Coating resin composition, polymer, method for producing polymer, coating film, and method for producing the same.

Abstract

A resin composition for coating, which contains a polymer having a structural unit represented by formula (I), a structural unit represented by formula (II) and a terminal structure represented by formula (III-A) or (III-B), wherein the content of the structural unit represented by formula (I) is 10% by mass or more and the content of the structural unit represented by formula (II) is 10% by mass or more in the polymer; this polymer; a method for producing a polymer having a structural unit represented by formula (II); a coating film which contains this polymer; and a method for forming a coating film.

Description

[Technical Field]

[0001] The present invention relates to a coating resin composition, a polymer, a method for producing a polymer, a coating film, and a method for producing the same. [Background technology]

[0002] Polyesters containing structural units derived from aromatic diol compounds and aromatic dicarboxylic acid compounds, and polycarbonates containing structural units derived from aromatic diol compounds and phosgene, are excellent in terms of heat resistance and mechanical strength, and are widely used industrially. For example, Patent Document 1 describes a film-forming resin mainly composed of a polyester comprising residues of divalent carboxylic acids having biphenyl, diphenyl ether, and cyclohexane structures, and residues of divalent phenols. It states that by controlling the amount of free divalent carboxylic acid to 0.01 to 300 ppm, the electrical properties can be stabilized when applied to capacitors, electrophotographic photoreceptors, etc. Furthermore, Patent Document 2 describes a resin composition comprising 100 parts by mass of a polymer resin composition in which 95 to 5% by mass of polyarylate component (A) and 5 to 95% by mass of polycarbonate component (B) are combined to make 100% by mass, and 0.01 to 1 part by mass of a silicone compound (C) having a glycidyl group of a specific structure. According to Patent Document 2, molded articles using this composition possess both heat resistance and transparency, and are suitable for automotive lamp peripheral parts, lighting fixture reflectors, and the like. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2008-31347 [Patent Document 2] Japanese Patent Publication No. 2003-292756 [Overview of the project] [Problems that the invention aims to solve]

[0004] In the industrial applications of polymers such as polyester and polycarbonate, it is common to mold the polymer to the desired shape or to dissolve the polymer in a solvent and apply it to a substrate to form a coating film. Furthermore, to impart desired functionality to the coating film, the functionality and mechanical properties of the polymer itself are improved, or the polymer is mixed with a functional material before application. To obtain a desired functional coating film by mixing a polymer with a functional material, compatibility between the polymer and the functional material is crucial, as is maintaining film-forming properties to achieve a uniform film without defects. Additionally, a coating film with low haze is easier to apply as an optical film, etc.

[0005] The present invention aims to provide a coating resin composition that can achieve excellent film-forming properties and enables the formation of a coating film with excellent heat resistance and abrasion resistance, a polymer suitable as a main component or binder of this coating resin composition, and a suitable method for producing the same. Furthermore, the present invention aims to provide a coating film that has excellent film-forming properties during its formation, excellent heat resistance and abrasion resistance in itself, and a method for producing the same. [Means for solving the problem]

[0006] The above-mentioned problems of the present invention were solved by the following means. <1> The polymer comprises a structural unit represented by the following formula (I), a structural unit represented by the following formula (II), and an end structure represented by the following formula (III-A) or (III-B). A coating resin composition comprising the above polymer, wherein the content of the structural unit represented by formula (I) is 10% by mass or more, and the content of the structural unit represented by formula (II) is 10% by mass or more. [ka] In the formula, Me represents methyl. [ka] [ka] In the formula, R a and R b R represents a monovalent organic group. In formula (III-A), R a is R a The carbon atom inside bonds with the oxygen atom shown in formula (III-A), and in formula (III-B), R b is R b The carbonyl group shown in formula (III-B) is bonded to the carbon dioxide within it. * indicates the bonding site. <2> The polymer contains 20% by mass or more of the structural unit represented by the above formula (I). <1> The coating resin composition described above. <3> The polymer contains 20% by mass or more of the structural unit represented by the above formula (II). <1> or <2> The coating resin composition described above. <4> In the above polymer, the terminal structure represented by the above formula (III-A) is represented by the following formula (III-A-1), <1> ~ <3> A coating resin composition as described in any one of the following. [ka] In the formula, R d represents an alkyl group, aryl group, or halogen atom, and s is an integer from 0 to 5. * indicates a bonding site. <5> Contains a solvent <1> ~ <4> A coating resin composition as described in any one of the following. <6> The functional material contains an aromatic ring compound including a benzene ring, and the mass ratio of the polymer content to the functional material content is such that the polymer / functional material = 90:10 to 50:50. <1> ~ <5> A coating resin composition as described in any one of the following. <7> It has a structural unit represented by the following formula (I), a structural unit represented by the following formula (II), and a terminal structure represented by the following formula (III-A) or (III-B). A polymer in which the structural unit represented by the above formula (I) is 10% by mass or more and the content of the structural unit represented by the above formula (II) is 10% by mass or more in the above polymer.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Advantages of the Invention

[0007] The coating resin composition of the present invention achieves excellent film-forming properties and enables the formation of a coating film with excellent heat resistance and abrasion resistance. The polymer of the present invention is suitable as a main component or binder of the above-mentioned coating resin composition. The polymer manufacturing method of the present invention allows for the efficient acquisition of a polymer with a molecular weight suitable for use as a constituent polymer of a coating film. The coating film of the present invention has excellent film-forming properties, excellent heat resistance, and excellent abrasion resistance. The coating film formation method of the present invention makes it possible to obtain a coating film that achieves excellent film-forming properties while also having excellent heat resistance and abrasion resistance. [Modes for carrying out the invention]

[0008] In the description of this invention, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower limit and upper limit, respectively. In the description of this invention, substituents, linking groups, etc. (hereinafter referred to as "substituents, etc.") that are not explicitly stated as substituted or unsubstituted are considered to have appropriate substituents. Therefore, even when simply referred to as "~group" (e.g., "alkyl group") in this specification, this "~group" (e.g., "alkyl group") includes not only the unsubstituted form (e.g., "unsubstituted alkyl group") but also the form having a substituent (e.g., "substituted alkyl group"). The same applies to compounds that are not explicitly stated as substituted or unsubstituted. Preferred substituents include those selected from substituent T described below. In the description of the present invention, when there are multiple substituents, or when multiple substituents are specified simultaneously or alternatively, it means that each substituent may be the same as or different from the others. Furthermore, even if not specifically stated otherwise, when multiple substituents are adjacent to each other, they may be linked to each other or fused to form a ring. In this specification, if a polymer has multiple components of the same designation (designated by the same general formula), each component may be identical or different from the others.

[0009] [Coating resin composition] The coating resin composition of the present invention comprises a polymer having a structural unit represented by the following formula (I), a structural unit represented by the following formula (II), and an end structure represented by formula (III-A) or (III-B). This polymer may hereafter be simply referred to as "the above polymer."

[0010] [ka]

[0011] In the formula, Me represents methyl. In formula (I), the substituent shown to the right of Me, which is bonded to the carbon atom to which Me is attached, is isobutyl.

[0012] In the above polymer, the content of the structural unit represented by formula (I) is 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 50% by mass or more. Furthermore, the content of the structural unit represented by formula (I) in the above polymer is usually 70% by mass or less, and is also preferably 65% ​​by mass or less.

[0013] [ka]

[0014] In the above polymer, the content of the structural unit represented by formula (II) is 10% by mass or more, preferably 20% by mass or more, more preferably 25% by mass or more, even more preferably 30% by mass or more, and particularly preferably 40% by mass or more. Furthermore, the content of the structural unit represented by formula (II) in the above polymer is usually 60% by mass or less, and is also preferably 50% by mass or less.

[0015] By setting the content of the structural units represented by formula (I) and formula (II) in the polymer within the above range, the polymer can be made to possess both rigidity and appropriate flexibility, thereby further enhancing the abrasion resistance of the coating film. Furthermore, when functional materials are used in combination, the compatibility between the functional materials and the polymer can be improved, ensuring the desired film-forming properties more reliably.

[0016] [ka]

[0017] In the formula, R a and R b R represents a monovalent organic group. In formula (III-A), R a is R a The carbon atom inside bonds with the oxygen atom shown in formula (III-A), and in formula (III-B), R b is R b The carbonyl group shown in formula (III-B) is bonded to the carbonic acid by the carbon atom inside. a and R b Preferably, it does not contain a fluorine atom. * indicates a bonding site. Note that * also indicates a bonding site in the following formula.

[0018] R a and R b The monovalent organic group that can be taken is preferably an alkyl group or an aryl group. a and R b The alkyl group that can be selected may be linear or branched, and its number of carbon atoms (including substituents if present) is preferably 1 to 13, more preferably 1 to 8, also preferably 1 to 6, and also preferably 1 to 3. a and R b In the case of an alkyl group, a smaller number of carbon atoms is preferable from the viewpoint of wear resistance. R a and R bThe aryl group that can be selected has a carbon number of 6 to 30 (including substituents if present), more preferably 6 to 25, even more preferably 6 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. a and R b The aryl group that can be selected is preferably a phenyl group.

[0019] The terminal structure represented by the above formula (III-A) is preferably represented by the following formula (III-A-1).

[0020] [ka]

[0021] In the formula, R d is an alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group (preferably an alkylcarbonyloxy group or arylcarbonyloxy group, more preferably an alkylcarbonyloxy group), or halogen atom, and s is an integer from 0 to 5. R d The group is preferably an alkyl group, an alkoxy group, an alkoxycarbonyl group, or an acyloxy group, more preferably an alkyl group or an alkoxy group, and even more preferably an alkyl group. R d The alkyl group that can be used may be a linear, branched, or cyclic alkyl group. d The number of carbon atoms in the alkyl group that can be selected (including the substituent if it has substituents) is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. d The alkyl group that can be selected is preferably a methyl group or a t-butyl group, with a methyl group being more preferred. d If the group is a methyl group, then s is preferably 2 or 3, and more preferably 3. R dThe number of carbon atoms in the aryl group that can be taken as (including the substituent if it has a substituent) is preferably 6 to 26, more preferably 6 to 20, even more preferably 6 to 15, particularly preferably 6 to 12, and most preferably 6 to 10. d Preferred specific examples of aryl groups that can be used include phenyl group, 4-methoxyphenyl group, 4-acetoxyphenyl group, 1-naphthyl group, and 2-naphthyl group. R d The number of carbon atoms (including substituents if substituents are present) of the alkoxy group, alkoxycarbonyl group, and acyloxy group that can be selected is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. This preferred number of carbon atoms for the alkoxycarbonyl group and acyloxy group is the number of carbon atoms excluding the carbon atoms that form the carbonyl group in each group. R d The aryl group in the aryloxy group and aryloxycarbonyl group that can be taken as is preferably 6 to 30 carbon atoms (including substituents if substituents are present), more preferably 6 to 25, even more preferably 6 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. d The aryl group that can be selected is preferably a phenyl group, a 4-methoxyphenyl group, or a 4-acetoxyphenyl group, and more preferably a phenyl group. s is preferably an integer between 0 and 3.

[0022] Examples of preferred terminal structures represented by the above formulas (III-A) to (III-A-1) include those represented by the following formulas.

[0023] [ka]

[0024] [ka]

[0025] A preferred terminal structure represented by the above formula (III-B) is, for example, one represented by the following formula.

[0026] [ka]

[0027] The proportion of the total terminal structures represented by formula (III-A) or (III-B) in all terminal structures of the above polymer is preferably 50 to 100 mol%, more preferably 70 to 100 mol%, and even more preferably 90 to 100 mol%. The terminal structures represented by formula (III-A) or (III-B) can be introduced, for example, by using monovalent phenol compounds or monovalent carboxylic acid chlorides as terminal encapsulants in solution polymerization or interfacial polymerization. Alternatively, after obtaining a polymer having phenolic hydroxyl groups as terminal structures, the structure of (III-B) can be derived by acyling the phenolic hydroxyl groups in a polymer reaction.

[0028] The polymer described above may contain, in its remainder after removing the structural units represented by formulas (I) and (II), at least one structural unit represented by, for example, the following formula (IA) or (IB). However, the structural unit represented by formula (IA) is excluded from the structural unit represented by formula (I).

[0029] [ka]

[0030] In the above formula (IA), R 1 (R) represents an unsubstituted chain-like branched alkyl group having 4 or more carbon atoms. 1 The chain-branched alkyl group has no substituents. 1 The number of carbon atoms is preferably 4 to 20, more preferably 4 to 15, even more preferably 4 to 10, and particularly preferably 4 to 8. 1 It is also preferable that the number of carbon atoms is 5 or more. Therefore, R1 The number of carbon atoms is preferably 5 to 20, preferably 6 to 15, preferably 6 to 10, and preferably 7 to 8. R 1 Preferred specific examples include 1-methylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 4-methylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1,3-dimethylpentyl group, 1,4-dimethylpentyl group, 2,4,4-trimethylpentyl group, 1-ethylheptyl group, 2-ethylheptyl group, 3-methylhexyl group, 11-methyldodecyl group, and the like. Among them, R 1 Preferred groups include 1-methylpropyl group, 1-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1-ethylbutyl group, 1-ethylpentyl group, 1-ethylhexyl group, 1-ethylheptyl group, and 2,4,4-trimethylpentyl group, with 1-ethylbutyl group, 1-ethylpentyl group, 2,4,4-trimethylpentyl group, and 1-ethylheptyl group being more preferred.

[0031] R 2 This represents a hydrogen atom, a linear alkyl group, or an aryl group. R 2 The number of carbon atoms in the linear alkyl group that can be selected is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. 2 The linear alkyl group that can be used is preferably a methyl group or an ethyl group, with a methyl group being more preferred. R 2 The number of carbon atoms in the aryl group that can be taken is preferably 6 to 26, more preferably 6 to 20, even more preferably 6 to 15, particularly preferably 6 to 12, and most preferably 6 to 10. 2Preferred specific examples of aryl groups that can be used include phenyl, 4-methoxyphenyl, 4-acetoxyphenyl, 1-naphthyl, and 2-naphthyl. R 2 Preferably, it is a hydrogen atom or a methyl group.

[0032] R 3 This represents a hydrogen atom, an alkyl group, or an aryl group. R 3 The alkyl group that can be used may be a linear, branched, or cyclic alkyl group. 3 The number of carbon atoms in the alkyl group that can be selected is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. 3 The alkyl group that can be selected is preferably a methyl group or an ethyl group, with a methyl group being more preferred. R 3 The aryl groups that can be taken as are R 2 This is synonymous with the aryl group that can be adopted, and the preferred form is also the same. R 3 Preferably, it is a hydrogen atom or a methyl group.

[0033] In the above equation (IA), R 1 and R 2 They do not bond to form a ring structure. Also, R 1 The number of carbon atoms and the two R 3 The total number of carbon atoms is 6 or more, preferably 6 to 20, more preferably 6 to 16, and even more preferably 6 to 13.

[0034] [ka]

[0035] In the above formula (IB), R 4 This represents a hydrogen atom, a linear alkyl group, or an aryl group. R 4 The linear alkyl groups that can be taken as are R 2 This is synonymous with a linear alkyl group that can be adopted, and the preferred form is also the same. R 4 The aryl group that can be taken as is R 2 This is synonymous with the aryl group that can be adopted, and the preferred form is also the same. R 5 R represents a hydrogen atom, an alkyl group, or an aryl group. 5 The alkyl groups or aryl groups that can be taken as are R 3 This is synonymous with an alkyl group or aryl group that can be adopted, and the preferred form is the same. R 5 Preferably, it is a hydrogen atom or a methyl group.

[0036] n is an integer between 2 and 20. Preferably, n is between 3 and 20, more preferably 4 and 20, even more preferably 4 and 15, particularly preferably 5 and 13, and most preferably 6 and 10.

[0037] If the above polymer has a structural unit represented by the above formula (IA), R 2 Preferably, R is a hydrogen atom, an unsubstituted linear alkyl group, or an unsubstituted aryl group. 1 and R 2 It is preferable that the whole is composed only of carbon atoms and hydrogen atoms.

[0038] Specific examples of the structural unit represented by the above formula (IA) are shown below, but the present invention is not limited to these specific examples. In the following formulas, Me represents methyl.

[0039] [ka]

[0040] Specific examples of structural units represented by the above formula (IB) are shown below, but the present invention is not limited to these specific examples.

[0041] [ka]

[0042] [ka]

[0043] The polymer described above may contain, for example, a structural unit represented by the following formula (IV) in the remainder after removing the structural units represented by formulas (I), (IA), (IB), and (II). The structural unit represented by the following formula (IV) is not incorporated into the polymer as a structural unit represented by formula (II).

[0044] [ka]

[0045] In formula (IV), R c represents an alkyl group, aryl group, or halogen atom, and r is an integer from 0 to 4. R c The alkyl and aryl groups that can be taken as are R 3 This is synonymous with alkyl groups and aryl groups that can be adopted, and the preferred form is the same. r is preferably between 0 and 3.

[0046] Specific examples of structural units represented by the above formula (IV) are shown below, but the present invention is not limited to these specific examples.

[0047] [ka]

[0048] The polymer described above, excluding the structural units represented by formulas (I), (IA), (IB), (II), and (IV), may contain, for example, at least one structural unit represented by the following formula (IC).

[0049] [ka]

[0050] In the above formula (IC), R c and r are R in equation (IV) above, respectively. c And is synonymous with r, and the preferred form is also the same. W 1 represents an oxygen atom, a sulfur atom, or a hydrocarbon group having 1 to 15 carbon atoms. However, the structural unit represented by formula (IC) is a different structural unit from the structural units represented by formulas (IA) and (IB). In other words, in this invention, even if a structure is included in the structural unit represented by formula (IC), if it is also included in the structural unit represented by either formula (IA) or (IB), it is interpreted as a structural unit represented by either formula (IA) or (IB), rather than a structural unit represented by formula (IC). W 1 As for hydrocarbon groups having 1 to 15 carbon atoms, hydrocarbon groups having 1 to 12 carbon atoms are preferred, and hydrocarbon groups having 1 to 10 carbon atoms are more preferred.

[0051] Divalent phenol compounds that derive the structural unit represented by the above formula (IC) include 1,1-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-methyl-2-hydroxyphenyl)methane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)methane (TM Bisphenol F), 1,1-bis(4-hydroxyphenyl)cyclohexane (Bisphenol Z), 2,2-bis(4-hydroxyphenyl)propane (Bisphenol A), and 2,2-bis(3-methyl-4-hydroxyphenyl). Propane (bisphenol C), 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane (TM bisphenol A), 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 1,1-bis(3-methyl-4-hydroxyphenyl)methane, 4,4'-biphenol, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-2-methylpropane, 1,1-bis(4-hydroxyphenyl)-1-phenylmethane, 1,1 -Bis(3-methyl-4-hydroxyphenyl)cyclohexane, 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane, bisphenol fluorene, 1,1-bis(2-methyl-4-hydroxy-5-tert-butylphenyl)-2-methylpropane, 4,4'-[1,4-phenylene-bis(2-propylidene] (n)-bis(3-methyl-4-hydroxyphenyl)], 1,1-bis(3-phenyl-4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxyphenyl ether, bis(2-hydroxyphenyl)methane, 2,4'-methylenebisphenol, bis(3-methyl-4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)propane, 1,1-bis(2-hydroxy-5-methylphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-3-methylbutane, bis(2-hydroxy-3,5-dimethylphenyl)methane, 1,1-Bis(4-hydroxyphenyl)cyclopentane, 1,1-Bis(3-methyl-4-hydroxyphenyl)cyclopentane, 3,3-Bis(4-hydroxyphenyl)pentane, 3,3-Bis(3-methyl-4-hydroxyphenyl)pentane, 3,3-Bis(3,5-dimethyl-4-hydroxyphenyl)pentane, 2,2-Bis(2-hydroxy-3,5-dimethylphenyl)propane, 1,1-Bis(3-methyl-4-hydroxyphenyl)-1-phenylethane, 1,1-Bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, Bis(2-hydroxy-3-tert-butyl-5-methylphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, terpene diphenol, 1,1-bis(3-tert-butyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(2-methyl-4-hydroxy-5-tert-butylphenyl)-2-methylpropane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3,5-di-tert-butyl-4-hydroxyphenyl)methane, 1,1-bis(3,5-disec-butyl-4-hydroxyphenyl) hydroxyphenyl)methane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(2-hydroxy-3,5-ditert-butylphenyl)ethane, bis(3-nonyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-ditert-butyl-4-hydroxyphenyl)propane, bis(2-hydroxy-3,5-ditert-butyl-6-methylphenyl)methane, 1,1-bis(3-phenyl-4-hydroxyphenyl)-1-phenylethane, bis(3-fluoro-4-hydroxyphenyl)meth , bis(2-hydroxy-5-fluorophenyl)methane, 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(3-fluoro-4-hydroxyphenyl)propane, bis(3-fluoro-4-hydroxyphenyl)-phenylmethane, bis(3-fluoro-4-hydroxyphenyl)-(p-fluorophenyl)methane, bis(4-hydroxyphenyl)-(p-fluorophenyl)methane, 2,2-bis(3-chloro-4-hydroxy-5-methylphenyl)propane, 2,2-bis(3,5-Dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 1,1-bis(3,5-dibromo-4-hydroxyphenyl)methane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(3-nitro-4-hydroxyphenyl)propane, 3,3'-dimethyl-4,4'-biphenol, 3,3',5,5'-tetramethyl-4,4'-biphenol, 3,3',5,5'-tetratert-butyl-4,4'-biphenol, bis(4-hydroxyphenyl) Biphenyl) ketone, 3,3'-difluoro-4,4'-biphenol, 3,3',5,5'-tetrafluoro-4,4'-biphenol, bis(4-hydroxyphenyl)dimethylsilane, bis(3-methyl-4-hydroxyphenyl) ether, bis(3,5-dimethyl-4-hydroxyphenyl) ether, bis(2,3,5-trimethyl-4-hydroxyphenyl)-phenylmethane, 1,1-bis(3-tert-butyl-4-hydroxyphenyl)-1-phenylethane, 1,1-bis(3,5-ditert-butyl-4-hydroxyphenyl) (Loxyphenyl)-1-phenylethane, 1,1-bis(2-methyl-4-hydroxy-5-cyclohexylphenyl)-2-methylpropane, 1,1-bis(2-hydroxy-3,5-ditert-butylphenyl)ethane, isatin bisphenol, isatin biscresol, 2,2',3,3',5,5'-hexamethyl-4,4'-biphenol, bis(2-hydroxyphenyl)methane, 2,4'-methylenebisphenol, 1,2-bis(4-hydroxyphenyl)ethane, 2-(4-hydroxyphenyl)-2-(2-hydro Xyphenyl)propane, bis(2-hydroxy-3-allylphenyl)methane, 1,1-bis(2-hydroxy-3,5-dimethylphenyl)-2-methylpropane, 1,1-bis(2-hydroxy-5-tert-butylphenyl)ethane, bis(2-hydroxy-5-phenylphenyl)methane, bis(2-methyl-4-hydroxy-5-cyclohexylphenyl)methane, 1,2-bis(3,5-ditert-butyl-4-hydroxyphenyl)ethane, bis(2-hydroxy-3,5-ditert-butylphenyl)methane, 2,2-Bis(3-styryl-4-hydroxyphenyl)propane, 1,1-Bis(4-hydroxyphenyl)-1-(p-nitrophenyl)ethane, Bis(3,5-difluoro-4-hydroxyphenyl)methane, Bis(3,5-difluoro-4-hydroxyphenyl)phenylmethane, Bis(3,5-difluoro-4-hydroxyphenyl)diphenylmethane, Bis(3-fluoro-4-hydroxyphenyl)diphenylmethane, 2,2-Bis(3-chloro-4-hydroxyphenyl)propane, 3,3 ',5,5'-tetratert-butyl-2,2'-biphenol, 2,2'-diallyl-4,4'-biphenol, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5,5-tetramethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,4-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3-dimethyl-5-ethyl-cyclohexane, 1,1-bis( 4-hydroxyphenyl)-3,3,5-trimethylcyclopentane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(3,5-diphenyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(3-phenyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1 ,1-bis(3,5-dichloro-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene, 1,1-bis(3,5-dibromo-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, bis(4-hydroxyphenyl)sulfone, bis(2-hydroxyphenyl)sulfone, bis(3,5-dimethyl-4-hydroxyphenyl)sulfone, bis(3,Examples include 5-diethyl-4-hydroxyphenyl)sulfone, bis(3-methyl-4-hydroxyphenyl)sulfone, bis(3-ethyl-4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfide, bis(3,5-dimethyl-4-hydroxyphenyl)sulfide, bis(3,5-diethyl-4-hydroxyphenyl)sulfide, bis(3-methyl-4-hydroxyphenyl)sulfide, bis(3-ethyl-4-hydroxyphenyl)sulfide, 2,4-dihydroxydiphenylsulfone, 4,4'-(α-methylbenzylidene)bisphenol, 1,1-bis(4-hydroxy-3-methylphenyl)ethane, and bisphenol E. In other words, the structural unit represented by the above formula (IC) can originate from the above-mentioned divalent phenol compounds.

[0052] Among the divalent phenol compounds mentioned above, structural units derived from compounds selected from 4,4'-(α-methylbenzylidene)bisphenol, 1,1-bis(4-hydroxy-3-methylphenyl)-ethane, bisphenol E, bisphenol C, and bisphenol Z are preferred from the viewpoint of further improving the abrasion resistance of the coating film.

[0053] The content of the structural unit represented by the above formula (IC) is preferably 0 to 40% by mass, more preferably 0 to 30% by mass, and even more preferably 0 to 20% by mass in the above polymer.

[0054] The polymer may also preferably contain, for example, dicarboxylic acid-derived structural units as described below, in the remainder of the polymer after removing the structural units represented by formulas (I), (IA), (IB), (II), (IV), and (IC). 4,4'-Diphenyl ether dicarboxylic acid, 1,4-Cyclohexane dicarboxylic acid, Terephthalic acid, Isophthalic acid, Orthophthalic acid, 1,4-Naphthalenedicarboxylic acid, 2,3-Naphthalenedicarboxylic acid, 2,6-Naphthalenedicarboxylic acid, Adipic acid, Pimelic acid, Suberic acid, Azelaic acid, Sebacic acid, Undecanediic acid, Dodecanediic acid, Tridecanediic acid, Tetradecanediic acid, Pentadecanediic acid, Octadecanedioic acid, Nonadecanedioic acid, Eicosanedioic acid, etc.

[0055] Among the dicarboxylic acid-derived structural units mentioned above, 4,4'-diphenyl ether dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and terephthalic acid-derived structural units are preferred from the viewpoint of further improving the wear resistance of the coating film.

[0056] Other terminal structures besides those represented by the above formulas (III-A) or (III-B) include those represented by the following formulas. *-H *-OH

[0057] If the polymer of the present invention has a structural unit represented by formula (I) as an end structure other than those represented by formula (III-A) or (III-B), the end can be represented, for example, as follows.

[0058] [ka]

[0059] If the polymer of the present invention has a structural unit represented by formula (IA) as an end structure other than those represented by formula (III-A) or (III-B), the end can be represented, for example, as follows.

[0060] [ka]

[0061] If the polymer of the present invention has a structural unit represented by the above formula (IB) as an end structure other than the above formula (III-A) or (III-B), the end can be represented, for example, as follows.

[0062] [ka]

[0063] If the polymer of the present invention has a structural unit represented by the above formula (IC) as an end structure other than the above formula (III-A) or (III-B), the end can be represented, for example, as follows.

[0064] [ka]

[0065] If the polymer of the present invention has a structural unit represented by formula (II) as an end structure other than those represented by formula (III-A) or (III-B), the end can be represented, for example, as follows.

[0066] [ka]

[0067] It is preferable that the end structures represented by *-H and *-OH are not included, but if they are included, they are preferably 0 to 50 mol%, more preferably 0 to 30 mol%, and even more preferably 0 to 10 mol% of all end structures of the polymer.

[0068] The weight-average molecular weight of the above polymer is preferably 50,000 to 250,000, more preferably 80,000 to 180,000, and even more preferably 100,000 to 150,000. In this invention, unless otherwise specified, the molecular weight of the polymer refers to the weight-average molecular weight. The weight-average molecular weight can be determined as the molecular weight in terms of polystyrene by gel permeation chromatography (GPC). Due to the solvent solubility of the polymer of this invention, tetrahydrofuran can be preferably used as the eluent. The above preferred range of weight-average molecular weight is based on the weight-average molecular weight in terms of polystyrene when tetrahydrofuran is used as the eluent.

[0069] Examples of substituent T include the following: Alkyl groups (preferably alkyl groups having 1 to 20 carbon atoms, e.g., methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl groups (preferably alkenyl groups having 2 to 20 carbon atoms, e.g., vinyl, allyl, oleyl, etc.), alkynyl groups (preferably alkynyl groups having 2 to 20 carbon atoms, e.g., ethynyl, butadiinyl, phenylethynyl, etc.), cycloalkyl groups (preferably cycloalkyl groups having 3 to 20 carbon atoms, e.g., cy (e.g., chloropropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl), aryl group (preferably an aryl group having 6 to 26 carbon atoms, for example, phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), heterocyclic group (preferably a heterocyclic group having 2 to 20 carbon atoms, more preferably a 5 or 6-membered heterocyclic ring having at least one oxygen atom, sulfur atom, or nitrogen atom. Heterocyclic groups include aromatic heterocyclic groups and aliphatic heterocyclic groups. For example, tetrahydropyran ring group, tetrahydro (Furan ring group, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, etc.), alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, e.g., methoxy, ethoxy, isopropyloxy, benzyloxy, etc.), aryloxy group (preferably an aryloxy group having 6 to 26 carbon atoms, e.g., phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), heterocyclic oxy group (a group in which an -O- group is bonded to the above heterocyclic group), alkoxycarbonyl group (preferably (Preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, e.g., ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), aryloxycarbonyl group (preferably an aryloxycarbonyl group having 6 to 26 carbon atoms, e.g., phenoxycarbonyl, 1-naphthyloxycarbonyl, 3-methylphenoxycarbonyl, 4-methoxyphenoxycarbonyl, etc.), amino group (preferably an amino group having 0 to 20 carbon atoms, an alkylamino group, or an arylamino group, e.g., amino(-NH2), N,N-dimethylamino, N,N-diethylamino, N-ethylamino, anilino, etc.), sulfamoyl group (preferably a sulfamoyl group having 0 to 20 carbon atoms, for example, N,N-dimethylsulfamoyl, N-phenylsulfamoyl, etc.), acyl group (including alkylcarbonyl group, alkenylcarbonyl group, alkynylcarbonyl group, arylcarbonyl group, heterocyclic carbonyl group, preferably an acyl group having 1 to 20 carbon atoms, for example, acetyl, propionyl, butyryl, octanoyl, hexadecanoyl, acryloyl, methacryloyl, crotonoyl, benzoyl, naphthoyl, nicotinoyl, etc.), acyloxy group (alkylcarbonyloxy group, aryl This includes kenylcarbonyloxy groups, alkynylcarbonyloxy groups, arylcarbonyloxy groups, and heterocyclic carbonyloxy groups, preferably acyloxy groups having 1 to 20 carbon atoms (e.g., acetyloxy, propionyloxy, butyryloxy, octanoyloxy, hexadecanoyloxy, acryloyloxy, methacryloyloxy, crotonoyloxy, benzoyloxy, naphthoyloxy, nicotinoyloxy, etc.), allyloyloxy groups (preferably allyloyloxy groups having 7 to 23 carbon atoms, for example, benzoyloxy, etc.), and carbamoyl groups (preferably carbamoyl groups having 1 to 20 carbon atoms, for example, N,N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.), acylamino group (preferably an acylamino group having 1 to 20 carbon atoms, e.g., acetylamino, benzoylamino, etc.), alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms, e.g., methylthio, ethylthio, isopropylthio, benzylthio, etc.), arylthio group (preferably an arylthio group having 6 to 26 carbon atoms, e.g., phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio, etc.), heterocyclic thio group (a group in which an -S- group is bonded to the above heterocyclic group), alkylsulfonyl group (preferably Or alkylsulfonyl groups having 1 to 20 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, etc.), arylsulfonyl groups (preferably arylsulfonyl groups having 6 to 22 carbon atoms, for example, benzenesulfonyl, etc.), alkylsilyl groups (preferably alkylsilyl groups having 1 to 20 carbon atoms, for example, monomethylsilyl, dimethylsilyl, trimethylsilyl, triethylsilyl, etc.), arylsilyl groups (preferably arylsilyl groups having 6 to 42 carbon atoms, for example, triphenylsilyl, etc.), phosphoryl groups (preferably phosphate groups having 0 to 20 carbon atoms, for example, -OP(=O)(R, P 2) A phosphonyl group (preferably a phosphonyl group having 0 to 20 carbon atoms, for example, -P(=O)(R P 2) A phosphinyle group (preferably a phosphinyle group having 0 to 20 carbon atoms, for example, -P(R P 2) Examples include sulfo groups (sulfonic acid groups), carboxyl groups, hydroxyl groups, sulfanyl groups, cyano groups, and halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.). P is a hydrogen atom or a substituent (preferably a group selected from substituent T). Furthermore, each of the groups listed as substituent T may have the above substituent T as a substituent.

[0070] The above polymer can be produced by polycondensing a monomer that gives a structural unit represented by formula (I) and a monomer that gives a structural unit represented by formula (II) with other monomers as needed, using a conventional method.

[0071] The method for producing the above polymer is not particularly limited. Examples include interfacial polymerization and solution polymerization, with interfacial polymerization being preferred. Interfacial polymerization is a polymerization method that obtains polyester by mixing a divalent carboxylic acid halide dissolved in an organic solvent that is immiscible with water with a divalent phenol dissolved in an alkaline aqueous solution. Literature on interfacial polymerization includes WM EARECKSON, J. Poly. Sci., XL399, 1959 and Japanese Patent Publication No. 40-1959. Compared to solution polymerization, interfacial polymerization has a faster reaction rate, which can suppress the hydrolysis of the acid halide, and as a result, a high molecular weight resin can be obtained. More specifically, an alkaline aqueous solution of divalent phenol is prepared as the aqueous phase, followed by the addition of a polymerization catalyst. Meanwhile, as the organic phase, a divalent carboxylic acid halide is dissolved in a solvent that is immiscible with water but dissolves the polymer. This solution is then mixed with the aforementioned alkaline solution, and the polymerization reaction is carried out at a temperature of preferably 50°C or lower for 1 to 8 hours while stirring to obtain the desired polymer solution. It is not necessary for all of the divalent carboxylic acid halide to dissolve in the organic phase.

[0072] In the polymer production method of the present invention, the following method A may be used. This method is particularly effective when the divalent carboxylic acid halide does not dissolve in the solvent of the organic layer, or has low solubility. <Method A> As the aqueous phase, an alkaline aqueous solution of divalent phenol is prepared, and then the polymerization catalyst is added. At this point, it is not necessary for the divalent phenol or its phenoxide to be completely dissolved in the alkaline aqueous solution of divalent phenol. Furthermore, as the organic phase, only an organic solvent that is immiscible with water and dissolves the polymer is mixed with the above alkaline solution and suspended by stirring. Solid 4,4'-biphenyldicarbonyl chloride, such as a powder, is then added to carry out the polymerization reaction. This method has three advantages. The first advantage is that, since 4,4'-biphenyldicarbonyl chloride is not prepared as a solution or solvent suspension beforehand, hydrolysis during the mixing process with the alkaline aqueous solution of divalent phenol can be suppressed. The second advantage is that, since a solvent suspension is not handled, the cumbersome operation of transferring the solvent suspension for mixing with the alkaline aqueous solution can be avoided. To avoid handling 4,4'-biphenyldicarbonyl chloride as a solvent suspension, it is conceivable to dilute it with a large amount of solvent to make a solution. In contrast, method A, which adds solid 4,4'-biphenyldicarbonyl chloride, has a third advantage: since it is not necessary to completely dissolve the 4,4'-biphenyldicarbonyl chloride itself, the amount of organic solvent used can be reduced, resulting in increased manufacturing efficiency and savings of organic solvents. Furthermore, the polymerization catalyst may be added to the aqueous layer or to the organic layer beforehand. Alkali used in preparing divalent phenol aqueous solutions include sodium hydroxide, potassium hydroxide, and lithium hydroxide. The amount of alkali used is generally 2 to 5 times the number of moles of divalent phenol, that is, 1 to 2.5 equivalents relative to the hydroxyl groups.

[0073] In the polymer production method of the present invention, the following method B may also be used. <Method B> As the organic layer, an organic solvent that is immiscible with water and dissolves the polymer is mixed with 4,4'-biphenyl dicarbonyl chloride and stirred to obtain a suspension. Meanwhile, in a separate container, an alkaline aqueous solution of divalent phenol is prepared as the aqueous phase, and then a polymerization catalyst is added. The resulting aqueous layer is added to the suspension, and the polymerization reaction is carried out. Method B described above can improve the reproducibility of the polymerization process by pre-suspending 4,4'-biphenyldicarbonyl chloride in an organic solvent. Furthermore, compared to the reverse procedure, where a solvent suspension of 4,4'-biphenyldicarbonyl chloride is added to an alkaline aqueous solution of divalent phenol, Method B does not involve a solvent suspension transfer step, thus reducing the complexity of the operation and minimizing concerns about hydrolysis of 4,4'-biphenyldicarbonyl chloride during the transfer step.

[0074] In the manufacturing method of the present invention, the following method C may also be used. <Method C> As described above, a general interfacial polymerization method involves preparing an alkaline aqueous solution of divalent phenol as the aqueous phase, followed by the addition of a polymerization catalyst. Meanwhile, a solution or solvent suspension of 4,4'-biphenyl dicarbonyl chloride is prepared as the organic phase and added to the alkaline solution to carry out the polymerization reaction.

[0075] In interfacial polymerization, an end-sealing agent may be used during polymerization to control the molecular weight of the polymer. Furthermore, from the viewpoint of controlling the properties of the polymer, it is preferable that the ends of the polymer are sealed with monohydric phenols, monohydric acid chlorides, monohydric alcohols, monohydric carboxylic acids, etc. Examples of monohydric phenols that can be used as such end-sealing agents include phenol, o-cresol, m-cresol, p-cresol, p-tert-butylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, and 2-phenyl-2-(4-hydroxyphenyl)propane (sometimes written as "p-(α-cumyl)phenol"). Examples include 2-phenyl-2-(2-hydroxyphenyl)propane and 2-phenyl-2-(3-hydroxyphenyl)propane. Monohydric chlorides used as end-captives include benzoyl chloride, methanesulfonyl chloride, phenyl chlorocarbonate, acetyl chloride, and lauroyl chloride. Monohydric alcohols used as end-captives include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, pentanol, hexanol, dodecyl alcohol, stearyl alcohol, benzyl alcohol, and phenethyl alcohol. Monocarboxylic acids used as end-captives include acetic acid, propionic acid, octanoic acid, cyclohexanecarboxylic acid, benzoic acid, toluic acid, phenylacetic acid, p-tert-butylbenzoic acid, and p-methoxyphenylacetic acid. In particular, the ends are preferably sealed with a monohydric phenol or monohydric acid chloride, and more preferably with p-tert-butylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, benzoyl chloride, or acetyl chloride.

[0076] Examples of polymerization catalysts for interfacial polymerization include quaternary ammonium salts such as tributylbenzylammonium halide, tetrabutylammonium halide, trimethylbenzylammonium halide, and triethylbenzylammonium halide, and quaternary phosphonium salts such as tributylbenzylphosphonium halide, tetrabutylphosphonium halide, trimethylbenzylphosphonium halide, and triethylbenzylphosphonium halide. Among these, those selected from tributylbenzylammonium halide, tetrabutylammonium halide, tributylbenzylphosphonium halide, and tetrabutylphosphonium halide are preferred because they readily promote polymerization.

[0077] As solvents for the organic phase in interfacial polymerization, chlorine-based solvents such as dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene, as well as aromatic hydrocarbons such as toluene, benzene, xylene, and anisole, can be used, and tetrahydrofuran can also be used. Among these, dichloromethane and o-dichlorobenzene are preferred as organic solvents for the organic layer. If the divalent carboxylic acid halide does not dissolve or has low solubility in the organic solvent of the organic layer, other organic solvents can be used. While it is preferable that the organic solvent of the organic layer is insoluble in water, some or all of the organic layer may be replaced with an organic solvent that is also soluble in water, in order to improve the solubility of the divalent carboxylic acid halide in the organic layer, or to increase the efficiency of the polymerization reaction, suppress hydrolysis of the divalent carboxylic acid halide, and obtain a polymer of a desired molecular weight. Examples of organic solvents effective in improving the solubility of divalent carboxylic acid halides in organic layers include tetrahydrofuran, N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), 1,4-dioxane, and 1,3-dioxolane. A higher polymer concentration in the organic solvent of the organic layer is preferable from the viewpoint of productivity. The amount of polymer relative to the liquid volume of the organic layer is preferably 2% by mass or more, more preferably 6% by mass or more, and even more preferably 10% by mass or more. Furthermore, the amount of polymer relative to the total volume of the aqueous layer and the organic layer is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more.

[0078] Acetic acid is added to the polymer solution obtained after polymerization to complete the polymerization. Then, the polymer solution is washed by repeatedly stirring it with water to remove ionic components such as sodium ions, potassium ions, lithium ions, chloride ions, and polymerization catalysts contained in the polymer solution. The water used for washing may be acidic or basic, and washing is repeated until the washing wastewater becomes neutral.

[0079] The obtained polymer solution is dropped into a poor solvent, causing the polymer to precipitate as a solid. The solid content concentration of the polymer solution is preferably 7% by mass or less. Furthermore, the volume of the poor solvent is preferably three times or more the volume of the polymer solution. Examples of poor solvents include methanol, ethanol, isopropyl alcohol, acetone, acetonitrile, and hexane.

[0080] By adding the polymer solution to a poor solvent, the residual monomers, alkali, and impurities derived from the polymerization catalyst contained in the polymer can be reduced. To reduce the content of residual monomers and impurities, it is particularly preferable to immerse the polymer in the poor solvent for at least one minute after the precipitation treatment. Furthermore, when using trimethylbenzylammonium halide or triethylbenzylammonium halide, which have relatively low polymerization activity, as the polymerization catalyst, it is preferable to immerse the polymer for at least three minutes. If the polymer is removed in less than three minutes, the removal of residual monomers and impurities from the polymer may be insufficient. To further reduce residual monomers and impurities, the above operation of dissolving the obtained polymer in the solvent again and adding it to the poor solvent for precipitation may be repeated.

[0081] When the above polymer is manufactured, insoluble impurities may be formed in relation to tetrahydrofuran or dichloromethane. One reason for this is thought to be the use of 4,4'-biphenyldicarbonyl chloride in introducing the structural unit represented by formula (II) above. In other words, it is thought that when 4,4'-biphenyldicarboxylic acid or 4-(4-carboxyphenyl)-benzoic acid chloride, which are impurities that may be contained in 4,4'-biphenyldicarbonyl chloride, are introduced into the manufacturing process of the above polymer, they form acid anhydride compounds as insoluble impurities, as shown in the scheme below. Furthermore, it is conceivable that 4,4'-biphenyldicarboxylic acid or 4-(4-carboxyphenyl)-benzoic acid chloride may be generated during the polymerization reaction in the manufacturing process, and subsequently, an acid anhydride compound may be formed as shown in the scheme below.

[0082] [ka]

[0083] Depending on the application of the polymer or coating film of the present invention, it is preferable that the polymer or coating film of the present invention does not contain such insoluble impurities. A method for obtaining a polymer that does not contain insoluble impurities is, for example, to remove the insoluble impurities by treating a solution containing both the polymer and the insoluble impurities with various adsorbents. Furthermore, in order to suppress the generation of insoluble impurities, it is preferable to use 4,4'-biphenyldicarbonyl chloride with a low content of 4,4'-biphenyldicarboxylic acid or 4-(4-carboxyphenyl)-benzoic acid chloride as impurities. In 4,4'-biphenyldicarbonyl chloride, the content of 4,4'-biphenyldicarboxylic acid and 4-(4-carboxyphenyl)-benzoic acid chloride is preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less.

[0084] The coating resin composition of the present invention typically contains a solvent in addition to the polymer described above. The polymer obtained as described above has high solubility in general-purpose solvents or mixtures thereof. Specifically, examples of solvents used alone or in mixtures include chlorine-based solvents such as dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, and o- and m-dichlorobenzene; aromatic hydrocarbons such as toluene, benzene, and xylene; and N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), 1,4-dioxane, and tetrahydrofuran.

[0085] The coating resin composition of the present invention may also preferably contain a functional material in order to impart a desired functionality to the resulting coating film of the present invention. The functionality imparted to the coating film of the present invention is not limited to a specific function. For example, in the coating resin composition or coating film of the present invention, the mass ratio of the polymer to the functional material can be 90:10 to 50:50, and it is also preferable that it be 80:20 to 50:50. The above functional materials are not particularly limited, but aromatic ring compounds containing benzene rings are preferred from the viewpoint of further enhancing compatibility and interaction with the above polymers. These aromatic ring compounds containing benzene rings preferably have 2 to 15 benzene rings, more preferably 3 to 12, and even more preferably 4 to 10. Furthermore, these aromatic ring compounds containing benzene rings preferably have a molecular weight of 200 to 2000, more preferably 250 to 1500, and even more preferably 300 to 1000. Among the aromatic ring compounds containing the benzene ring described above, compounds represented by the following formula (V) are preferred.

[0086] [ka]

[0087] In the formula, X represents an oxygen atom, a sulfur atom, an optionally substituted hydrocarbon group, or an optionally substituted imino group. n1 represents an integer from 0 to 4. R represents a monovalent organic group or a hydroxyl group. The hydrocarbon group that may have substituents as X is preferably a hydrocarbon group containing an aromatic ring with 6 to 35 carbon atoms, and more preferably a hydrocarbon group containing an aromatic ring with 6 to 25 carbon atoms. A preferred n1 is an integer from 0 to 2, and a more preferred n1 is 0 or 1. A preferred monovalent organic group that can be taken as R is a linear alkyl group.

[0088] The aromatic compound represented by formula (V) contains multiple benzene rings, heteroatoms such as oxygen, sulfur, and nitrogen atoms, and has a large mass ratio of benzene rings in the aromatic compound represented by formula (V), resulting in a rigid structure. This enhances the compatibility and interaction between the polymer and the functional material, thereby improving the mechanical properties of the resulting coating film. Furthermore, it is expected to densify the coating film and reduce its moisture permeability.

[0089] The molecular weight of the aromatic compound represented by the above formula (V) is preferably 200 to 2000, more preferably 250 to 1500, and even more preferably 300 to 1000. The number of benzene rings in formula (V) above is preferably 2 to 15, more preferably 3 to 12, and even more preferably 4 to 10. The aromatic compound represented by the above formula (V) preferably has at least one of an oxygen atom and a nitrogen atom.

[0090] [Method for producing polymers] Preferred embodiments of the polymer production method of the present invention will be described. In the interfacial polymerization of divalent carboxylic acid halides and divalent phenols, as described above, it has generally been considered preferable to add the divalent carboxylic acid halide to the alkaline aqueous solution of the divalent phenol as a solution or slurry mixed with an organic solvent, from the viewpoint of preventing hydrolysis of the divalent carboxylic acid halide or from the viewpoint of reproducibility of the polymerization reaction. On the other hand, as a result of diligent research by the present inventors, it has been found that a polymer of the desired molecular weight can be efficiently obtained even when a solid such as 4,4'-biphenyldicarbonyl chloride powder is directly added to a mixture containing an alkaline aqueous solution of divalent phenol, a polymerization catalyst, and an organic solvent in the organic layer.

[0091] The polymer production method of the present invention is suitable as a polymer production method having a structural unit represented by the following formula (II) (hereinafter also referred to as "the production method of the present invention"), and includes the step of mixing a mixture containing an alkaline aqueous solution of divalent phenol and an organic solvent with solid 4,4'-biphenyldicarbonyl chloride. The production method of the present invention more preferably includes the step of adding solid 4,4'-biphenyldicarbonyl chloride to a mixture containing an alkaline aqueous solution of divalent phenol and an organic solvent that is being stirred. In the present invention, "solid 4,4'-biphenyldicarbonyl chloride" means solid 4,4'-biphenyldicarbonyl chloride itself, not a state mixed with an organic solvent (solution or slurry).

[0092] [ka]

[0093] The manufacturing method of the present invention can be carried out, for example, by method A described above. The advantages of method A are as described above.

[0094] In the manufacturing method (Method A) of the present invention, from the viewpoint of improving the properties of the obtained polymer, it is preferable to use a compound represented by the following formula, which gives a structural unit represented by the above formula (I), as the divalent phenol component.

[0095] [Chemical formula]

[0096] From the viewpoint of workability during production, it is preferable that solid 4,4'-biphenyldicarbonyl chloride does not contain an organic solvent. When 4,4'-biphenyldicarbonyl chloride can contain an organic solvent, the content of the organic solvent with respect to the total amount of solid 4,4'-biphenyldicarbonyl chloride and the organic solvent is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less.

[0097] In the interfacial polymerization of the production method of the present invention, from the viewpoint of enhancing the properties of the obtained polymer and further controlling the molecular weight during polymerization, it is preferable to use a compound represented by the following formula together with the dihydric phenol. H-O-R a In the formula, R a is the same monovalent organic group as R in the above formula (III-A), and the preferred forms are also the same. a Examples of the compound represented by H-O-R a include the monohydric phenol or monohydric alcohol used in the production method of the above polymer. In all the terminal structures of the polymer obtained by the production method of the present invention, the proportion occupied by the total of the terminal structures derived from the compound represented by H-O-R a is preferably the same as the proportion occupied by the total of the terminal structures derived from the compound represented by the above formula (III-A) in all the terminal structures of the above polymer.

[0098] Furthermore, it is also preferable to use a compound represented by the following formula together with 4,4'-biphenyldicarbonyl chloride.

[0099] [Chemical formula]

[0100] In the formula, R bR in equation (III-B) above is b It is the same monovalent organic group, and its preferred form is also the same. Examples of compounds represented by the above formula include monovalent acid chlorides used in the above polymer manufacturing method. In the production method of the present invention, a monovalent carboxylic acid used in the above polymer production method may be used together with 4,4'-biphenyldicarbonyl chloride. In the polymer produced by the manufacturing method of the present invention, the proportion of terminal structures derived from the above compound among all terminal structures is preferably the same as the proportion of terminal structures derived from the compound represented by formula (III-B) among all terminal structures of the polymer.

[0101] In the production method of the present invention, monomers that give at least one of the above-mentioned structural units derived from the dicarboxylic acid unit, formulas (IA), (IB), (IV), (IC), and the above-mentioned structural units used in the production method of the polymer may be used. The content of formulas (II), (I), (IA), (IB), (IV), (IC), and the above-mentioned structural units derived from the dicarboxylic acid unit in the polymer obtained by the production method of the present invention is preferably the same as the content of these structural units in the above-mentioned polymer. Furthermore, the weight-average molecular weight of the polymer obtained by the production method of the present invention is preferably the same as the weight-average molecular weight of the above-mentioned polymer. Furthermore, the polymerization catalyst and organic solvent used in the manufacturing method of the present invention are the same as the polymerization catalyst and organic solvent used in the above polymer manufacturing method, and the preferred polymerization catalyst and organic solvent are also the same.

[0102] The reason why the desired polymer solution can be obtained despite the low solvent solubility of 4,4'-biphenyldicarbonyl chloride is thought to be that the components of the added solid 4,4'-biphenyldicarbonyl chloride that dissolve in the organic layer are gradually consumed, and eventually some or all of the 4,4'-biphenyldicarbonyl chloride dissolves and undergoes polymerization. Furthermore, the reason why the desired polymer can be obtained with little effect from hydrolysis despite the addition of solid 4,4'-biphenyldicarbonyl chloride is thought to be that the reaction between the phenoxide of the divalent phenol and 4,4'-biphenyldicarbonyl chloride is very rapid, so even when the solid surface of 4,4'-biphenyldicarbonyl chloride is in direct contact with the alkaline aqueous solution, the desirable polymerization reaction becomes dominant. From the viewpoint of further suppressing the hydrolysis of 4,4'-biphenyldicarbonyl chloride, it is preferable to reduce the amount of alkali used when preparing the alkaline aqueous solution of the divalent phenol.

[0103] In the manufacturing method of the present invention, the post-treatment described in the above polymer manufacturing method may be performed.

[0104] [Coating film] The coating film of the present invention may be composed of the polymer of the present invention, or may contain other components in addition to the polymer of the present invention. Examples of other components include the functional materials described above. The coating film of the present invention has excellent film-forming properties during its formation, and the coating film itself has excellent heat resistance and abrasion resistance. An example of a coating film combined with a functional material is a low-moisture-permeability film, such as the one described in Japanese Patent Publication No. 2016-69468. That is, by adding a phenol compound as a functional material to a polymer, the polymer and the functional material exhibit high compatibility, and moisture permeability can be effectively suppressed. Another example of a composite coating film containing functional materials is the charge transport layer of an electrophotographic photoreceptor. That is, the charge transport layer comprises the polymer as a binder and a charge transport material, and the binder is required to have high compatibility with the charge transport material. By using the coating film of the present invention as a charge transport layer comprising the polymer and an aromatic compound as a charge transport material, a charge transport layer with excellent abrasion resistance can be obtained. The coating film of the present invention can be preferably applied as, for example, a metal wire coating film, a polarizing plate protective film for a display device, and the like.

[0105] The coating film of the present invention can also be used with other layers placed on top of it. For example, durability can be further enhanced by forming a protective layer in contact with the coating film of the present invention.

[0106] The method for forming the coating film of the present invention is not particularly limited as long as a film containing the above polymer can be formed. For example, it can be formed by applying the coating resin composition of the present invention onto a substrate and drying the coating film. The application method and drying method themselves can be any method that is normally used in the application and drying of coating liquids. The substrate is not particularly limited, and a wide range of materials, components, etc. having a surface to be coated can be applied. [Examples]

[0107] The present invention will be described in more detail below based on examples, but the present invention is not limited thereto. In the structural formula shown below, Me represents a methyl group.

[0108] [Preparation of polymers constituting the coating film composition] <Example 1> -Preparation of polymer (1)- Polymer (1) was prepared according to the following scheme.

[0109] [ka]

[0110] Into a reaction vessel equipped with a stirring device, 11.4493 g of 2,2-bis(4-hydroxyphenyl)-4-methylpentane (manufactured by Honshu Chemical Industry Co., Ltd.), 0.1750 g of 2,3,5-trimethylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.0572 g of sodium hydrosulfite (manufactured by Fujifilm Wako Pure Chemical Corporation), and 230 mL of water were added to form a suspension. To this suspension, while stirring, at a temperature of room temperature (20 °C), 4.8378 g of sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Corporation), 0.1981 g of benzyltributylammonium chloride (manufactured by Fujifilm Wako Pure Chemical Corporation), and 150 mL of water were added, and the mixture was stirred for 30 minutes under a nitrogen atmosphere to obtain a solution in which the solids were generally dissolved (there was some turbidity). 210 mL of o-dichlorobenzene (manufactured by Fujifilm Wako Pure Chemical Corporation) was added to this aqueous solution, and after stirring for 30 minutes under a nitrogen atmosphere, 12.0000 g of 4,4'-biphenyldicarbonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a powder. After the addition was completed, the temperature was maintained at room temperature (20 °C), and the reaction was allowed to proceed by stirring for 4 hours under a nitrogen atmosphere. The solution after polymerization was diluted with 300 mL of o-dichlorobenzene, and the aqueous layer was removed. After washing with a dilute acetic acid solution and ion-exchanged water, the solution was poured into methanol (manufactured by Fujifilm Wako Pure Chemical Corporation) to precipitate the polymer. The precipitated polymer was filtered and dried at 50 °C. This polymer was redissolved in 900 mL of tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Corporation), and the solution was poured into methanol to precipitate the polymer. The precipitated polymer was filtered, washed with methanol, and dried at 50 °C to obtain 17.8 g of a white polymer (1). The weight-average molecular weight (Mw) of polymer (I) determined as the molecular weight in terms of polystyrene by gel permeation chromatography (GPC, using tetrahydrofuran as the eluent) was 120,000. Polymer (1) is 1Based on the calculation of the unit molar ratio of each structure by 1H NMR, it was confirmed that the structure is composed of 56% by mass of diol structural units derived from 2,2-bis(3-methyl-4-hydroxyphenyl)-4-methylpentane, 43% by mass of dicarboxylic acid structural units derived from 4,4'-biphenyldicarbonyl chloride, and 1% by mass of terminal structures derived from 2,3,5-trimethylphenol. The above method involves adding 4,4'-biphenyldicarbonyl chloride in powder form, which corresponds to Method A.

[0111] <Example 2> -Preparation of polymer (2)- A white polymer (2) was prepared according to the following scheme.

[0112] [ka]

[0113] In a reaction vessel equipped with a stirring device, 43.0952 g of 2,2-bis(4-hydroxyphenyl)-4-methylpentane (manufactured by Honshu Chemical Industry Co., Ltd.), 33.0645 g of triethylamine (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.), and 260 mL of methylene chloride (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.) were added to a solution. While stirring this solution at a temperature of 5°C, 45.0000 g of 4,4'-biphenyldicarbonyl chloride (manufactured by Tokyo Chemical Industries Co., Ltd.) was added in powder form. After the addition was complete, the temperature was raised to 30°C and the reaction was allowed to proceed by stirring under a nitrogen atmosphere for 4 hours. The polymerized solution was diluted with 3000 mL of tetrahydradofuran and added to methanol to precipitate the polymer. The precipitated polymer was filtered, washed with methanol, and dried at 50°C. This polymer was redissolved in 3000 mL of tetrahydradofuran and added to methanol to precipitate the polymer. The precipitated polymer was filtered, washed with methanol, and dried at 50°C to obtain 68.9 g of a white polymer. The above method is a solution polymerization method, not an interfacial polymerization method. Therefore, it does not fall under any of Method A, Method B, or Method C. In a reaction vessel equipped with a stirring device, 10.0000 g of this polymer, 1.2941 g of triethylamine, and 110 mL of methylene chloride were added to form a solution. While stirring this solution at a temperature of 5°C, 1.7121 g of benzoyl chloride (manufactured by Fujifilm Wako Pure Chemical Industries) was added. After the addition was complete, the temperature was raised to 30°C and the reaction was allowed to proceed by stirring under a nitrogen atmosphere for 4 hours. The polymerized solution was diluted with 400 mL of tetrahydrofuran and added to methanol to precipitate the polymer. The precipitated polymer was filtered, washed with methanol, and dried at 50°C. This polymer was redissolved in 400 mL of tetrahydrofuran and added to methanol to precipitate the polymer. The precipitated polymer was filtered, washed with methanol, and dried at 50°C to obtain 8.7 g of white polymer (2). The weight-average molecular weight of polymer (1), determined in the same manner as in Example 1, and the content of the calculated structural units are shown in Table 1.

[0114] <Example 3> -Preparation of polymer (3)- A white polymer (3) composed of the structural units shown in Table 1 was prepared according to the scheme below, in accordance with Example 2.

[0115] [ka]

[0116] Table 1 shows the weight-average molecular weight of polymer (3), determined in the same manner as in Example 1, and the content of the calculated structural units.

[0117] <Example 4> -Preparation of polymer (4)- A white polymer (4) composed of the structural units shown in Table 1 was prepared according to the scheme below.

[0118] [ka]

[0119] In a reaction vessel equipped with a stirring device, 11.4493 g of 2,2-bis(4-hydroxyphenyl)-4-methylpentane (manufactured by Honshu Chemical Industry Co., Ltd.), 0.1930 g of pt-butylphenol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.0572 g of sodium hydrosulfite (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 230 mL of water were added to form a suspension. To this suspension, under stirring at room temperature (20°C), 4.8378 g of sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.1981 g of benzyltributylammonium chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 150 mL of water were added, and the mixture was stirred under a nitrogen atmosphere for 30 minutes to obtain a solution in which the solids were mostly dissolved (the solution was slightly turbid). To this aqueous solution, a mixture of 12.0000 g of 4,4'-biphenyldicarbonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 210 mL of methylene chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added (in slurry form in Example 4). After the addition was complete, the reaction was allowed to proceed by stirring at room temperature (20°C) under a nitrogen atmosphere for 4 hours. The polymerized solution was diluted with 300 mL of methylene chloride, and the aqueous layer was removed. After washing with dilute acetic acid solution and deionized water, the polymer was precipitated by adding it to methanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The precipitated polymer was filtered and dried at 50°C. This polymer was redissolved in 900 mL of tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and the polymer was precipitated by adding it to methanol. The precipitated polymer was filtered, washed with methanol, and dried at 50°C to obtain 14.0 g of white polymer (4). Table 1 shows the weight-average molecular weight of polymer (4), determined in the same manner as in Example 1, and the content of the calculated structural units. The above method corresponds to Method C because it involves adding 4,4'-biphenyldicarbonyl chloride as a mixture (slurry) with methylene chloride. The slurry mixture contains a precipitate of 4,4'-biphenyldicarbonyl chloride, and the process of adding this mixture to the alkaline solution, without leaving any precipitate, is a complicated operation. In particular, when producing polymers on a 1 kg or 1 ton scale, Method C is considered to be significantly more inefficient than Method A.

[0120] <Example 5> -Preparation of polymer (5)- A white polymer (5) composed of the structural units shown in Table 1 was prepared according to the scheme below.

[0121] [ka]

[0122] In a reaction vessel equipped with a stirring device, 34.3484 g of 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 0.5270 g of 2,3,5-trimethylphenol, 0.1717 g of sodium hydrosulfite, and 690 mL of water were added to form a suspension. To this suspension, under stirring at room temperature (20°C), 14.5000 g of sodium hydroxide, 0.5955 g of benzyltributylammonium chloride, and 460 mL of water were added, and the mixture was stirred under a nitrogen atmosphere for 30 minutes to obtain a solution in which the solids were mostly dissolved (the solution was slightly turbid). To this aqueous solution, 630 mL of o-dichlorobenzene was added, and the mixture was stirred under a nitrogen atmosphere for 30 minutes, after which 36.0000 g of 4,4'-biphenyldicarbonyl chloride was added in powder form. After the addition was complete, the reaction was allowed to proceed by stirring at room temperature (20°C) under a nitrogen atmosphere for 4 hours. The polymerized solution was diluted with 900 mL of o-dichlorobenzene, and the aqueous layer was removed. After washing with dilute acetic acid solution and deionized water, the polymer was precipitated by adding it to methanol. The precipitated polymer was filtered and dried at 50°C. This polymer was redissolved in 2700 mL of tetrahydrofuran and precipitated by adding it to methanol. The precipitated polymer was filtered, washed with methanol, and dried at 50°C to obtain 55.3 g of white polymer (5). Table 1 shows the weight-average molecular weight of polymer (5), determined in the same manner as in Example 1, and the content of the calculated structural units. The terminal structures of polymer (5) were mainly terminal structure A derived from 2,3,5-trimethylphenol, but also included some terminal structures B and C. 1 This was confirmed by 1H NMR. 1 Based on 1H NMR, it was estimated that terminal structure A comprised 100 mol%, while terminal structures B and C each comprised approximately 2 mol%. The above method involves adding 4,4'-biphenyldicarbonyl chloride in powder form, which corresponds to Method A.

[0123] <Comparative Example 1> -Preparation of comparative polymer (1)- According to the scheme below, a white comparative polymer (1) composed of the structural units shown in Table 2 was prepared as a polymer equivalent to Resin-2 in Japanese Patent Publication No. 6500996. Since the synthesis conditions for Resin-2 are not disclosed, the synthesis conditions were the same as in Example 1. However, the obtained polymer did not have sufficient solubility in tetrahydrofuran, and it was not possible to form a film for evaluation sample preparation. The weight-average molecular weight of comparative polymer (1), determined in the same manner as in Example 1, and the content of the calculated structural units are shown in Table 2. The weight-average molecular weight was measured relative to the tetrahydrofuran-soluble component.

[0124] [ka]

[0125] <Comparative Example 2> -Preparation of comparative polymer (2)- A white comparative polymer (2), composed of the structural units shown in Table 2, was prepared according to the scheme below, in accordance with Synthesis Example 17 of Japanese Patent Application Publication No. 2017-215584. Note that in Synthesis Example 17 described in Table 1 of Japanese Patent Application Publication No. 2017-215584, the structure represented by general formula (I) is given as I-1 / I-24(90 / 10), but since the specific structure of I-24 is not disclosed, it was prepared as I-1 / I-4(90 / 10). Table 2 shows the weight-average molecular weight of comparative polymer (2), determined in the same manner as in Example 1, and the content of the calculated structural units.

[0126] [ka]

[0127] <Comparative Example 3> -Preparation of comparative polymer (3)- A white comparative polymer (3), composed of the structural units shown in Table 2, was prepared according to the scheme below, in accordance with Example 3 of Japanese Patent Publication No. 4927690. The weight-average molecular weight of comparative polymer (3), determined in the same manner as in Example 1, and the content of the calculated structural units are shown in Table 2.

[0128] [ka]

[0129] <Comparative Example 4> -Preparation of comparative polymer (4)- A white comparative polymer (4), composed of the structural units shown in Table 2, was prepared according to the scheme below, in accordance with Example 4 of Japanese Patent Publication No. 4927690. The weight-average molecular weight of comparative polymer (4), determined in the same manner as in Example 1, and the content of the calculated structural units are shown in Table 2.

[0130] [ka]

[0131] <Comparative Example 5> -Preparation of comparative polymer (5)- A white comparative polymer (4) composed of the structural units shown in Table 3 was prepared according to the scheme below, in accordance with Example 5 of Japanese Patent No. 4927690. The weight-average molecular weight of comparative polymer (5), determined in the same manner as in Example 1, and the content of the calculated structural units are shown in Table 3.

[0132] [ka]

[0133] <Comparative Example 6> -Preparation of comparative polymer (6)- A white comparative polymer (6), composed of the structural units shown in Table 3, was prepared according to the scheme below, in accordance with Example 6 of Japanese Patent Publication No. 4927690. The weight-average molecular weight of comparative polymer (6), determined in the same manner as in Example 1, and the content of the calculated structural units are shown in Table 3.

[0134] [ka]

[0135] <Comparative Example 7> -Preparation of comparative polymer (7)- A white comparative polymer (7), composed of the structural units shown in Table 3, was prepared according to the scheme below, in accordance with Example 1 of Japanese Patent No. 5117006. The weight-average molecular weight of comparative polymer (7), determined in the same manner as in Example 1, and the content of the calculated structural units are shown in Table 3.

[0136] [ka]

[0137] <Comparative Example 8> -Preparation of comparative polymer (8)- A white comparative polymer (8), composed of the structural units shown in Table 4, was prepared according to the following scheme, in accordance with Production Example 14 of Japanese Patent No. 5481829. The weight-average molecular weight of comparative polymer (8), determined in the same manner as in Example 1, and the content of the calculated structural units are shown in Table 4.

[0138] [ka]

[0139] <Comparative Example 9> -Preparation of comparative polymer (9)- A white comparative polymer (9), composed of the structural units shown in Table 4, was prepared according to the following scheme, in accordance with Production Example 3 of Japanese Patent No. 4246621. The weight-average molecular weight of comparative polymer (9), determined in the same manner as in Example 1, and the content of the calculated structural units are shown in Table 4.

[0140] [ka]

[0141] <Comparative Example 10> -Preparation of comparative polymer (10)- A white comparative polymer (10) composed of the structural units shown in Table 4 was prepared according to the scheme below, in accordance with Comparative Production Example 1 of Japanese Patent No. 4246621. The weight-average molecular weight of the comparative polymer (10), determined in the same manner as in Example 1, and the content of the calculated structural units are shown in Table 4.

[0142] [ka]

[0143] <Comparative Example 11> -Preparation of comparative polymer (11)- A white comparative polymer (11) composed of the structural units shown in Table 4 was prepared according to the scheme below, as the structure of I-15 in Japanese Patent Application Publication No. 2005-156605. Since the synthesis conditions for I-15 are not disclosed, the synthesis conditions were the same as in Example 1. The weight-average molecular weight of comparative polymer (11), determined in the same manner as in Example 1, and the content of the calculated structural units are shown in Table 4. The ratio (molar ratio) of structural units derived from terephthalate chloride and isophthalate chloride in comparative polymer (11) was 1:1.

[0144] [ka]

[0145] <Comparative Example 12> -Preparation of Comparative Polymer (12)- According to the following scheme, a white comparative polymer (12) composed of the structural units shown in Table 4 was prepared with the structure of I-14 in JP-A-2005-156605. Since the synthesis conditions of I-14 were not disclosed, the synthesis conditions were in accordance with Example 1. Table 4 shows the weight average molecular weight of the comparative polymer (12) determined in the same manner as in Example 1 and the calculated content of the structural units. The ratio (molar ratio) of the structural units derived from terephthalic acid chloride and isophthalic acid chloride in the comparative polymer (12) was 1:1.

[0146]

Chemical formula

[0147] <Comparative Example 13> -Preparation of Comparative Polymer (13)- According to the following scheme, a white comparative polymer (13) composed of the structural units shown in Table 5 was prepared in accordance with Synthesis Example 12 of JP-A-2017-151425. Table 5 shows the weight average molecular weight of the comparative polymer (13) determined in the same manner as in Example 1 and the calculated content of the structural units.

[0148]

Chemical formula

[0149] <Comparative Example 14> -Preparation of Comparative Polymer (14)- According to the following scheme, a white comparative polymer (15) composed of the structural units shown in Table 5 was prepared in accordance with Example 5 of Japanese Patent No. 6455025. Table 5 shows the weight average molecular weight of the comparative polymer (14) determined in the same manner as in Example 1 and the calculated content of the structural units. The ratio (molar ratio) of the structural units derived from terephthalic acid chloride and isophthalic acid chloride in the comparative polymer (14) was 1:1.

[0150]

Chemical formula

[0151] <Comparative Example 15> -Preparation of comparative polymer (15)- A white comparative polymer (15) composed of the structural units shown in Table 5 was prepared according to the scheme below, in accordance with Example 5 of Japanese Patent No. 6815025. The weight-average molecular weight of comparative polymer (15), determined in the same manner as in Example 1, and the content of the calculated structural units are shown in Table 5. The ratio (molar ratio) of structural units derived from terephthalate chloride and isophthalate chloride in comparative polymer (15) was 1:1.

[0152] [ka]

[0153] <Comparative Example 16> -Preparation of comparative polymer (16)- A white comparative polymer (16), composed of the structural units shown in Table 6, was prepared according to the scheme below, as a polymer equivalent to Resin-11 in Japanese Patent Publication No. 6500996. Since the synthesis conditions for Resin-11 are not disclosed, the synthesis conditions were the same as those in Example 1. The weight-average molecular weight of the comparative polymer (16), determined in the same manner as in Example 1, and the content of the calculated structural units are shown in Table 6.

[0154] [ka]

[0155] [Creation of evaluation samples (1)] 1.2 g of each of the polymers (1) to (5) and comparative polymers (1) to (16) prepared above and 18 g of tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Corporation) as a solvent were mixed to prepare each coating solution corresponding to each polymer. Each coating solution was dropped into a petri dish and dried to obtain a cast film with a film thickness of 10 to 50 μm corresponding to each polymer as a coating film. This cast film was peeled off from the petri dish and used as an evaluation sample.

[0156] <Wear Resistance Test (1)> Each cast film prepared in Preparation of Evaluation Sample (1) was attached to S-36 (manufactured by Taber) to obtain an evaluation sample for the wear resistance test. Each prepared evaluation sample was set in a rotary abrasion tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and using a wear wheel CS-10 (manufactured by Taber), it was rotated 2000 times under the conditions of a load of 500 gf and a rotation speed of 60 rpm to conduct a wear evaluation test. The wear loss (mg / 2000 rotations), which is the mass change of the sample before and after the wear evaluation test, was measured. Based on the obtained wear loss, the wear resistance of each evaluation sample was evaluated according to the following criteria. The results are shown in Tables 1 to 5. In addition, the evaluation samples formed from polymers (1) to (5) were used as evaluation samples for the wear resistance test (1) of Examples 1 to 5, respectively, and the evaluation samples formed from comparative polymers (2) to (16) were used as evaluation samples for the wear resistance test (1) of Comparative Examples 2 to 16, respectively.

[0157] -Evaluation Criteria for Wear Resistance- A: Wear loss is less than 7 mg B: Wear loss is 7 mg or more and less than 8 mg C: Wear loss is 8 mg or more and less than 10 mg D: Wear loss is 10 mg or more and less than 13 mg E: Wear loss is 13 mg or more

[0158] [Preparation of Evaluation Sample (2)] 800 mg each of the polymers (1) to (5) and comparative polymers (2) to (16) prepared above, 400 mg of 4,4'-(α-methylbenzylidene)bisphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) as an aromatic ring compound (functional material), and 18 g of tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a solvent were mixed to prepare coating solutions corresponding to each polymer. Each coating solution was dropped onto a petri dish to obtain cast films with a thickness of 10 to 50 μm corresponding to each polymer as coating films. These cast films were peeled off from the petri dishes and used as evaluation samples.

[0159] <Evaluation of film-forming properties (compatibility)> For each polymer, the cloudiness of the film was visually observed for both the cast film without functional materials, prepared in evaluation sample preparation (1), and the cast film containing functional materials, prepared in evaluation sample preparation (2). (For example, when using polymer (1), the cloudiness or wrinkles of the film were visually observed for both the cast film containing polymer (1) but without functional materials, and the cast film containing polymer (1) and functional materials.) This allowed for the evaluation of film-forming properties based on the compatibility between each polymer and the functional material. The results are shown in Tables 1-6.

[0160] -Evaluation criteria for film-forming properties- OK: Cast films containing functional materials exhibited the same level of transparency as cast films without functional materials. NG: Cast films containing functional materials were noticeably more cloudy or wrinkled than cast films without functional materials.

[0161] <Heat resistance evaluation> The cast films containing the functional material, prepared in (2) for evaluation, were placed in a forced-air constant-temperature incubator set to 170°C and heated in an air atmosphere for 15 minutes. After that, the clouding, discoloration, or leakage of the functional material of each cast film was visually observed. Visual evaluation was conducted to determine whether clouding was accelerated after heating compared to before heating, whether discoloration was accelerated after heating compared to before heating, or whether leakage of the functional material was observed. The results are shown in Tables 1-5. - Criteria for evaluating heat resistance - OK: No clouding or discoloration was accelerated after heating. No leakage of functional materials was observed. NG: Clouding was clearly accelerated after heating, discoloration was accelerated, or the functional material bleed was observed.

[0162] <Abrasion resistance test (2)> Each cast film prepared in (2) of the evaluation sample preparation was attached to S-36 (manufactured by Taber) to serve as an evaluation sample for abrasion resistance testing. Each prepared evaluation sample was set in a rotary abrasion tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and an abrasion evaluation test was conducted using a CS-10 abrasion wheel (manufactured by Taber) under conditions of a load of 500 gf and a rotation speed of 60 rpm for 2000 rotations. The abrasion loss (mg / 2000 rpm), which is the change in mass of the sample before and after the abrasion evaluation test, was measured. Based on the obtained abrasion loss, the abrasion resistance of each evaluation sample was evaluated according to the following criteria. The results are shown in Tables 1 to 5. The evaluation samples formed from polymers (1) to (5) were used as evaluation samples for abrasion resistance test (2) of Examples 1 to 5, respectively, and the evaluation samples formed from comparative polymers (2) to (16) were used as evaluation samples for abrasion resistance test (2) of Comparative Examples 2 to 16, respectively. The abrasion resistance of each evaluation sample was evaluated according to the following criteria. The results are shown in Tables 1 to 5.

[0163] - Criteria for evaluating wear resistance - A: Wear loss is less than 7 mg B: Wear loss of 7 mg or more, less than 8 mg C: Wear loss of 8 mg or more, but less than 10 mg D: Wear loss of 10 mg or more, but less than 13 mg E: Wear loss of 13 mg or more

[0164] [Table 1]

[0165] [Table 2]

[0166] [Table 3]

[0167] [Table 4]

[0168] [Table 5]

[0169] [Table 6]

[0170] Comparative polymers (1) to (7) and (13) do not have the structural unit represented by formula (I) above. Furthermore, the content of the structural unit represented by formula (II) above in comparative polymer (2) is less than 10% by mass. Comparative polymers (8) to (12) do not have either the structural unit represented by formula (I) or (II) above. Comparative polymers (14) and (15) do not have the structural unit represented by formula (II) above. Furthermore, the terminal structures of comparative polymers (1), (3) to (6), (11) and (12) are neither formula (III-A) nor (III-B) above. Furthermore, comparative polymer (16) has either the structural unit represented by formula (I) or (II) above, but its terminal structure is neither formula (III-A) nor (III-B) above. Comparative polymer (1) was insoluble in tetrahydrofuran, and therefore could not be used to form a film. The cast films formed from each comparative polymer other than comparative polymer (1) exhibited poor abrasion resistance. Furthermore, each comparative polymer showed poor film-forming ability or poor heat resistance when used in combination with functional materials.

[0171] In contrast, each cast film produced from the polymers defined in this invention exhibited excellent abrasion resistance, excellent film formation properties even in the presence of functional materials, and excellent heat resistance.

[0172] Although we have described the present invention along with its embodiments, we do not intend to limit our invention in any detail of the description unless specifically designated, and we believe that it should be interpreted broadly without contradicting the spirit and scope of the invention as set forth in the appended claims.

[0173] This application claims priority based on Japanese Patent Application No. 2021-082815, filed in Japan on 14 May 2021, the contents of which are incorporated herein by reference as part of this specification.

Claims

1. The polymer comprises a structural unit represented by the following formula (I), a structural unit represented by the following formula (II), and an end structure represented by the following formula (III-A) or (III-B). A coating resin composition wherein the polymer contains 10% by mass or more of the structural unit represented by formula (I) and 10% by mass or more of the structural unit represented by formula (II). 【Chemistry 1】 In the formula, Me represents methyl. 【Chemistry 2】 【Transformation 3】 In the formula, R ａ and R ｂ R represents a monovalent organic group. In formula (III-A), R ａ is R ａ The carbon atom inside is bonded to the oxygen atom shown in formula (III-A), and in formula (III-B), R ｂ is R ｂ The carbonyl group shown in formula (III-B) is bonded to the carbon dioxide within it. * indicates the bonding site.

2. The coating resin composition according to claim 1, wherein the polymer contains 20% by mass or more of the structural unit represented by formula (I).

3. The coating resin composition according to claim 1 or 2, wherein the polymer contains 20% by mass or more of the structural unit represented by formula (II).

4. The coating resin composition according to claim 1 or 2, wherein the end structure represented by formula (III-A) in the polymer is represented by the following formula (III-A-1). 【Chemistry 4】 In the formula, R ｄ represents an alkyl group, aryl group, or halogen atom, and s is an integer from 0 to 5. * indicates a bonding site.

5. A coating resin composition according to claim 1 or 2, comprising a solvent.

6. A coating resin composition according to claim 1 or 2, comprising a functional material consisting of an aromatic ring compound containing a benzene ring, wherein the mass ratio of the polymer content to the functional material content is polymer / functional material = 90:10 to 50:

50.

7. A polymer having a structural unit represented by the following formula (I), a structural unit represented by the following formula (II), and an end structure represented by the following formula (III-A) or (III-B), A polymer in which the structural unit represented by formula (I) is present in an amount of 10% by mass or more, and the structural unit represented by formula (II) is present in an amount of 10% by mass or more. 【Transformation 5】 In the formula, Me represents methyl. 【Transformation 6】 【Transformation 7】 In the formula, R ａ and R ｂ represent monovalent organic groups. In formula (III-A), R ａ is bonded to the oxygen atom shown in formula (III-A) by the carbon atom in R ａ , and in formula (III-B), R ｂ is bonded to the carbonyl group shown in formula (III-B) by the carbon atom in R ｂ . * indicates the bonding site.

8. A method for producing a polymer having a structural unit represented by the following formula (II), comprising the step of mixing a mixture containing an alkaline aqueous solution of a divalent phenol and an organic solvent with solid 4,4'-biphenyldicarbonyl chloride. 【Transformation 8】

9. A method for producing a polymer according to claim 8, wherein the polymer is the polymer described in claim 7.

10. A coating film comprising the polymer described in claim 7.

11. A method for forming a coating film, comprising coating a substrate with the coating resin composition described in claim 1 or 2.

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