Copolymer, film, and method for producing copolymer

Abstract

A copolymer represented by formula (1) (where, l is an integer of 1 or more; m1 and m2 each are an integer of 0 or more, and m1+m2 is 1 or more; R1 and R2 each are a C1-20 chain alkylene group; R3 is a C2-12 chain alkylene group or a C6-12 arylene group; n1 and n2 each are an integer of 1 or more; p1 and p2 each are an integer of 1-11; and X1 is a C1-12 chain aliphatic hydrocarbon group, a C6-12 arylene group, a C4 or C5 heteroarylene group, or a group represented by formula -X2-Z1-X3- or formula -R4-Z2-R5- (X2 and X3 each are a C6-12 arylene group; R4 and R5 each are a C1 or higher chain aliphatic hydrocarbon groups; and Z1 and Z2 each are a heteroatom or a heteroatom-containing group)).

Description

Copolymer, film, and method for producing copolymer

[0001] The present invention relates to a copolymer, a film, and a method for producing the copolymer. This application claims priority to Japanese Patent Application No. 2024-110570, filed on July 9, 2024, the contents of which are incorporated herein by reference.

[0002] Block copolymers having both a polyamide backbone and a polyester backbone in the main chain can be designed to combine the properties derived from these two backbones. For example, a polyamide backbone is advantageous for constructing a polymer with high heat resistance and mechanical strength, a polyester backbone is advantageous for constructing a polymer with high moldability, and 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), and a method for producing a block copolymer in which repeating units derived from ε-caprolactone and 2-pyrrolidone are randomly arranged by using a polyamide having a structure in which ε-caprolactone is sequentially reacted and having 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 having isocyanate groups at both ends. Known methods include a method for 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 for 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).

[0004] International Publication No. 2023 / 238706

[0005] Atsuyoshi Nakayama, Naoko Yamano, Norioki Kawasaki, Yasuhide Nakayama, Polym. Degrad. Stab. 2013, 98, 1882-1888.Seda Cakir, Rene Kierkels, Cor Koning, J. Polym. Sci. PartA: Polym. Chem. 2011, 49, 2823-2833.

[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.

[0008] In order to solve the above problems, the present invention employs the following configuration: [1] A compound represented by the following general formula (1):

[0009] (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; 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; R ３is 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; 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; 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; 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:

[0010] [2] The X １ is the general formula "-X ２１ -O-X３１ - (wherein, X ２１ and X ３１ [3] The copolymer according to [1], wherein R is a group represented by the formula (I) １ and R ２ are each independently a chain alkylene group having 3 to 5 carbon atoms. [4] The copolymer according to [1] or [2]. ３ is a chain alkylene group having 3 to 5 carbon atoms. [5] The copolymer according to any one of [1] to [3]. １ and m ２ The copolymer according to any one of [1] to [4], wherein the sum of p is 1 to 120. [6] １ and p ２ [5] The copolymer according to any one of [1] to [5], wherein each independently represents an integer of 1 to 4.

[0011] [7] The n １ and n ２ [8] The copolymer according to any one of [1] to [6], wherein the sum of R １ and R ２ are identical to each other, and said p １ and p ２ [9] A film containing the copolymer according to any one of [1] to [8].

[10] A film containing a copolymer according to the following general formula (11):

[0012] (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 more; 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 R２ may be the same or different; R ３ is a chain alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms; １ and p ２ and each independently represents an integer of 1 to 11.

[0013] (In the formula, n １ and n ２ are each independently an integer of 1 or more; 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; 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.

[0014] (In the formula, m １ , m ２ , R １ , R２ , 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 from each other.

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

[0016] Compound (15) obtained in Production Example 1 １ The results of H-NMR analysis of compound (13) obtained in Production Example 4 are shown below. １ The results of H-NMR analysis of compound (12) obtained in Production Example 7 are shown below. １ The results of H-NMR analysis of copolymer (1) obtained in Example 1 are shown below. １1H-NMR analysis results. ...

[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 with the symbols attached. For example, in this specification, a copolymer represented by the general formula (1) described below may be referred to as "copolymer (1)".

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

[0019] (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; 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; 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; n１ 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; 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; 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.) (In this specification, this copolymer may be referred to as "copolymer (1)").

[0020] The 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 copolymer (1) can be increased, for example, by adjusting the structure and size of the polyamide backbone. On the other hand, the moldability of copolymer (1) can be increased, for example, by adjusting the structure and size of the polyester backbone. That is, in copolymer (1), the balance of properties derived from these backbones can be adjusted by adjusting the ratio of polyamide backbone and the ratio of polyester backbone. Furthermore, since both the polyamide backbone and the polyester backbone have biodegradability depending on their structure, the biodegradability of copolymer (1) can be improved by adjusting the structure of these backbones.

[0022] In general formula (1), l defines the molecular size of copolymer (1) and is an integer of 1 or more. On the other hand, the upper limit of l is not particularly limited. For example, in terms of facilitating the production of copolymer (1), such as facilitating the purification of copolymer (1), l 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 general formula (1), m １ is represented by the general formula "-O-R １ The number of groups represented by "-C(=O)-" is specified, and is an integer of 0 or more. １ When m is 2 or more, the group is a repeating unit in a block containing a polyester skeleton, and m １ Similarly, in the general formula (1), m ２ is represented by the general formula "-C(=O)-R ２ The number of groups represented by "-O-" is specified, and is an integer of 0 or more. ２ When m is 2 or more, the group is a repeating unit in a block containing a polyester skeleton, and m ２ is the number of repetitions.

[0024] m １ is 0 or more, and may be, for example, 1 or more, 2 or more, 5 or more, 8 or more, 11 or more, 15 or more, or 22 or more. １ There is no particular limitation on the upper limit of m １ The copolymer (1) having m of 60 or less can be more easily produced. １ may be, for example, any of 50 or less, 35 or less, 28 or less, 21 or less, 15 or less, and 8 or less. １ can be appropriately set within a numerical range that is set by arbitrarily combining any of the above lower limit values ​​and any of the above upper limit values, for example.

[0025] When l is 2 or more, l m １ may be the same or different. １ Not only in the case of (1), but also in the case of (2), the fact that the objects to be compared "may be the same or different from each other" means that all of them may be the same, all of them may be different, or only some of them may be the same. １ If the m １ The combination is not particularly limited.

[0026] m ２ is 0 or more, and may be, for example, 1 or more, 2 or more, 5 or more, 8 or more, 11 or more, 15 or more, or 22 or more. ２ There is no particular limitation on the upper limit of m ２ The copolymer (1) having m of 60 or less can be more easily produced. ２ may be, for example, any of 50 or less, 35 or less, 28 or less, 21 or less, 15 or less, and 8 or less. ２ can be appropriately set within a numerical range that is set by arbitrarily combining any of the above lower limit values ​​and any of the above upper limit values, for example.

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

[0028] However, in the general formula (1), m １ and m ２ None of the values ​​are 0, and m １ and m ２ At least one of the above is an integer of 1 or more.

[0029] m １ +m ２ (m １ and m ２ The sum of m is 1 or more, and may be, for example, 2 or more, 4 or more, 10 or more, 16 or more, 22 or more, 30 or more, or 44 or more. １ +m ２ There is no particular limitation on the upper limit of m １ +m ２ The copolymer (1) having m of 120 or less can be more easily produced. １ +m ２ may be, for example, 100 or less, 70 or less, 56 or less, 42 or less, 30 or less, or 16 or less. １ +m ２ can be appropriately set within a numerical range that is set by arbitrarily combining any of the above lower limit values ​​and any of the above upper limit values. １ +m ２ 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 m １ +m ２ is an example of m １ +m ２ are not limited to these.

[0030] m １ and m ２may be the same as or different from each other. For example, m １ and m ２ The copolymer (1) having different valences 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 R may be either linear or branched. 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 in the alkylene group in may be, for example, any one of 1 to 17, 1 to 14, 1 to 11, 1 to 8, and 1 to 5, or any one of 3 to 20, 6 to 20, 9 to 20, 12 to 20, and 15 to 20, or may be 3 to 5. For example, R １and R ２ is an alkylene group having 3 to 5 carbon atoms, the symbol m １ and m ２ The polyester skeleton to which the group is attached has high biodegradability, and copolymer (1) has more preferable properties.

[0034] l and m １ If either or both of these are 2 or more, then l × m １ R １ may be the same or different. ２ If either or both of these are 2 or more, then l × m ２ 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. ３ The alkylene group in R may be either linear or branched. 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 number of carbon atoms of the alkylene group in the formula (I) may be, for example, any one of 2 to 9, 2 to 7, and 2 to 5, any one of 3 to 12, 6 to 12, and 9 to 12, or 3 to 9.

[0037] R ３ The arylene group in R is preferably monocyclic. ３Examples 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 a toluene-2,6-diyl group (2-methylbenzene-1,3-diyl group), a toluene-2,5-diyl group, a toluene-2,4-diyl group, a toluene-2,3-diyl group, and a toluene-3,5-diyl group; xylylenediyl groups such as an o-xylene-3,4-diyl group, an o-xylene-3,5-diyl group, an o-xylene-3,6-diyl group, an m-xylene-2,4-diyl group, an m-xylene-2,5-diyl group, an m-xylene-2,6-diyl group, a p-xylene-2,3-diyl group, a p-xylene-2,5-diyl group, and a p-xylene-2,6-diyl group; 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] In this specification, 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 formula (I). Therefore, for example, a group having a structure in which one or more hydrogen atoms have been removed from biphenyl is defined as a monocyclic group 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), n １ is represented by the general formula "-C(=O)-(CH ２ ) p １ The number of groups represented by "-NH-" is an integer of 1 or more. The group is a repeating unit in a block containing a polyamide skeleton, and n １ Similarly, in the general formula (1), n ２ is represented by the general formula "-NH-(CH ２ ) p ２ The number of groups represented by "-C(=O)-" is an integer of 1 or more. The group is a repeating unit in a block containing a polyamide skeleton, and n ２ is the number of repetitions.

[0042] n １ is 1 or more, and may be, for example, 4 or more, 6 or more, 9 or more, 13 or more, or 16 or more. １ There is no particular limitation on the upper limit of n １ The copolymer (1) having n of 120 or less can be more easily produced. １may be, for example, any of 60 or less, 45 or less, 35 or less, 25 or less, 15 or less, and 8 or less. １ can be appropriately set within a numerical range that is set by arbitrarily combining any of the above lower limit values ​​and any of the above upper limit values, for example.

[0043] If l is 2 or more, l n １ may be the same or different, and l n １ The combination is not particularly limited.

[0044] n ２ is 1 or more, and may be, for example, 4 or more, 6 or more, 9 or more, 13 or more, or 16 or more. ２ There is no particular limitation on the upper limit of n ２ The copolymer (1) having n of 120 or less can be more easily produced. ２ 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. ２ can be appropriately set within a numerical range that is set by arbitrarily combining any of the above lower limit values ​​and any of the above upper limit values, for example.

[0045] If l is 2 or more, l n ２ may be the same or different, and l n ２ The combination is not particularly limited.

[0046] In the general formula (1), n １ and n ２ may be 1, but n １ and n ２ At least one of these is preferably an integer of 2 or more.

[0047] n １ +n ２ (n １ and n ２ The sum of n is 2 or more, and may be, for example, 8 or more, 12 or more, 18 or more, 26 or more, or 32 or more. １ +n ２There is no particular limitation on the upper limit of n １ +n ２ The copolymer (1) having n of 240 or less can be more easily produced. １ +n ２ may be, for example, 120 or less, 90 or less, 70 or less, 50 or less, 30 or less, or 16 or less. １ +n ２ can be appropriately set within a numerical range that is set by arbitrarily combining any of the above lower limit values ​​and any of the above upper limit values. For example, in one embodiment, n １ +n ２ 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 n １ and n ２ is an example of １ and n ２ are not limited to these.

[0048] n １ and n ２ may be the same as or different from each other. For example, １ and n ２ The copolymer (1) having different valences can be more easily produced.

[0049] In general formula (1), p １ and p ２ are all methylene groups (-CH ２ -) and each independently represents an integer of 1 to 11. That is, p １ and p ２ may be the same or different from each other. In terms of facilitating the production of the copolymer (1), １ and p ２ are preferably the same as each other.

[0050] p １ and p ２may be, for example, independently 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), p １ and p ２ are preferably each independently an integer of 1 to 4.

[0051] l and n １ If either one or both of these is 2 or more, then l × n １ p １ may be the same or different. ２ If either one or both of these is 2 or more, then l × n ２ p ２ may be the same or different from each other.

[0052] In the copolymer (1), R １ and R ２ are identical to each other, and p １ and p ２ are the same, which makes it easier to produce such a copolymer (1).

[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 - (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.

[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 can be mentioned.

[0056] X １ Examples of the unsaturated aliphatic hydrocarbon group in the above formula (1) include divalent groups having 2 to 12 carbon atoms, in which one or more single bonds (C-C) between carbon atoms in the saturated aliphatic hydrocarbon group (alkylene group) are replaced with double bonds (C=C) or triple bonds (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 even 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 X is preferably monocyclic. 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 Examples of heteroatoms constituting the aromatic ring skeleton in the heteroarylene group having 4 or 5 carbon atoms in the formula (I) include an oxygen atom, a nitrogen atom, a sulfur atom, etc. The number of heteroatoms constituting the aromatic ring skeleton in the heteroarylene group may be 1 or 2 or more, and when there are 2 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 furan-2,3-diyl group, furan-2,4-diyl group, furan-2,5-diyl group, furan-3,4-diyl group, furan-2,5-diyl group, furan-3,5-diyl group, etc. 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, pyridine-3,5-diyl group, etc.; and pyrrole-diyl groups such as pyrrole-2,3-diyl group, pyrrole-2,4-diyl group, pyrrole-2,5-diyl group, pyrrole-3,4-diyl group, etc. 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 In the general formula (1), the carbon atom in the other carbonyl group is bonded to the carbon atom in the other carbonyl group. 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 X３ 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. １ Among these, preferred examples of the heteroatom include an oxygen atom (O) and a sulfur atom (S). 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 dimethylsilylene groups (—Si(CH ３ ) ２ Among the heteroatom-containing groups, examples of the divalent group having a phosphorus atom (phosphorus atom-containing group) include a phenylphosphanylene group (-P(C ６ H ５ )-) and other arylphosphanylene groups.

[0065] General formula “-X ２ -Z １ -X ３ Among the groups represented by "-", X ２ and X ３When 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 ３ The group represented by "-" is not limited to these.

[0066] (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 R in the group represented by "-" ４ is bonded to a carbon atom in one of the carbonyl groups in the general formula (1), and R ５ In the general formula (1), the carbon atom in the other carbonyl group is bonded to the carbon atom in the other carbonyl group. 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. ４ the number of carbon atoms in the aliphatic hydrocarbon group in 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 in R ５ The aliphatic hydrocarbon groups in each independently have 1 to 19 carbon atoms.

[0068] R ４ and R ５ The 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 above formula (1) include divalent groups having 2 to 19 carbon atoms, in which one or more single bonds (C-C) between carbon atoms in the saturated aliphatic hydrocarbon group (alkylene group) are replaced with double bonds (C=C) or triple bonds (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 even 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. ２ Among these, preferred examples of the heteroatom include an oxygen atom and a sulfur atom.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 silylene groups (—SiH ２ Among the heteroatom-containing groups, examples of the divalent group having a phosphorus atom (phosphorus atom-containing group) include a phosphanylene group (-PH-).

[0074] X １ is represented by 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 When the alkylene group has 1 to 3 carbon atoms, preferred examples of the alkylene 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: -CH ２ -O-CH ２ - - (CH ２ ) ２ -O-(CH ２ ) ２ - - (CH ２ ) ３ -O-(CH ２ ) ３ - -CH ２ -S-CH ２ - - (CH ２ ) ２ -S-(CH ２ ) ２ - - (CH ２ ) ３ -S-(CH ２ )３ - -CH ２ -NH-CH ２ - - (CH ２ ) ２ -NH-(CH ２ ) ２ - - (CH ２ ) ３ -NH-(CH ２ ) ３ - -CH ２ -SiH ２ -CH ２ - - (CH ２ ) ２ -SiH ２ - (CH ２ ) ２ - - (CH ２ ) ３ -SiH ２ - (CH ２ ) ３ - -CH ２ -PH-CH ２ - - (CH ２ ) ２ -PH-(CH ２ ) ２ - - (CH ２ ) ３ -PH-(CH ２ ) ３ -

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

[0077] X １ is represented by the general formula "-X ２１ -Z １１ -X ３１ - (wherein, 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 In the general formula (1), the carbon atom in the other carbonyl group is bonded to the carbon atom in the other carbonyl group. 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 ３１ The 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, those having 6 to 9 carbon atoms can be mentioned. ２１ and X ３１More specifically, 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 a toluene-2,6-diyl group (2-methylbenzene-1,3-diyl group), a toluene-2,5-diyl group, a toluene-2,4-diyl group, a toluene-2,3-diyl group, and a toluene-3,5-diyl group; xylenediyl groups such as o-xylene-3,4-diyl group, o-xylene-3,5-diyl group, o-xylene-3,6-diyl group, m-xylene-2,4-diyl group, m-xylene-2,5-diyl group, m-xylene-2,6-diyl group, p-xylene-2,3-diyl group, p-xylene-2,5-diyl group and p-xylene-2,6-diyl group; 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; and the like.

[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. 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 represented by the general formula "-X ２１ -O-X ３１ - (wherein, X ２１ and X ３１ are each independently an arylene group having 6 to 9 carbon atoms. Such a copolymer (1) has better properties and can be produced more easily.

[0082] The number average molecular weight (Mn) of 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 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 copolymer (1) is equal to or greater than the lower limit, the strength of copolymer (1) and a film containing it, which will be described later, is increased. When the number average molecular weight or weight average molecular weight of copolymer (1) is equal to or less than the upper limit, the formability of copolymer (1) and a film containing it, which will be described later, is 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 the copolymer (1), when the polyester skeleton side is the terminal part of the copolymer (1), the terminal part is represented by the symbol p １ or p ２ An amino group (-NH ２ ), 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 end of the copolymer (1), the terminal end is represented by the symbol p １ or p ２ The carboxyl group (-C(=O)-OH) may be bonded to a methylene group having a carboxyl group attached thereto, or the carboxyl group may be an anion (-C(=O)-OH) － The salt may be a salt formed from a metal ion, an ammonium ion (NH ４ ＋ ) and other inorganic cations; ＋) is added to the cation, such as an ammonium ion.

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

[0086] (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 more; 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; R ３ is a chain alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms; １ and p ２ and each independently represent an integer of 1 to 11.) (hereinafter, this may be referred to as "compound (11)") and a compound represented by the following general formula (12):

[0087] (In the formula, n １ and n ２ are each independently an integer of 1 or more; 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; X １represents 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.))) is reacted with a compound represented by the following general formula (1):

[0088] (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 m２ 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 from each other.) (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)> Compound (11) is represented by the general formula (11) above. Compound (11) is a raw material compound for forming the polyester skeleton and a part of the polyamide skeleton in copolymer (1).

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

[0092] Compound (11) may be used in which the amino group forms a salt, such as a hydrochloride, sulfate, or nitrate salt formed by reaction with an inorganic acid.

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

[0094] n in the general formula (12) １ , n ２ , p １ , p ２ and X １ respectively represent n in the general formula (1). １ , n ２ , p １ , p ２ and X １ is the same as １ -1 is 0 or greater, and n １ -1 is 2 or more (n １ is 3 or more), then n １ -1 p １ may be the same or different, and n １ -1 p １ The combination of is not particularly limited. ２ -1 is 0 or greater, and n ２ -1 is 2 or more (n ２ is 3 or more), then n ２ -1 p ２ may be the same or different, and n ２ -1 p ２ The combination of n in the general formula (12) is not particularly limited. １ , n ２ , p １ , p ２ and X １ The preferred embodiments of are the same as those of the general formula (1). Therefore, further explanation of these symbols will be omitted below. Next, various conditions for the production method of this embodiment will be described.

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

[0096] The compound (11) and the compound (12) used in the reaction may each be one kind or two or more kinds, and 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 , p １ and p ２ As compound (12), p １ , p ２ and X １ It is preferable to use compounds having the same p １ and p ２ It is more preferable to use those in which these 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). Examples of such a solvent 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 or two or more types. When two or more types are used, the combination and ratio thereof can be selected as desired 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 to improve the solubility of compound (12) in the reaction solution. This can improve 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 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 the salt relative to the solvent ([amount of salt used (g)] / [amount of solvent used (L)]) is 10 to 200 g / L.

[0100] In order to improve the reaction rate, it is preferable to use a condensing agent when reacting compound (11) with compound (12). The condensing agent may be a known one, and specific examples thereof include carbodiimide compounds (compounds having a carbodiimide skeleton (—N═C═N—)) and compounds other than carbodiimide compounds that can activate a carboxy group (—C(═O)—OH).

[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). tetrafluorophosphate (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 kind or two or more kinds. When two or more kinds 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 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 other than the carbodiimide compounds that can activate carboxy groups is preferably 0.2 to 1.5 times, and may be, for example, 0.4 to 1.0 times, the molar amount of the carbodiimide compounds 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 for compound (11) with 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 solution is then post-treated as necessary. Thereafter, compound (11) may be isolated from the reaction solution or the post-treatment product and subjected to a reaction with compound (12), or compound (11) may be subjected to a reaction with compound (12) without being isolated. When compound (11) is isolated, it can be isolated by a known method.

[0107] (In the formula, G １ and G ２ are each independently a protecting group; m １ , m ２ , R １ , R ２ , R ３ , p １ and p ２ is the same as above.)

[0108] In general formula (13), G １ and G ２ are each independently a protecting group. １and a protecting group in G ２ The 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 may be a known group, and specific examples thereof include groups that can be deprotected under acidic conditions, such as a tert-butoxycarbonyl group (Boc group).

[0110] Deprotection of compound (13) (removal of the protecting group) can be carried out 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 time 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] Regardless of whether 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 bicarbonate. 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, the base is preferably an organic base in terms of its high solubility in the reaction solution. The base used in the reaction may be one type or two or more types. When two or more types are used, the combination and ratio thereof can be selected as desired 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 potassium carbonate (K ２ CO ３ ), sodium sulfate (Na ２ SO ４ ) or other salt is added. Addition of the salt promotes precipitation of the target product (copolymer (1)). Next, the insoluble matter (precipitate, precipitate) is recovered, and the recovered insoluble matter is further washed with water and dried as necessary, this process is repeated once or twice or more times, and the finally obtained washed matter is dried to obtain copolymer (1).

[0116] The washed product may be dried under normal pressure or under reduced pressure (vacuum drying). The washed product 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 product may be combined as desired depending on the purpose. The obtained copolymer (1) may be further purified by repeating water washing and drying one or more times.

[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] (In the formula, m １ , m ２ , R １ , R ２ , R ３ , p １ , p ２ , 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 compound (1811) and compound (1812) are not used, m １ is 0, and when compound (1821) and compound (1822) are not used, m ２ is 0.

[0123] (In the formula, R １ , R ２ , R ３ , m １ and m ２ is the same as above.)

[0124] Compound (1811) and 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 the catalyst 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, n １ is 1, and when compound (16b2) is not used, n ２ is 1.

[0127] (In the formula, X １ , n １ , n ２ , p １ and p ２ is 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 reacting compound (12) with thionyl chloride (SOCl ２ ) can be obtained by a known method.

[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] (In the formula, X １ , p １ and p２ is 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 according to this embodiment contains copolymer (1), which gives it high mechanical strength and good film properties. Furthermore, by adjusting the type of copolymer (1), the film according to this embodiment has high transparency and moldability. Then, a molded article can be obtained by molding the film according to this embodiment.

[0133] The degree of mechanical strength of the film of the present 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 performing 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, 10 MPa or more, 15 MPa or more, 20 MPa or more, 25 MPa or more, or 30 MPa or more. On the other hand, a film having the maximum stress of 50 MPa or less can be more easily realized.

[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, a 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 the present embodiment can be produced by using a composition containing copolymer (1). For example, the film can be formed by applying a liquid composition containing copolymer (1) and a solvent to the surface of an object on which the film is to be formed, and then drying the composition (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 solvent, in addition to the copolymer (1). Examples of the other components include various additives known in the film field, such as antioxidants, antistatic agents, and antiblocking agents.

[0140] The copolymer (1) and the other components contained in the film may each be one type or two or more types, and when two or more types are contained, the combination and ratio thereof can be selected arbitrarily depending on the purpose. The copolymer (1), solvent, and the other components contained in the composition may each be one type or two or more types, and when two or more types 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 the film (parts by mass)] / [total mass of the 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 ratio 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 can be obtained by blending copolymer (1), the solvent as needed, and the other components as needed. The temperature and time during addition and mixing of 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.

[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, compound (13) in Production Examples 4 to 6, and compound (14) in Production Example 7, １ When measuring H-NMR, a sample of the target substance (10 mg) was dissolved in deuterated chloroform (CDCl ３ A measurement sample was prepared by dissolving the compound in 1 mL of tetramethylsilane (manufactured by Kanto Chemical Co., Ltd., deuteration rate of 99.8% or more, containing 0.03 vol% tetramethylsilane). １ When measuring H-NMR, deuterated methanol (CD) containing calcium chloride at a concentration of 10 wt / v% (mass / volume%) was used. ３ A measurement sample was prepared by dissolving a target sample (10 mg) in 1 mL of OD (manufactured by Kanto Chemical Co., Ltd., deuteration rate 99.8%). １ When measuring H-NMR, deuterated trifluoroacetic acid (CF ３ A measurement sample was prepared by dissolving a target sample (10 mg) in 1 mL of COOD (manufactured by Kanto Chemical Co., Inc., deuteration rate 99.8%).

[0148] In the following examples, gel permeation chromatography (GPC) measurements were performed using 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 contained in the eluent were removed under reduced pressure (23.0 kPa). A JASCO "PU-4185" pump was used as the solvent delivery pump, and the eluent flow rate was set to 0.15 mL / min. A JASCO "AS-4150" autosampler was used, and the sample loop volume was set to 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" RI detector was used. The GPC columns used were "LF-404" and "LF-G" manufactured by Showa Denko K.K. The molecular weight of the sample was calculated from a calibration curve prepared using polymethyl methacrylate standard samples (manufactured by Showa Denko K.K., molecular weights: 7290, 20100, 72000, 224000, 539000, 1020000).

[0149] <<Preparation of Starting Compounds>> <Preparation of Compound (15)> Compounds (15)-101, (15)-102 and (15)-103 were prepared according to the following procedures.

[0150]

[0151] [Production 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, and the mixture was 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%). １ H-NMR (600MHz, CDCl ３The analysis results are shown in Figure 1. From the peak area ratio of 8 and 3 in Figure 1, the average degree of polymerization (m １ +m ２ ) was calculated to be 10. The reagents and apparatus used in Production Examples 2 and 3 described below are the same as those used here unless otherwise specified.

[0152] [Production 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%). １ H-NMR (600MHz, CDCl ３ ) from the analysis results, the average degree of polymerization (m １ +m ２ ) was calculated to be 20.

[0153] [Production 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%). １ H-NMR (600MHz, CDCl ３ ) from the analysis results, the average degree of polymerization (m １ +m ２ ) was calculated to be 37.

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

[0155]

[0156] Preparation 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%). １ H-NMR (600MHz, CDCl ３ The analysis results for 2 and 7 and 10 are shown in Figure 2. From the peak area ratios of 2 and 7 and 10 in Figure 2, the average degree of polymerization (m １ +m ２ ) was calculated to be 11. The reagents and apparatus used in Production Examples 5 and 6 described below are the same as those used here unless otherwise specified.

[0157] [Production 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, cooled in an ice bath, and 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 pure water (500 mL) and dried under reduced pressure at 40°C to obtain compound (13)-102 (yield: 126 g, 94%). The resulting compound (13)-102 １ H-NMR (600MHz, CDCl ３ ) was analyzed by the same method as in Production Example 4, the average degree of polymerization (m １ +m ２ ) was calculated to be 20.

[0158] [Production 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 then 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%). １ H-NMR (600MHz, CDCl ３ ) was analyzed by the same method as in Production Example 4, the average degree of polymerization (m １ +m ２ ) was calculated to be 38.

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

[0160]

[0161] [Production Example 7] 4,4'-oxybisbenzoic acid (104 g, 404 mmol, manufactured by BLD Pharmatech), dichloromethane (150 mL), thionyl chloride (147 mL, 2020 mmol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and dimethylformamide (0.50 g, 6.8 mmol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 500 mL recovery flask, and the resulting mixture was heated to 50°C and stirred under reflux for 7 hours. Next, a vacuum line was attached to the flask, and the reaction product was dried under reduced pressure. The resulting dried product (4,4'-oxybis(benzoyl chloride), yield 120 g, 101%) was used directly in the next reaction without purification. The resulting 4,4'-oxybis(benzoyl chloride) １ The results of the H-NMR analysis are shown below. １ H-NMR (600MHz, CDCl ３ ) δ8.34-8.05 (m, 2H), 7.34-7.03 (m, 2H).

[0162] 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.) were added to a 1 L recovery flask, and the resulting mixture was stirred for 3 hours while being heated to 90°C in an oil bath. Next, the flask was removed from the oil bath and allowed to cool, after which dichloromethane (1.0 L) was 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 solution (500 mL), dried over magnesium sulfate, and then concentrated under reduced pressure using an evaporator. Hexane (300 mL) was added to the resulting concentrate, and the resulting solid was collected and dried in vacuo at 45°C to obtain compound (14)-101 (yield: 98.3 g, 84%). １ The results of the H-NMR analysis are shown below. １ H-NMR (600MHz, CDCl ３ ) δ 7.68-7.66 (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 dichloromethane was distilled off. Heating was continued at 30 °C for 24 hours under reduced pressure to obtain a solid. Next, 6 M hydrochloric acid (520 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 (88 mL) and stirred for 6 hours. As a result, a solid precipitated. The solid matter was recovered by decantation and washed successively with acetone (900 mL) twice, acetone (500 mL) four times, a mixture of acetone (450 mL) and pure water (50 mL) twice, pure water (500 mL) once, and acetone (500 mL) twice. The washed solid matter was recovered by filtration and dried under reduced pressure at 45°C to obtain compound (12)-101 (yield: 109 g, 70%). １ H-NMR (600MHz, CD ３ The analytical results for 10 wt / v% calcium chloride (OD) are shown in Figure 3. The average degree of polymerization (n １ +n ２ −2) was calculated to be 11. The reagents and apparatus used in Production Examples 8 and 9 described below are the same as those used here unless otherwise specified.

[0164] [Production 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 dichloromethane was distilled off. Heating was continued at 30°C for 24 hours under reduced pressure 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) 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 pure water (500 mL), and dried under reduced pressure at 60°C. The dried matter obtained was washed twice with pure 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%). １ H-NMR (600MHz, CD ３ From the results of analysis at 10 wt / v % calcium chloride, the average degree of polymerization (n １ +n ２ -2) was calculated to be 18.

[0165] [Production 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 dichloromethane was distilled off. Heating was continued 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, and 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 matter was collected by filtration, washed once with acetone (1.0 L), and dried under reduced pressure at 60°C. The resulting dried matter was washed twice with pure water (500 mL) and once with acetone (500 mL), successively. The washed dried matter was dried under reduced pressure at 60°C to obtain compound (12)-103 (yield: 112 g, 67%). １ H-NMR (600MHz, CD ３ From the results of analysis at 10 wt / v % calcium chloride, the average degree of polymerization (n １ +n ２ -2) was calculated to be 36.

[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]

[0168] Example 1 Compound (13)-101 (33.7 g, 20 mmol), trifluoroacetic acid (50.2 g, 440 mmol, manufactured by 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, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was added to the resulting reaction solution, which was then concentrated under reduced pressure at 35°C to distill off 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, and then allowed to cool 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 the mixture was stirred for 20 hours. The resulting reaction solution was added dropwise to pure water (500 mL) to obtain a rubbery precipitate. This precipitate was collected by filtration and washed once with pure 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%). １ H-NMR (600MHz, CF ３ The analysis results of the 2- and 7-mercapto-3-based copolymer are shown in Figure 4. The average degree of polymerization (m １ +m ２ ) was calculated to be 11, and the average degree of polymerization (n １ +n ２ The number average molecular weight (Mn) 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 ３ The average degree of polymerization (m １ +m ２ ), average degree of polymerization (n １ +n ２ From the molecular weight (Mn) and the number average molecular weight (Mn), l was calculated to be 4. Unless otherwise specified, the reagents and apparatus used in Examples 2 to 9 described below are the same as those used here.

[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 and deprotect it, thereby obtaining compound (11)-101. N,N-dimethylacetamide (75.9 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. N,N-diisopropylethylamine (42.7 g, 331 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 (27.0 g, 15 mmol) in N,N-dimethylacetamide (81.0 g) containing lithium chloride at a concentration of 5% by mass at 70°C was then added. As a result, a solid matter precipitated. Next, the reaction solution containing this precipitate was transferred to a 1 L flask, and N,N-dimethylacetamide (261 g) containing lithium chloride at a concentration of 5% by mass (100%) was added thereto. 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 obtained solution, and the mixture was stirred for 18 hours. The obtained reaction solution was added dropwise to pure water (1.4 L) to precipitate a solid matter. The solid matter was recovered by filtration and washed twice with pure water (500 mL). The obtained solid matter was dried under reduced pressure at 60°C to obtain copolymer (1)-102 (yield: 42.6 g, 88%). １ H-NMR (600MHz, CF３ From the analysis results of the polyester backbone, the average degree of polymerization (m １ +m ２ ) was calculated to be 10, and the average degree of polymerization (n １ +n ２ ) was calculated to be 19. Furthermore, by GPC measurement, the number average molecular weight (Mn) was 11.5 × 10 ３ , weight average molecular weight (Mw) is 37.3 × 10 ３ The average degree of polymerization (m １ +m ２ ), average degree of polymerization (n １ +n ２ ) 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 and deprotect it, thereby obtaining compound (11)-101. N,N-dimethylacetamide (50.6 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. N,N-diisopropylethylamine (28.5 g, 221 mmol) was added to the solution after vacuum concentration, and the temperature was raised to 70°C. A solution obtained by dissolving compound (12)-103 (33.6 g, 10 mmol) in N,N-dimethylacetamide (234 g) containing lithium chloride at a concentration of 5% by mass at 70°C was then added. As a result, a solid matter precipitated. Next, the reaction solution containing this precipitate was transferred to a 1 L flask, and N,N-dimethylacetamide (219 g) containing lithium chloride at a concentration of 5% by mass (100%) was added thereto. 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 obtained solution, and the mixture was stirred for 18 hours. The obtained reaction solution was added dropwise to pure water (3.0 L) to precipitate a solid matter. The solid matter was recovered by filtration and washed twice with pure water (500 mL). The obtained solid matter was dried under reduced pressure at 60°C to obtain copolymer (1)-103 (yield: 41.2 g, 86%). １ H-NMR (600MHz, CF ３ From the analysis results of the polyester backbone, the average degree of polymerization (m １ +m ２ ) was calculated to be 12, and the average degree of polymerization (n １ +n ２ The number average molecular weight (Mn) was calculated to be 38. Furthermore, by GPC measurement, the number average molecular weight (Mn) was 14.9 × 10 ３ , and the weight average molecular weight (Mw) is 47.7 × 10 ３The average degree of polymerization (m １ +m ２ ), average degree of polymerization (n １ +n ２ ) 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, thereby deprotecting the compound and obtaining compound (11)-102. N,N-dimethylacetamide (105 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 (59.1 g, 457 mmol) was added, and the temperature was raised to 70 ° C. After that, a solution obtained by dissolving compound (12)-101 (14.9 g, 13 mmol) in N,N-dimethylacetamide (44.6 g) containing lithium chloride at a concentration of 5% by mass at 70 ° C. was 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), and a solid precipitated. 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 H-NMR (600MHz, CF ３ From the analysis results of the polyester backbone, the average degree of polymerization (m １ +m ２ ) was calculated to be 20, and the average degree of polymerization (n １ +n ２ Furthermore, the number average molecular weight (Mn) was calculated to be 13.0 × 10 ３, weight average molecular weight (Mw) is 36.8 × 10 ３ The average degree of polymerization (m １ +m ２ ), average degree of polymerization (n １ +n ２ ) 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, resulting in deprotection and obtaining compound (11)-102. N,N-dimethylacetamide (92.1 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. N,N-diisopropylethylamine (52.4 g, 405 mmol) was added to the solution after vacuum concentration, and the temperature was raised to 70°C. After this, a solution obtained by dissolving compound (12)-102 (19.8 g, 11 mmol) in N,N-dimethylacetamide (158 g) containing lithium chloride at a concentration of 5% by mass at 70°C was added. To the resulting reaction solution, N,N-dimethylacetamide (154 g) containing lithium chloride at a concentration of 5% by mass was further added, 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 the mixture was stirred for 18 hours. The resulting reaction solution was added dropwise to pure water (2.5 L), and potassium carbonate (180 g) was added, resulting in the precipitation of a solid. This solid was collected by filtration, washed twice with pure 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 H-NMR (600MHz, CF ３ From the analysis results of the polyester backbone, the average degree of polymerization (m １ +m ２ ) was calculated to be 21, and the average degree of polymerization (n１ +n ２ ) was calculated to be 20. Furthermore, by GPC measurement, the number average molecular weight (Mn) was 11.0 × 10 ３ , weight average molecular weight (Mw) is 31.3 × 10 ３ The average degree of polymerization (m １ +m ２ ), average degree of polymerization (n １ +n ２ ) 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 and deprotect it, thereby obtaining compound (11)-102. N,N-dimethylacetamide (16.7 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. N,N-diisopropylethylamine (9.46 g, 73 mmol) was added to the solution after vacuum concentration, and the temperature was raised to 70°C. A solution obtained by dissolving compound (12)-103 (6.71 g, 2.0 mmol) in N,N-dimethylacetamide (53.7 g) containing lithium chloride at a concentration of 5% by mass at 70°C was then added. To the resulting reaction solution, 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, 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. This solid was collected by filtration and washed twice with pure water (300 mL). The resulting solid was freeze-pulverized using liquid nitrogen, washed again with pure water, and dried at 60°C under reduced pressure to obtain copolymer (1)-106 (yield: 9.70 g, 85%). １ H-NMR (600MHz, CF ３ From the analysis results of the polyester backbone, the average degree of polymerization (m１ +m ２ ) was calculated to be 19, and the average degree of polymerization (n １ +n ２ ) was calculated to be 40. Furthermore, by GPC measurement, the number average molecular weight (Mn) was 13.3 × 10 ３ , weight average molecular weight (Mw) is 38.6 × 10 ３ The average degree of polymerization (m １ +m ２ ), average degree of polymerization (n １ +n ２ ) 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 and deprotect it, thereby obtaining compound (11)-103. N,N-dimethylacetamide (122 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 (68.4 g, 529 mmol) was added, and the temperature was raised to 70°C. A solution obtained by dissolving compound (12)-101 (10.1 g, 8.5 mmol) in N,N-dimethylacetamide (30.3 g) containing lithium chloride at a concentration of 5% by mass at 70°C was then 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. When the resulting reaction solution was added dropwise to pure water (2.0 L), a solid precipitated. The solid was collected by filtration, washed twice with pure water (500 mL), and dried under reduced pressure at 60°C. The obtained dried product (solid product) 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, yield: 93%). １H-NMR (600MHz, CF ３ From the analysis results of the polyester backbone, the average degree of polymerization (m １ +m ２ ) was calculated to be 36, and the average degree of polymerization (n １ +n ２ ) was calculated to be 14. Furthermore, by GPC measurement, the number average molecular weight (Mn) was 11.4 × 10 ３ , weight average molecular weight (Mw) is 33.7 × 10 ３ The average degree of polymerization (m １ +m ２ ), average degree of polymerization (n １ +n ２ ) 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 from compound (13)-103, resulting in deprotection and the production of compound (11)-103. N,N-dimethylacetamide (114 g) containing 5% by mass of lithium chloride was added to the resulting reaction solution, followed by vacuum concentration at 45°C to distill off dichloromethane and decomposition products of the Boc group. N,N-diisopropylethylamine (64.4 g, 498 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 (14.4 g, 8.0 mmol) in N,N-dimethylacetamide (115 g) containing 5% by mass of lithium chloride at 70°C was then added. To the resulting reaction solution, 1-hydroxy-7-azabenzotriazole (2.40 g, 18 mmol) and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (6.75 g, 35 mmol) were added, and the mixture was stirred for 18 hours. The resulting reaction solution was added dropwise to pure water (2.5 L), and sodium sulfate (400 g) was added, resulting in the precipitation of a solid. This solid was collected by filtration, washed three times with pure water (500 mL), and dried under reduced pressure at 60°C. The resulting dried product (solid) was washed twice more with pure water (300 mL), and dried under reduced pressure at 60°C, yielding copolymer (1)-108 (yield: 44.9 g, 89%). １ H-NMR (600MHz, CF ３ From the analysis results of the polyester backbone, the average degree of polymerization (m １ +m ２ ) was calculated to be 36, and the average degree of polymerization (n １ +n ２ ) was calculated to be 21. Furthermore, by GPC measurement, the number average molecular weight (Mn) was 11.7 × 10 ３ , and the weight average molecular weight (Mw) is 34.7 × 10 ３ The average degree of polymerization (m １ +m ２ ), average degree of polymerization (n１ +n ２ ) 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, thereby obtaining compound (11)-103. N,N-dimethylacetamide (85.8 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. N,N-diisopropylethylamine (48.1 g, 372 mmol) was added to the solution after vacuum concentration, 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 lithium chloride at a concentration of 5% by mass at 70°C was then added. Further, N,N-dimethylacetamide (142 g) containing lithium chloride at a concentration of 5% by mass was added to obtain a solution with a homogeneous appearance. 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 obtained reaction solution, and the mixture was stirred for 18 hours. The obtained reaction solution was dropped into pure water (2.5 L), and sodium sulfate (150 g) was added, resulting in the precipitation of a solid. This solid was recovered by filtration, washed twice with pure water (500 mL), and dried under reduced pressure at 60°C. The obtained 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 H-NMR (600MHz, CF ３ From the analysis results of the polyester backbone, the average degree of polymerization (m １ +m ２ ) was calculated to be 37, and the average degree of polymerization (n １ +n ２The number average molecular weight (Mn) was calculated to be 39. Furthermore, by GPC measurement, the number average molecular weight (Mn) was 11.5 × 10 ３ , and the weight average molecular weight (Mw) is 31.1 × 10 ３ The average degree of polymerization (m １ +m ２ ), average degree of polymerization (n １ +n ２ ) and the number average molecular weight (Mn), l was calculated to be 1.

[0177] <<Film Production>> [Example 10] 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 solution composition. 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 of this film, along with image data from 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>> Dumbbell-shaped No. 7 test pieces according to JIS K 6251:2017 were cut out from the film obtained above. A tensile test was performed on the test pieces at room temperature in accordance with JIS K 6251:2017 using a precision universal testing machine (Shimadzu Corporation, "EZ-SX") at a tensile 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 performed on each of these test pieces, for a total of five tensile tests. The average values ​​of the five measured values ​​of maximum stress and elongation at break were calculated, and these average values ​​were used as the measured values ​​of maximum stress and elongation at break, respectively. The results are shown in Table 1.

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

[0180] Example 16 A solution composition was obtained by dissolving the copolymer (1)-106 (1.5 g) obtained in Example 7 in formic acid (3 mL). The composition was applied to one side of a polytetrafluoroethylene (PTFE) sheet heated to 60°C by a bar coating method with a gap thickness of 0.25 mm. The composition was then heated to remove the solvent component from the composition, thereby producing a transparent film (thickness: approximately 100 μm) containing the copolymer (1)-106. Image data of this film are shown in FIG. 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. １ From the results of H-NMR analysis, the average degree of polymerization (n １ +n ２ -2) was calculated to be 146. Furthermore, by GPC measurement, the number average molecular weight (Mn) was 22.9 × 10 ３ , and the weight average molecular weight (Mw) is 84.2 × 10 ３ The calculated value was: Compound (12)-104 (0.5 g) was dissolved in formic acid (3 mL) and filtered through a cotton plug to obtain a solution composition. As in Example 1, the composition was poured onto one side of a glass plate, and then the composition was heated to 60°C to remove the solvent component from the composition, thereby attempting to prepare a film containing Compound (12)-104. However, as shown in Figure 6, cracks occurred in most of the obtained film, 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 solution composition. 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 was obtained, and instead a hard and brittle solid was obtained.

[0183]

[0184] As is clear from the above results, in Examples 1 to 9, copolymer (1) was obtained in good yield. Furthermore, 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 FIG. 5, these films had high transparency.

[0185] In contrast, as is clear from FIG. 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 FIG. 7, in Comparative Example 2, a film itself could not be formed.

[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) (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; 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; 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; 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; 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; 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 above 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 above R １ and R ２ and each independently represent a chain alkylene group having 3 to 5 carbon atoms.

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

7. The above n １ and n ２ The copolymer according to claim 1 or 2, wherein the total value of 8. The above 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 containing the copolymer according to claim 1 or 2.

10. The following general formula (11): (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 more; 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; R ３ is a chain alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms; １ and p ２ and each independently represents an integer of 1 to 11. (In the formula, n １ and n ２ are each independently an integer of 1 or more; 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; 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. (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 from each other.

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