000, 224000, 539000, 1020000).

[0149] <<Manufacturing raw material compounds>> <Production of compound (15)> Compounds (15)-101, (15)-102 and (15)-103 were prepared according to the following procedure.

[0150] [ka]

[0151] [Manufacturing Example 1] 1,4-Butanediol (9.01 g, 100 mmol, Fujifilm Wako Pure Chemical Industries, Ltd.), tin(II) 2-ethylhexanoate (4.05 g, 10 mmol, Tokyo Chemical Industry Co., Ltd.), and ε-caprolactone (114 g, 1000 mmol, Tokyo Chemical Industry Co., Ltd.) were added to a 300 mL recovery flask, heated to 100 °C, and stirred for 18 hours. After stirring, the solution was washed twice with hexane (400 mL) to obtain a white precipitate. The white precipitate was collected and dried under reduced pressure at room temperature to obtain compound (15)-101 (yield: 119 g, 97%). The obtained compound (15)-101 1 The results of H-NMR (600 MHz, CDCl3) analysis are shown in Figure 1. From the peak area ratio of 8 and 3 in Figure 1, the average degree of polymerization (m1 + m2) was calculated to be 10. The reagents and devices used in Production Examples 2 and 3 described below are the same as those used here unless otherwise specified.

[0152] [Manufacturing Example 2] 1,4-Butanediol (4.51 g, 50 mmol), tin(II) 2-ethylhexanoate (2.03 g, 5.0 mmol), and ε-caprolactone (114 g, 1000 mmol) were added to a 200 mL recovery flask, heated to 100 °C, and stirred for 18 hours. After stirring, the solution was washed twice with hexane (400 mL) to obtain a white precipitate. The white precipitate was collected and dried under reduced pressure at room temperature to obtain compound (15)-102 (yield: 117 g, 99%). The obtained compound (15)-102 1 From the results of analysis by 1 H-NMR (600 MHz, CDCl 3 ), the average degree of polymerization (m1+m2) was calculated to be 20 using the same method as in Production Example 1.

[0153] [Manufacturing Example 3] 1,4-Butanediol (2.25 g, 25 mmol), tin(II) 2-ethylhexanoate (1.01 g, 2.5 mmol), and ε-caprolactone (114 g, 1000 mmol) were added to a 300 mL recovery flask, heated to 100 °C, and stirred for 18 hours. After stirring, the solution was washed twice with hexane (400 mL) to obtain a white precipitate. The white precipitate was collected and dried under reduced pressure at room temperature to obtain compound (15)-103 (yield: 115 g, 99%). The obtained compound (15)-103 1 From the results of analysis by 1 H-NMR (600 MHz, CDCl 3 ), the average degree of polymerization (m1+m2) was calculated to be 37 using the same method as in Production Example 1.

[0154] <Production of compound (13)> Compounds (13)-101, (13)-102 and (13)-103 were prepared according to the following procedure.

[0155] [ka]

[0156] [Manufacturing Example 4] Compound (15)-101 (116 g, 92 mmol), N-Boc-4-aminobutyric acid (41.1 g, 202 mmol, Combi-Blocks), 4-dimethylaminopyridine (7.19 g, 59 mmol, Fujifilm Wako Pure Chemical Industries, Ltd.), and dichloromethane (466 mL) were added to a 1 L recovery flask and cooled in an ice bath. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (84.7 g, 442 mmol, Apollo Scientific) was added. The flask was removed from the ice bath and stirred at room temperature for an additional 3.5 hours. The resulting reaction solution was sequentially distributed and washed with 1 M hydrochloric acid (250 mL), a mixture of 1 M hydrochloric acid (250 mL) and methanol (75 mL), and a mixture of saturated saline (250 mL) and methanol (75 mL). The organic layer was collected, dried over magnesium sulfate, concentrated under reduced pressure using an evaporator, and dried under reduced pressure at 60°C overnight to obtain compound (13)-101 (yield: 145 g, 96%). The obtained compound (13)-101 1 The results of H-NMR (600 MHz, CDCl3) analysis are shown in Figure 2. From the peak area ratio of 2 and 7 to 10 in Figure 2, the average degree of polymerization (m1 + m2) was calculated to be 11. The reagents and devices used in Production Examples 5 and 6 described below are the same as those used here unless otherwise specified.

[0157] [Manufacturing Example 5] Compound (15)-102 (116 g, 48 mmol), N-Boc-4-aminobutyric acid (21.5 g, 106 mmol), 4-dimethylaminopyridine (3.75 g, 31 mmol), and dichloromethane (464 mL) were added to a 1 L recovery flask and cooled in an ice bath. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (44.2 g, 230 mmol) was added. After stirring for 30 minutes, the flask was removed from the ice bath and stirred at room temperature for an additional 3.5 hours. The resulting reaction solution was concentrated under reduced pressure using an evaporator and further dried under reduced pressure at 35 °C overnight. The resulting dried product was washed four times with purified water (500 mL) and dried under reduced pressure at 40 °C to obtain compound (13)-102 (yield: 126 g, 94%). The obtained compound (13)-102 1 From the results of analysis by 1 H-NMR (600 MHz, CDCl 3 ), the average degree of polymerization (m1+m2) was calculated to be 20 using the same method as in Production Example 4.

[0158] [Manufacturing Example 6] Compound (15)-103 (113 g, 27 mmol), N-Boc-4-aminobutyric acid (11.8 g, 58 mmol), 4-dimethylaminopyridine (2.07 g, 17 mmol), and dichloromethane (452 ​​mL) were added to a 1 L recovery flask and cooled in an ice bath. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (24.4 g, 127 mmol) was added. The flask was removed from the ice bath and stirred at room temperature for an additional 3 hours. The resulting reaction solution was concentrated under reduced pressure using an evaporator and further dried under reduced pressure at 35 °C overnight. The resulting dried product was washed four times with pure water (500 mL) and dried under reduced pressure at 40 °C to obtain compound (13)-103 (yield: 123 g, 100%). The obtained compound (13)-103 1 From the results of analysis by 1 H-NMR (600 MHz, CDCl 3 ), the average degree of polymerization (m1+m2) was calculated to be 38 using the same method as in Production Example 4.

[0159] <Production of compound (12)> Compounds (12)-101, (12)-102, and (12)-103 were prepared via 4,4'-oxybis(benzoyl chloride) and compound (14)-101 according to the procedure shown below.

[0160] [ka]

[0161] [Manufacturing Example 7] A 500 mL recovery flask was charged with 4,4'-oxybisbenzoic acid (104 g, 404 mmol, BLD Pharmatech), dichloromethane (150 mL), thionyl chloride (147 mL, 2020 mmol, FUJIFILM Wako Pure Chemical Industries, Ltd.), and dimethylformamide (0.50 g, 6.8 mmol, FUJIFILM Wako Pure Chemical Industries, Ltd.). The resulting mixture was heated to 50 °C and stirred under reflux for 7 hours. The flask was then fitted with a vacuum line, and the reaction mixture was dried under reduced pressure. The resulting dried product (4,4'-oxybis(benzoyl chloride), 120 g, 101% yield) was used directly in the next reaction without further purification. The obtained 4,4'-oxybis(benzoyl chloride) 1 The results of the H-NMR analysis are shown below. 1 H-NMR (600MHz, CDCl3) δ8.34-8.05(m, 2H),7.34-7.03(m, 2H).

[0162] A 1-L recovery flask was charged with 4,4'-oxybis(benzoyl chloride) (88.5 g, 300 mmol), pyridine (97 mL, 1200 mmol, Fujifilm Wako Pure Chemical Industries, Ltd.), and 2-pyrrolidone (300 mL, Fujifilm Wako Pure Chemical Industries, Ltd.). The resulting mixture was heated to 90 °C in an oil bath and stirred for 3 hours. The flask was then removed from the oil bath and allowed to cool. Dichloromethane (1.0 L) was then added to the reaction mixture. The resulting solution was washed twice with 2 M hydrochloric acid (500 mL) and four times with saturated aqueous sodium bicarbonate (500 mL). The mixture was then dried over magnesium sulfate and concentrated under reduced pressure using an evaporator. Hexane (300 mL) was added to the concentrate, and the resulting solid was collected and dried under vacuum at 45 °C to obtain compound (14)-101 (yield: 98.3 g, 84%). The obtained compound (14)-101 1 The results of the H-NMR analysis are shown below. 1 H-NMR (600MHz, CDCl3) δ7.68-7.66(m, 2H), 7.08-7.06(m, 2H), 3.98(t, J=7.0Hz, 2H), 2.64(t, J=8.1Hz, 2H), 2.20-2.15(m, 2H).

[0163] 2-Pyrrolidone (119 g, 1400 mmol, Fujifilm Wako Pure Chemical Industries, Ltd.) and lithium methoxide (2.13 g, 56 mmol, Tokyo Chemical Industry Co., Ltd.) were added to a 1 L recovery flask and dried under reduced pressure at 80 °C for 3 hours. The resulting reaction solution was cooled to 30 °C, and a solution of compound (14)-101 (54.7 g, 140 mmol) dissolved in dichloromethane (100 mL) was added. A vacuum line was attached to the reaction system, and the dichloromethane was distilled off. The reaction system was heated at 30 °C for 24 hours under reduced pressure to obtain a solid. Next, 6 M hydrochloric acid (520 mL) was added and stirred overnight to dissolve the solid. The resulting solution was then added dropwise to a mixture of acetone (4.4 L) and N,N-diisopropylethylamine (88 mL) and stirred for 6 hours. As a result, a solid precipitated. The solid was collected by decantation and washed twice with acetone (900 mL), four times with acetone (500 mL), twice with a mixture of acetone (450 mL) and purified water (50 mL), once with purified water (500 mL), and twice with acetone (500 mL). The washed solid was collected by filtration and dried under reduced pressure at 45 °C to give compound (12)-101 (yield: 109 g, 70%). The obtained compound (12)-101 1 The results of H-NMR (600 MHz, CD3OD (containing 10 wt / v% calcium chloride)) analysis are shown in Figure 3. From the peak area ratio of 1 and 5 in Figure 3, the average degree of polymerization (n1 + n2 - 2) was calculated to be 11. The reagents and devices used in Production Examples 8 and 9 described below are the same as those used here unless otherwise specified.

[0164] [Manufacturing Example 8] 2-Pyrrolidone (143 g, 1680 mmol) and lithium methoxide (2.55 g, 67 mmol) were added to a 1 L recovery flask and dried under reduced pressure at 80 °C for 3.5 hours. The resulting reaction solution was cooled to 30 °C, and a solution of compound (14)-101 (32.8 g, 84 mmol) dissolved in dichloromethane (66 mL) was added. A vacuum line was attached to the reaction system, and the dichloromethane was distilled off. The reaction system was heated at 30 °C for 24 hours under reduced pressure to obtain a solid. Next, 6 M hydrochloric acid (530 mL) was added and stirred overnight to dissolve the solid. The resulting solution was then added dropwise to a mixture of acetone (4.4 L) and N,N-diisopropylethylamine (440 mL) and stirred for a while. As a result, a solid precipitated. The solid matter was collected by filtration, washed once with acetone (1.0 L) and once with purified water (500 mL), and dried under reduced pressure at 60° C. The dried matter was washed twice with purified water (500 mL) and once with acetone (500 mL), and dried under reduced pressure at 45° C. to obtain compound (12)-102 (yield: 128 g, 78%). The obtained compound (12)-102 1 From the results of H-NMR (600 MHz, CD3OD (containing 10 wt / v % calcium chloride)), the average degree of polymerization (n1+n2−2) was calculated to be 18 using the same method as in Production Example 7.

[0165] [Manufacturing Example 9] 2-Pyrrolidone (157 g, 1840 mmol) and lithium methoxide (2.79 g, 74 mmol) were added to a 1 L recovery flask and dried under reduced pressure at 80 °C for 3 hours. The resulting reaction solution was cooled to 30 °C, and a solution of compound (14)-101 (18.0 g, 46 mmol) dissolved in dichloromethane (36 mL) was added. A vacuum line was attached to the reaction system, and the dichloromethane was distilled off. The reaction system was then heated at 30 °C under reduced pressure for 24 hours to obtain a solid. Next, 6 M hydrochloric acid (530 mL) was added and the mixture was stirred overnight to dissolve the solid. The resulting solution was then added dropwise to a mixture of acetone (4.4 L) and N,N-diisopropylethylamine (440 mL). As a result, a solid precipitated. The solid was collected by filtration, washed once with acetone (1.0 L), and dried under reduced pressure at 60 °C. The dried product was washed twice with pure water (500 mL) and once with acetone (500 mL), followed by drying under reduced pressure at 60 °C to obtain compound (12)-103 (yield: 112 g, 67%). The obtained compound (12)-103 1 From the results of H-NMR (600 MHz, CD3OD (containing 10 wt / v % calcium chloride)), the average degree of polymerization (n1+n2−2) was calculated to be 36 using the same method as in Production Example 7.

[0166] <<Production of Copolymer (1)>> According to the procedure shown below, compounds (11)-101 to (11)-103 were produced using compounds (13)-101 to (13)-103, and these compounds (11)-101 to (11)-103 were reacted with compounds (12)-101 to (12)-103 to produce copolymers (1)-101 to (1)-109.

[0167] [ka]

[0168] [Example 1] Compound (13)-101 (33.7 g, 20 mmol), trifluoroacetic acid (50.2 g, 440 mmol, Fujifilm Wako Pure Chemical Industries, Ltd.), and dichloromethane (34 mL) were added to a 500 mL recovery flask and stirred at room temperature for 1 hour to remove the Boc group in compound (13)-101, resulting in deprotection and obtaining compound (11)-101. N,N-Dimethylacetamide (173 g, Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the resulting reaction solution, which was then concentrated under reduced pressure at 35°C to remove dichloromethane and decomposition products of the Boc group. To the solution after vacuum concentration, N,N-diisopropylethylamine (56.9 g, 440 mmol, Tokyo Chemical Industry Co., Ltd.) and lithium chloride (17.3 g, 407 mmol, Fujifilm Wako Pure Chemical Industries, Ltd.) were added, and the mixture was heated to 70 °C. Compound (12)-101 (23.8 g, 20 mmol) was then added. The mixture was heated to 120 °C to dissolve the insoluble matter, then cooled to 45 °C. 1-Hydroxy-7-azabenzotriazole (5.99 g, 44 mmol, Tokyo Chemical Industry Co., Ltd.) and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (16.9 g, 88 mmol, Apollo Scientific) were added and stirred for 20 hours. The resulting reaction solution was added dropwise to purified water (500 mL) to obtain a rubbery precipitate. The precipitate was collected by filtration and washed once with purified water (500 mL). The obtained precipitate was freeze-pulverized using liquid nitrogen, washed once again with pure water (500 mL), and dried under reduced pressure at 60°C to obtain copolymer (1)-101 (yield: 50.1 g, 95%). The obtained copolymer (1)-101 1 The results of H-NMR (600 MHz, CF3COOD) analysis are shown in Figure 4. From the peak area ratio of 2 and 7 to 3 in Figure 4, the average degree of polymerization (m1 + m2) in the polyester skeleton was calculated to be 11, and from the peak area ratio of a to d, the average degree of polymerization (n1 + n2) in the polyamide skeleton was calculated to be 13. Furthermore, gel permeation chromatography (GPC) measurement revealed that the number average molecular weight (Mn) was 10.9 × 10 3 , weight average molecular weight (Mw) is 32.0 × 10 3Then, from the average degree of polymerization (m1 + m2), the average degree of polymerization (n1 + n2) and the number average molecular weight (Mn), l was calculated to be 4. The reagents and devices used in Examples 2 to 9 described below are the same as those used here unless otherwise specified.

[0169] [Example 2] Compound (13)-101 (25.3 g, 15 mmol), trifluoroacetic acid (37.7 g, 331 mmol), and dichloromethane (25 mL) were added to a 500 mL recovery flask and stirred at room temperature for 2 hours to remove the Boc group from compound (13)-101, resulting in deprotection and obtaining compound (11)-101. N,N-dimethylacetamide (75.9 g) containing 5% by mass of lithium chloride was added to the resulting reaction solution, which was then concentrated under reduced pressure at 45°C to remove dichloromethane and decomposition products of the Boc group. To the solution after vacuum concentration, N,N-diisopropylethylamine (42.7 g, 331 mmol) was added, and the mixture was heated to 70 °C. A solution obtained by dissolving compound (12)-102 (27.0 g, 15 mmol) in N,N-dimethylacetamide (81.0 g) containing 5% by mass of lithium chloride at 70 °C was added. As a result, a solid precipitated. The reaction solution containing this precipitate was then transferred to a 1 L flask, and N,N-dimethylacetamide (261 g) containing 5% by mass of lithium chloride was added. The mixture was heated to 70 °C to obtain a homogeneous solution. 1-Hydroxy-7-azabenzotriazole (4.49 g, 33 mmol) and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (12.7 g, 66 mmol) were added to the resulting solution, and the mixture was stirred for 18 hours. The resulting reaction solution was added dropwise to pure water (1.4 L) to precipitate a solid, which was then collected by filtration and washed twice with pure water (500 mL). The resulting solid was dried under reduced pressure at 60°C to obtain copolymer (1)-102 (yield: 42.6 g, 88%). The obtained copolymer (1)-102 1From the results of H-NMR (600 MHz, CF3COOD) analysis, the average degree of polymerization (m1 + m2) in the polyester skeleton was calculated to be 10, and the average degree of polymerization (n1 + n2) in the polyamide skeleton was calculated to be 19, using the same method as in Example 1. Furthermore, GPC measurement revealed that the number average molecular weight (Mn) was 11.5 × 10 3 , weight average molecular weight (Mw) is 37.3 × 10 3 Then, from the average degree of polymerization (m1 + m2), the average degree of polymerization (n1 + n2) and the number average molecular weight (Mn), l was calculated to be 3.

[0170] [Example 3] Compound (13)-101 (16.9 g, 10 mmol), trifluoroacetic acid (25.2 g, 221 mmol), and dichloromethane (17 mL) were added to a 500 mL recovery flask and stirred at room temperature for 2 hours to remove the Boc group from compound (13)-101, resulting in deprotection and obtaining compound (11)-101. N,N-dimethylacetamide (50.6 g) containing 5% by mass of lithium chloride was added to the resulting reaction solution, which was then concentrated under reduced pressure at 45°C to remove dichloromethane and decomposition products of the Boc group. To the solution after vacuum concentration, N,N-diisopropylethylamine (28.5 g, 221 mmol) was added and the mixture was heated to 70 °C. A solution of compound (12)-103 (33.6 g, 10 mmol) dissolved in N,N-dimethylacetamide (234 g) containing 5% by mass of lithium chloride at 70 °C was added. As a result, a solid precipitated. The reaction solution containing this precipitate was then transferred to a 1 L flask, and N,N-dimethylacetamide (219 g) containing 5% by mass of lithium chloride was added. The mixture was heated to 70 °C to obtain a homogeneous solution. 1-Hydroxy-7-azabenzotriazole (3.00 g, 22 mmol) and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (8.44 g, 44 mmol) were added to the resulting solution, and the mixture was stirred for 18 hours. The resulting reaction solution was added dropwise to purified water (3.0 L) to precipitate a solid, which was then collected by filtration and washed twice with purified water (500 mL). The resulting solid was dried under reduced pressure at 60°C to obtain copolymer (1)-103 (yield: 41.2 g, 86%). The obtained copolymer (1)-103 1 From the results of H-NMR (600 MHz, CF3COOD) analysis, the average degree of polymerization (m1 + m2) in the polyester skeleton was calculated to be 12, and the average degree of polymerization (n1 + n2) in the polyamide skeleton was calculated to be 38, using the same method as in Example 1. Furthermore, GPC measurement revealed that the number average molecular weight (Mn) was 14.9 × 10 3 , weight average molecular weight (Mw) is 47.7 × 10 3 Then, from the average degree of polymerization (m1 + m2), the average degree of polymerization (n1 + n2) and the number average molecular weight (Mn), l was calculated to be 3.

[0171] [Example 4] Compound (13)-102 (34.9 g, 13 mmol), trifluoroacetic acid (52.1 g, 457 mmol), and dichloromethane (35 mL) were added to a 500 mL recovery flask and stirred at room temperature for 1.5 hours to remove the Boc group from compound (13)-102 and deprotect it, yielding compound (11)-102. N,N-dimethylacetamide (105 g) containing 5% by mass of lithium chloride was added to the resulting reaction solution, which was then concentrated under reduced pressure at 45 °C to remove the dichloromethane and decomposition products of the Boc group. N,N-diisopropylethylamine (59.1 g, 457 mmol) was added to the solution after vacuum concentration, and the temperature was raised to 70 °C. A solution obtained by dissolving compound (12)-101 (14.9 g, 13 mmol) in N,N-dimethylacetamide (44.6 g) containing 5% by mass of lithium chloride at 70 °C was then added. The resulting reaction solution was allowed to cool to 45°C, and 1-hydroxy-7-azabenzotriazole (3.74 g, 28 mmol) and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (10.5 g, 55 mmol) were added and stirred for 18 hours. The resulting reaction solution was added dropwise to pure water (500 mL), resulting in the precipitation of a solid. The solid was collected by filtration, washed twice with pure water (500 mL), and dried under reduced pressure at 60°C to obtain copolymer (1)-104 (yield: 45.5 g, 97%). The obtained copolymer (1)-104 1 From the results of H-NMR (600 MHz, CF3COOD) analysis, the average degree of polymerization (m1 + m2) in the polyester skeleton was calculated to be 20, and the average degree of polymerization (n1 + n2) in the polyamide skeleton was calculated to be 13, using the same method as in Example 1. Furthermore, GPC measurement revealed that the number average molecular weight (Mn) was 13.0 × 10 3 , weight average molecular weight (Mw) is 36.8 × 10 3 Then, from the average degree of polymerization (m1 + m2), the average degree of polymerization (n1 + n2) and the number average molecular weight (Mn), l was calculated to be 3.

[0172] [Example 5] Compound (13)-102 (30.7 g, 11 mmol), trifluoroacetic acid (46.2 g, 405 mmol), and dichloromethane (31 mL) were added to a 1 L recovery flask and stirred at room temperature for 1.5 hours to remove the Boc group from compound (13)-102 and deprotect it, yielding compound (11)-102. N,N-dimethylacetamide (92.1 g) containing 5% by mass of lithium chloride was added to the resulting reaction solution, which was then concentrated under reduced pressure at 45 °C to remove the dichloromethane and decomposition products of the Boc group. N,N-diisopropylethylamine (52.4 g, 405 mmol) was added to the solution after vacuum concentration, and the temperature was raised to 70 °C. A solution obtained by dissolving compound (12)-102 (19.8 g, 11 mmol) in N,N-dimethylacetamide (158 g) containing 5% by mass of lithium chloride at 70 °C was then added. The resulting reaction mixture was further added with N,N-dimethylacetamide (154 g) containing 5% by mass of lithium chloride, and the mixture was heated to 70 °C. 1-Hydroxy-7-azabenzotriazole (3.29 g, 24 mmol) and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (9.29 g, 48 mmol) were added and stirred for 18 hours. The resulting reaction mixture was added dropwise to purified water (2.5 L), and potassium carbonate (180 g) was added, resulting in the precipitation of a solid. The solid was collected by filtration, washed twice with purified water (500 mL), and dried under reduced pressure at 60 °C to obtain copolymer (1)-105 (yield: 35.0 g, 73%). The obtained copolymer (1)-105 1 From the results of H-NMR (600 MHz, CF3COOD) analysis, the average degree of polymerization (m1 + m2) in the polyester skeleton was calculated to be 21, and the average degree of polymerization (n1 + n2) in the polyamide skeleton was calculated to be 20, using the same method as in Example 1. Furthermore, GPC measurement revealed that the number average molecular weight (Mn) was 11.0 × 10 3 , weight average molecular weight (Mw) is 31.3 × 10 3 Then, from the average degree of polymerization (m1 + m2), the average degree of polymerization (n1 + n2) and the number average molecular weight (Mn), l was calculated to be 2.

[0173] [Example 6] Compound (13)-102 (5.58 g, 2.0 mmol), trifluoroacetic acid (8.34 g, 73 mmol), and dichloromethane (6 mL) were added to a 500 mL recovery flask and stirred at room temperature for 1 hour to remove the Boc group from compound (13)-102, resulting in deprotection and obtaining compound (11)-102. N,N-dimethylacetamide (16.7 g) containing 5% by mass of lithium chloride was added to the resulting reaction solution, which was then concentrated under reduced pressure at 45°C to remove dichloromethane and decomposition products of the Boc group. To the solution after vacuum concentration, N,N-diisopropylethylamine (9.46 g, 73 mmol) was added and the mixture was heated to 70 °C. A solution of compound (12)-103 (6.71 g, 2.0 mmol) dissolved in N,N-dimethylacetamide (53.7 g) containing 5% by mass of lithium chloride at 70 °C was added. 1-Hydroxy-7-azabenzotriazole (0.60 g, 4.4 mmol) and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (1.69 g, 8.8 mmol) were added to the resulting reaction solution, and the mixture was stirred for 18 hours. The resulting reaction solution was added dropwise to pure water (500 mL), resulting in the precipitation of a solid. The solid was collected by filtration and washed twice with pure water (300 mL). The obtained solid was freeze-pulverized using liquid nitrogen, washed again with pure water, and dried under reduced pressure at 60°C to obtain copolymer (1)-106 (yield: 9.70 g, 85%). The obtained copolymer (1)-106 1 From the results of H-NMR (600 MHz, CF3COOD) analysis, the average degree of polymerization (m1 + m2) in the polyester skeleton was calculated to be 19, and the average degree of polymerization (n1 + n2) in the polyamide skeleton was calculated to be 40, using the same method as in Example 1. Furthermore, GPC measurement revealed that the number average molecular weight (Mn) was 13.3 × 10 3 , weight average molecular weight (Mw) is 38.6 × 10 3 Then, from the average degree of polymerization (m1 + m2), the average degree of polymerization (n1 + n2) and the number average molecular weight (Mn), l was calculated to be 2.

[0174] [Example 7] Compound (13)-103 (40.5 g, 8.5 mmol), trifluoroacetic acid (60.3 g, 529 mmol), and dichloromethane (41 mL) were added to a 500 mL recovery flask and stirred at room temperature for 1.5 hours to remove the Boc group from compound (13)-103, resulting in deprotection and obtaining compound (11)-103. N,N-dimethylacetamide (122 g) containing 5% by mass of lithium chloride was added to the resulting reaction solution, which was then concentrated under reduced pressure at 45°C to remove dichloromethane and decomposition products of the Boc group. To the solution after vacuum concentration, N,N-diisopropylethylamine (68.4 g, 529 mmol) was added, and the mixture was heated to 70 °C. A solution of compound (12)-101 (10.1 g, 8.5 mmol) dissolved in N,N-dimethylacetamide (30.3 g) containing 5% by mass of lithium chloride at 70 °C was added. 1-Hydroxy-7-azabenzotriazole (2.55 g, 19 mmol) and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (7.17 g, 37 mmol) were added to the resulting reaction solution, and the mixture was stirred for 18 hours. The resulting reaction solution was added dropwise to purified water (2.0 L), resulting in the precipitation of a solid. The solid was collected by filtration, washed twice with purified water (500 mL), and dried under reduced pressure at 60 °C. The obtained dried product (solid) was freeze-pulverized using liquid nitrogen, washed twice with pure water (300 mL), and dried under reduced pressure at 60°C to obtain copolymer (1)-107 (yield: 45.2 g, 93%). The obtained copolymer (1)-107 1 From the results of H-NMR (600 MHz, CF3COOD) analysis, the average degree of polymerization (m1 + m2) in the polyester skeleton was calculated to be 36, and the average degree of polymerization (n1 + n2) in the polyamide skeleton was calculated to be 14, using the same method as in Example 1. Furthermore, GPC measurement revealed that the number average molecular weight (Mn) was 11.4 × 10 3 , weight average molecular weight (Mw) is 33.7 × 10 3 Then, from the average degree of polymerization (m1 + m2), the average degree of polymerization (n1 + n2) and the number average molecular weight (Mn), l was calculated to be 2.

[0175] [Example 8] Compound (13)-103 (38.1 g, 8.0 mmol), trifluoroacetic acid (56.8 g, 498 mmol), and dichloromethane (38 mL) were added to a 1 L recovery flask and stirred at room temperature for 1.5 hours to remove the Boc group in compound (13)-103, resulting in deprotection and obtaining compound (11)-103. N,N-dimethylacetamide (114 g) containing lithium chloride at a concentration of 5% by mass was added to the resulting reaction solution, and the mixture was then concentrated under reduced pressure at 45°C to distill off dichloromethane and decomposition products of the Boc group. To the solution after vacuum concentration, N,N-diisopropylethylamine (64.4 g, 498 mmol) was added, and the mixture was heated to 70 °C. A solution of compound (12)-102 (14.4 g, 8.0 mmol) dissolved in N,N-dimethylacetamide (115 g) containing 5% by mass of lithium chloride at 70 °C was added. 1-Hydroxy-7-azabenzotriazole (2.40 g, 18 mmol) and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (6.75 g, 35 mmol) were added to the resulting reaction solution, and the mixture was stirred for 18 hours. The resulting reaction solution was added dropwise to purified water (2.5 L), and sodium sulfate (400 g) was added, resulting in the precipitation of a solid. The solid was collected by filtration, washed three times with purified water (500 mL), and dried at 60 °C under reduced pressure. The obtained dried product (solid) was washed twice with pure water (300 mL) and dried under reduced pressure at 60° C. to obtain copolymer (1)-108 (yield: 44.9 g, 89%). The obtained copolymer (1)-108 1 From the results of H-NMR (600 MHz, CF3COOD) analysis, the average degree of polymerization (m1 + m2) in the polyester skeleton was calculated to be 36, and the average degree of polymerization (n1 + n2) in the polyamide skeleton was calculated to be 21, using the same method as in Example 1. Furthermore, GPC measurement revealed that the number average molecular weight (Mn) was 11.7 × 10 3 , weight average molecular weight (Mw) is 34.7 × 10 3 Then, from the average degree of polymerization (m1 + m2), the average degree of polymerization (n1 + n2) and the number average molecular weight (Mn), l was calculated to be 2.

[0176] [Example 9] Compound (13)-103 (28.6 g, 6.0 mmol), trifluoroacetic acid (42.5 g, 372 mmol), and dichloromethane (29 mL) were added to a 1 L recovery flask and stirred at room temperature for 1 hour to remove the Boc group from compound (13)-103 and deprotect it to obtain compound (11)-103. N,N-dimethylacetamide (85.8 g) containing 5% by mass of lithium chloride was added to the resulting reaction solution, and the mixture was concentrated under reduced pressure at 45°C to remove the dichloromethane and decomposition products of the Boc group. To the solution after vacuum concentration, N,N-diisopropylethylamine (48.1 g, 372 mmol) was added, and the temperature was raised to 70 °C. A solution obtained by dissolving compound (12)-103 (20.1 g, 6.0 mmol) in N,N-dimethylacetamide (161 g) containing 5% by mass of lithium chloride at 70 °C was then added. Furthermore, N,N-dimethylacetamide (142 g) containing 5% by mass of lithium chloride was added to obtain a homogeneous solution. 1-Hydroxy-7-azabenzotriazole (1.80 g, 13 mmol) and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (5.06 g, 26 mmol) were added to the resulting reaction solution, and the mixture was stirred for 18 hours. The resulting reaction solution was added dropwise to purified water (2.5 L), and sodium sulfate (150 g) was added, resulting in the precipitation of a solid. The solid was collected by filtration, washed twice with pure water (500 mL), and dried under reduced pressure at 60° C. The resulting dried product (solid) was freeze-pulverized using liquid nitrogen, washed again with pure water, and dried under reduced pressure at 60° C. to obtain copolymer (1)-109 (yield: 43.0 g, 91%). The obtained copolymer (1)-109 1 From the results of H-NMR (600 MHz, CF3COOD) analysis, the average degree of polymerization (m1 + m2) in the polyester skeleton was calculated to be 37, and the average degree of polymerization (n1 + n2) in the polyamide skeleton was calculated to be 39, using the same method as in Example 1. Furthermore, GPC measurement revealed that the number average molecular weight (Mn) was 11.5 × 10 3 , weight average molecular weight (Mw) is 31.1 × 10 3Then, from the average degree of polymerization (m1 + m2), the average degree of polymerization (n1 + n2) and the number average molecular weight (Mn), l was calculated to be 1.

[0177] <<Film manufacturing>> [Example 10] The copolymer (1)-101 (0.5 g) obtained in Example 1 was dissolved in formic acid (3 mL) and filtered through a cotton plug to obtain a composition in the form of a solution. A 6 cm x 6 cm area was outlined on one side of a glass plate, and the composition was poured into this area. The composition was then heated to 60°C to remove the solvent component from the composition, thereby producing a transparent film (approximately 100 μm thick) containing copolymer (1)-101. Image data for this film, along with image data for other examples below, are shown in Figure 5. In Figure 5, a color print is placed on the other side of the glass plate to make it easier to determine the degree of transparency of the film.

[0178] <<Film evaluation>> From the film obtained above, a dumbbell-shaped No. 7 test piece according to JIS K 6251: 2017 was cut out. A tensile test was performed on the test piece at room temperature in accordance with JIS K 6251: 2017 using a precision universal testing machine ("EZ-SX" manufactured by Shimadzu Corporation) at a tension speed of 10 mm / min, and the maximum stress (MPa) and elongation at break (%) were measured. Four test pieces were separately prepared, and the tensile test was carried out for each of these test pieces, for a total of five tests. The five measured values ​​of the maximum stress and the elongation at break were averaged, and these average values ​​were used as the measured values ​​of the maximum stress and the elongation at break, respectively. The results are shown in Table 1.

[0179] <<Film production and evaluation>> [Examples 11 to 15, 17, and 18] Using the copolymers (1) obtained in Examples 2 to 6, 8, and 9, films (thickness: approximately 100 μm) were prepared and evaluated in the same manner as in Example 10. Image data of these films are shown in FIG. 5, and the measured values ​​of the maximum stress and elongation at break of these films are shown in Table 1.

[0180] [Example 16] The copolymer (1)-106 (1.5 g) obtained in Example 7 was dissolved in formic acid (3 mL) to obtain a composition in the form of a solution. The composition was applied to one side of a polytetrafluoroethylene (PTFE) sheet heated to 60°C by bar coating with a gap thickness of 0.25 mm. The composition was then heated to remove the solvent component from the composition, producing a transparent film (thickness: approximately 100 μm) containing copolymer (1)-106. Image data of this film are shown in Figure 5.

[0181] [Comparative Example 1] Compound (12)-104 was produced in the same manner as in the production of compounds (12)-101 to 103 in Production Examples 7 to 9, except that some conditions were changed. The obtained compound (12)-104 1 From the results of H-NMR analysis, the average degree of polymerization (n1 + n2 - 2) was calculated to be 146 using the same method as in Production Example 7. Furthermore, by GPC measurement, the number average molecular weight (Mn) was 22.9 × 10 3 , weight average molecular weight (Mw) is 84.2 × 10 3 It was calculated that: Compound (12)-104 (0.5 g) was dissolved in formic acid (3 mL) and filtered through a cotton plug to obtain a composition in the form of a solution. As in Example 1, an attempt was made to produce a film containing compound (12)-104 by pouring the composition onto one side of a glass plate and then heating the composition to 60°C to remove the solvent component from the composition. However, as shown in Figure 6, most of the obtained film was cracked, and a homogeneous film was not obtained.

[0182] Comparative Example 2 Polycaprolactone (Sigma-Aldrich, number average molecular weight (Mn) 10.0 × 10 3 , weight average molecular weight (Mw) 14.0×10 3 ) (0.5 g) was dissolved in formic acid (3 mL) and filtered through a cotton plug to obtain a composition in the form of a solution. As in Example 1, the composition was poured onto one side of a glass plate and then heated to 60°C to remove the solvent component from the composition. However, as shown in Figure 7, no film-like substance was obtained, and instead a hard and brittle solid was obtained.

[0183] [Table 1]

[0184] As is clear from the above results, in Examples 1 to 9, copolymer (1) was obtained in good yield. In Examples 10 to 18, which used these copolymers (1), films with high mechanical strength were obtained, with maximum stress and elongation at break exceeding specific values. Furthermore, as is clear from Figure 5, these films had high transparency.

[0185] In contrast, as is clear from Figure 6, in Comparative Example 1, in which a polymer other than copolymer (1) was used, a film could not be formed normally, and as is clear from Figure 7, in Comparative Example 2, a film itself could not be formed. [Industrial Applicability]

[0186] The present invention can be used to produce protective films, packaging films, and packaging materials that are molded film bodies.

Claims

1. The following general formula (1) 【Chemistry 1】 (wherein l is an integer of 1 or more; m １ and m ２ are each independently an integer of 0 or more, provided that m １ and m ２ At least one of the following is an integer of 1 or more; when l is 2 or more, l m １ may be the same or different, and l m ２ may be the same or different from each other; R １ and R ２ are each independently a chain alkylene group having 1 to 20 carbon atoms, and l and m １ When at least one of is 2 or more, l × m １ R １ may be the same or different, and l and m ２ When at least one of is 2 or more, l × m ２ R ２ may be the same or different from each other; R ３ is a chain alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms, and when l is 2 or more, l R ３ may be the same or different from each other; n １ and n ２ are each independently an integer of 1 or more, and when l is 2 or more, １ may be the same or different, and l n ２ may be the same or different from each other; p １ and p ２ are each independently an integer of 1 to 11, and l and n １ When at least one of is 2 or more, l × n １ p １ may be the same or different, and l and n ２ When at least one of is 2 or more, l × n ２ p ２ may be the same or different from each other; X １ represents a chain aliphatic hydrocarbon group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, a heteroarylene group having 4 or 5 carbon atoms, or a group represented by the general formula "-X ２ -Z １ -X ３ - (wherein, X ２ and X ３ are each independently an arylene group having 6 to 12 carbon atoms; Z １ is a heteroatom or a heteroatom-containing group.)) or a group represented by the general formula "-R ４ -Z ２ -R ５ - (wherein, R ４ and R ５ are each independently a chain aliphatic hydrocarbon group having one or more carbon atoms, provided that the total number of carbon atoms in these aliphatic hydrocarbon groups is 20 or less; Z ２ is a heteroatom or a heteroatom-containing group. １ may be the same or different.) A copolymer represented by the formula:

2. The X １ is the general formula "-X ２１ -O-X ３１ - (wherein, X ２１ and X ３１ and each independently represents an arylene group having 6 to 9 carbon atoms.

3. The R １ and R ２ and each independently represent a chain alkylene group having 3 to 5 carbon atoms.

4. The R ３ is a chain alkylene group having 3 to 5 carbon atoms.

5. Said m １ and m ２ The copolymer according to claim 1 or 2, wherein the total value of

6. The p １ and p ２ and each independently represent an integer of 1 to 4.

7. The n １ and n ２ The copolymer according to claim 1 or 2, wherein the total value of

8. The R １ and R ２ are identical to each other, and said p １ and p ２ The copolymer according to claim 1 or 2, wherein are the same as each other.

9. A film comprising the copolymer according to claim 1 or 2.

10. The following general formula (11) 【Chemistry 2】 (In the formula, m １ and m ２ are each independently an integer of 0 or more, provided that m １ and m ２ at least one of is an integer of 1 or greater; R １ and R ２ are each independently a chain alkylene group having 1 to 20 carbon atoms, m １ When m is 2 or more, １ R １ may be the same or different, m ２ When m is 2 or more, ２ R ２ may be the same or different from each other; R ３ represents a chain alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms; p １ and p ２ are each independently an integer from 1 to 11. and a compound represented by The following general formula (12) 【Transformation 3】 (In the formula, n １ and n ２ are each independently an integer of 1 or more; p １ and p ２ are each independently an integer from 1 to 11, and n １ When n is 3 or more, １ -1 p １ may be the same or different, and n ２ When n is 3 or more, ２ -1 p ２ may be the same or different from each other; X １ represents a chain aliphatic hydrocarbon group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, a heteroarylene group having 4 or 5 carbon atoms, or a group represented by the general formula "-X ２ -Z １ -X ３ - (wherein, X ２ and X ３ are each independently an arylene group having 6 to 12 carbon atoms; Z １ is a heteroatom or a heteroatom-containing group.)) or a group represented by the general formula "-R ４ -Z ２ -R ５ - (wherein, R ４ and R ５ are each independently a chain aliphatic hydrocarbon group having one or more carbon atoms, provided that the total number of carbon atoms in these aliphatic hydrocarbon groups is 20 or less; Z ２ is a heteroatom or a heteroatom-containing group.) and a compound represented by By reacting the following general formula (1) 【Chemistry 4】 (In the formula, m １ , m ２ , R １ , R ２ , R ３ , n １ , n ２ , p １ , p ２ and X １ is the same as above; l is an integer of 1 or more; when l is 2 or more, l m １ may be the same or different, and l m ２ may be the same or different, and l n １ may be the same or different, and l n ２ may be the same or different, and l R ３ may be the same or different, and 1 X １ may be the same or different; l and m １ When at least one of is 2 or more, l × m １ R １ may be the same or different; l and m ２ When at least one of is 2 or more, l × m ２ R ２ may be the same or different; l and n １ When at least one of is 2 or more, l × n １ p １ may be the same or different; l and n ２ When at least one of is 2 or more, l × n ２ p ２ may be the same or different.) A method for producing a copolymer, wherein the copolymer is obtained by:

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