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

Abstract

The present invention provides a coating resin composition and a polymer, the coating resin composition comprising a polymer having 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), wherein the content of the structural unit represented by the formula (I) in the polymer is 10% by mass or more and the content of the structural unit represented by the formula (II) is 10% by mass or more. The present invention also provides a method for producing a polymer having a structural unit represented by the following formula (II), a coating film comprising the polymer, and a method for forming the coating film. #imgabs0#*-O-R a (III‑A)#imgabs1#

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 Art

[0002] Polyesters containing structural units derived from aromatic diol compounds and structural units derived from aromatic dicarboxylic acid compounds, polycarbonates containing structural units derived from aromatic diol compounds and structural units derived from phosgene, and the like are excellent in heat resistance and mechanical strength and are widely used industrially.

[0003] For example, Patent Document 1 describes a film-forming resin with polyester as the main component, wherein the polyester is composed of residues of dicarboxylic acids having a biphenyl structure, a diphenyl ether structure, and a cyclohexane structure, and residues of dihydric phenols, and describes the following: by controlling the free dicarboxylic acid to 0.01 to 300 ppm, the electrical properties can be stabilized when applied to capacitors, electronic photographic photoreceptors, etc.

[0004] Patent Document 2 also describes a resin composition comprising 100 parts by mass of a polymer resin composition comprising 95-5% by mass of a polyarylate component (A) and 5-95% by mass of a polycarbonate component (B) mixed to make 100% by mass, and 0.01-1 part by mass of a silicone compound (C) having a glycidyl group with a specific structure. According to Patent Document 2, molded articles using this composition exhibit both heat resistance and transparency, making them suitable for automotive lighting peripheral components, reflectors for lighting fixtures, and the like.

[0005] Previous technical literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2008-31347

[0008] Patent Document 2: Japanese Patent Application Laid-Open No. 2003-292756 Summary of the Invention

[0009] Technical issues to be solved by the invention

[0010] In the industrial use of polymers such as polyesters and polycarbonates, the polymers are often molded into a desired shape, or the polymers are dissolved in a solvent and applied to a substrate to form a coating. Furthermore, in order to impart the desired functionality to the coating, the following steps are performed: improving the functionality and mechanical properties of the polymer itself, or mixing the polymer with a functional material for coating. In order to obtain the desired functional coating by mixing the polymer and the functional material, the compatibility between the polymer and the functional material is important, and it is also important to ensure film-forming properties without damaging a defect-free, uniform film. Furthermore, if a coating with low haze can be obtained, it is readily applicable as an optical film, etc.

[0011] The present invention aims to provide a coating resin composition that achieves excellent film-forming properties and can form a coating film having excellent heat resistance and abrasion resistance, a polymer suitable as a main component or binder of the coating resin composition, and a suitable method for producing the same. Furthermore, the present invention aims to provide a coating film that exhibits excellent film-forming properties when formed and exhibits excellent heat resistance and abrasion resistance, and a method for producing the same.

[0012] Means for solving technical problems

[0013] The above-mentioned problems of the present invention are solved by the following means.

[0014] <1>

[0015] A coating resin composition comprising a polymer having 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),

[0016] In the polymer, the content of the structural unit represented by the formula (I) is 10% by mass or more, and the content of the structural unit represented by the formula (II) is 10% by mass or more,

[0017] [Chemical Formula 1]

[0018]

[0019] In the formula, Me represents a methyl group,

[0020] [Chemical Formula 2]

[0021]

[0022] [Chemical Formula 3]

[0023]

[0024] Where R a and R brepresents a monovalent organic group, in formula (III-A), R a By R a The carbon atom in the formula (III-A) is bonded to the oxygen atom shown in the formula (III-B). b By R b The carbon atom in is bonded to the carbonyl group represented by formula (III-B), and * represents a bonding site.

[0025] <2>

[0026] The coating resin composition according to <1>, wherein

[0027] In the polymer, the content of the structural unit represented by the formula (I) is 20% by mass or more.

[0028] <3>

[0029] The coating resin composition according to <1> or <2>, wherein

[0030] In the polymer, the content of the structural unit represented by formula (II) is 20% by mass or more.

[0031] <4>

[0032] The coating resin composition according to any one of <1> to <3>, wherein

[0033] The terminal structure represented by the formula (III-A) in the above polymer is represented by the following formula (III-A-1),

[0034] [Chemical Formula 4]

[0035]

[0036] Where R d represents an alkyl group, an aryl group or a halogen atom, s is an integer of 0 to 5, and * represents a bonding site.

[0037] <5>

[0038] The coating resin composition according to any one of <1> to <4>, comprising a solvent.

[0039] <6>

[0040] The coating resin composition according to any one of <1> to <5>, comprising:

[0041] The functional material is composed of an aromatic ring-containing compound including a benzene ring, and the mass ratio of the polymer content to the functional material content is, that is, the polymer / the functional material = 90:10 to 50:50.

[0042] <7>

[0043] A polymer having 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),

[0044] In the polymer, the content of the structural unit represented by the formula (I) is 10% by mass or more, and the content of the structural unit represented by the formula (II) is 10% by mass or more,

[0045] [Chemical Formula 5]

[0046]

[0047] In the formula, Me represents a methyl group,

[0048] [Chemical Formula 6]

[0049]

[0050] [Chemical Formula 7]

[0051]

[0052] Where R a and R b represents a monovalent organic group, in formula (III-A), R a By R a The carbon atom in the formula (III-A) is bonded to the oxygen atom shown in the formula (III-B). b By R b The carbon atom in is bonded to the carbonyl group represented by formula (III-B), and * represents a bonding site.

[0053] <8>

[0054] A method for producing a polymer, comprising the following steps:

[0055] A mixture of an alkaline aqueous solution containing a dihydric phenol and an organic solvent and solid 4,4'-biphenyldicarboxylic acid chloride are mixed, wherein the polymer has a structural unit represented by the following formula (II),

[0056] [Chemical Formula 8]

[0057]

[0058] <9>

[0059] The method for producing a polymer according to <8>, wherein the polymer is the polymer according to <7>.

[0060] <10>

[0061] A coating film comprising the polymer described in <7>.

[0062] <11>

[0063] A method for forming a coating film comprises the following steps:

[0064] A substrate is coated with the coating resin composition according to any one of <1> to <6>.

[0065] Effects of the Invention

[0066] The coating resin composition of the present invention can achieve excellent film-forming properties and can form a coating film that is not only excellent in heat resistance but also excellent in friction resistance. The polymer of the present invention is suitable as a main component or adhesive of the above-mentioned coating resin composition. According to the method for producing the polymer of the present invention, a polymer with a molecular weight suitable as a constituent polymer of the coating film can be effectively obtained. The coating film of the present invention has excellent film-forming properties and heat resistance, and also excellent friction resistance. According to the method for forming a coating film of the present invention, a coating film that achieves excellent film-forming properties and is excellent in both heat resistance and friction resistance can be obtained. DETAILED DESCRIPTION

[0067] In the description of the present invention, a numerical range represented by “to” means a range including the numerical values ​​described before and after “to” as the lower limit and the upper limit.

[0068] In the description of the present invention, regarding substituents, linking groups, etc. (hereinafter referred to as substituents, etc.) that are not indicated as substituted or unsubstituted, it means that the group may have a suitable substituent. Therefore, in this specification, even when simply described as a "group" (e.g., "alkyl"), the "group" (e.g., "alkyl") includes not only forms without substituents (e.g., "unsubstituted alkyl"), but also forms with substituents (e.g., "substituted alkyl"). This also applies to compounds that are not indicated as substituted or unsubstituted. As preferred substituents, there can be mentioned substituents selected from the substituent T described below.

[0069] In the description of the present invention, when multiple substituents are present, or when multiple substituents are specified simultaneously or selectively, these substituents may be the same or different from each other. Furthermore, even if not otherwise specified, when multiple substituents are adjacent, these substituents may be linked or fused to form a ring.

[0070] In this specification, when a polymer has a plurality of constituent components having the same representation (represented by the same general formula), the constituent components may be the same as or different from each other.

[0071] [Coating resin composition]

[0072] 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 a terminal structure represented by formula (III-A) or (III-B). Hereinafter, this polymer may be simply referred to as "the above polymer."

[0073] [Chemical Formula 9]

[0074]

[0075] In the formula, Me represents a methyl group. In formula (I), the substituent shown on the right side of Me that is bonded to the carbon atom to which Me is bonded is an isobutyl group.

[0076] 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, further preferably 40% by mass or more, and particularly preferably 50% by mass or more. In addition, in the above polymer, the content of the structural unit represented by formula (I) is usually 70% by mass or less, and preferably 65% ​​by mass or less.

[0077] [Chemical Formula 10]

[0078]

[0079] 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, further preferably 30% by mass or more, and particularly preferably 40% by mass or more. In addition, in the above polymer, the content of the structural unit represented by formula (II) is usually 60% by mass or less, and preferably 50% by mass or less.

[0080] By setting the content of the structural unit represented by formula (I) and the structural unit represented by formula (II) in the polymer within the above range, the polymer can be provided with both rigidity and appropriate flexibility, further improving the abrasion resistance of the coating film. Furthermore, when a functional material is used simultaneously, the compatibility between the functional material and the polymer can be improved, thereby more reliably ensuring the desired film-forming properties.

[0081] [Chemical Formula 11]

[0082]

[0083] Where R a and R b represents a monovalent organic group. In formula (III-A), R a By R aThe carbon atom in the formula (III-A) is bonded to the oxygen atom shown in the formula (III-B). b By R b The carbon atom in R is bonded to the carbonyl group represented by formula (III-B). a and R b It preferably does not contain fluorine atoms. * represents a bonding site. In the following formulae, * also represents a bonding site.

[0084] Can be used as R a and R b The monovalent organic group is preferably an alkyl group or an aryl group. a and R b The alkyl group may be straight-chain or branched, and the number of carbon atoms (including the number of carbon atoms of the substituent when it has a substituent) is preferably 1 to 13, more preferably 1 to 8, also preferably 1 to 6, and even more preferably 1 to 3. a and R b In the case of an alkyl group, the number of carbon atoms is preferably as small as possible from the viewpoint of friction resistance.

[0085] Can be used as R a and R b The number of carbon atoms of the aryl group (when it has a substituent, the number of carbon atoms including the substituent) is preferably 6 to 30, more preferably 6 to 25, further preferably 6 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. a and R b The aryl group is preferably a phenyl group.

[0086] The terminal structure represented by the above formula (III-A) is preferably represented by the following formula (III-A-1).

[0087] [Chemical Formula 12]

[0088]

[0089] Where R d represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group (preferably an alkylcarbonyloxy group or an arylcarbonyloxy group, more preferably an alkylcarbonyloxy group) or a halogen atom, and s is an integer of 0 to 5.

[0090] R d An alkyl group, an alkoxy group, an alkoxycarbonyl group or an acyloxy group is preferred, an alkyl group or an alkoxy group is more preferred, and an alkyl group is further preferred.

[0091] Can be used as R d The alkyl group can be any of a straight chain, a branched chain, and a cyclic alkyl group. dThe number of carbon atoms of the alkyl group (including the number of carbon atoms of the substituent when it has a substituent) is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4. d The alkyl group is preferably methyl or tert-butyl, more preferably methyl. d When it is a methyl group, s is preferably 2 or 3, more preferably 3.

[0092] Can be used as R d The number of carbon atoms of the aryl group (when having a substituent, the number of carbon atoms including the substituent) is preferably 6 to 26, more preferably 6 to 20, further preferably 6 to 15, particularly preferably 6 to 12, and most preferably 6 to 10. d Preferred specific examples of the aryl group include phenyl, 4-methoxyphenyl, 4-acetoxyphenyl, 1-naphthyl, and 2-naphthyl.

[0093] Can be used as R d The number of carbon atoms in the alkoxy group, alkoxycarbonyl group, and acyloxy group (when having a substituent, the number of carbon atoms including the substituent) is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. For the alkoxycarbonyl group and acyloxy group, the preferred number of carbon atoms is the number of carbon atoms excluding the carbon atom forming the carbonyl group in each group.

[0094] Can be used as R d The number of carbon atoms of the aryl group in the aryloxy group and the aryloxycarbonyl group (including the carbon atoms of the substituent when having a substituent) is preferably 6 to 30, more preferably 6 to 25, further preferably 6 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. d The aryl group is preferably phenyl, 4-methoxyphenyl or 4-acetoxyphenyl, more preferably phenyl.

[0095] s is preferably an integer of 0-3.

[0096] Preferred terminal structures represented by the above formula (III-A) or (III-A-1) include, for example, terminal structures represented by the following formulas.

[0097] [Chemical Formula 13]

[0098]

[0099] [Chemical Formula 14]

[0100]

[0101] Preferred terminal structures represented by the above formula (III-B) include, for example, terminal structures represented by the following formulas.

[0102] [Chemical Formula 15]

[0103]

[0104] The total proportion of the terminal structures represented by the formula (III-A) or (III-B) in all terminal structures of the polymer is preferably 50 to 100 mol%, more preferably 70 to 100 mol%, and even more preferably 90 to 100 mol%.

[0105] Furthermore, the terminal structure represented by formula (III-A) or (III-B) can be introduced using a monophenol compound or a monovalent carboxylic acid chloride as an end-capping agent, for example, in solution polymerization or interfacial polymerization. Furthermore, after obtaining a polymer having a phenolic hydroxyl group as a terminal structure, the phenolic hydroxyl group can be acylated by a polymer reaction, thereby introducing the phenolic hydroxyl group into the structure of (III-B).

[0106] The polymer may contain, in addition to the structural units represented by the above formulae (I) and (II), at least one structural unit represented by, for example, the following formula (IA) or (IB). However, the structural unit represented by the above formula (I) is excluded from the structural unit represented by the following formula (IA).

[0107] [Chemical Formula 16]

[0108]

[0109] In the above formula (IA), R 1 represents an unsubstituted chain branched alkyl group having 4 or more carbon atoms (R 1 The chain branched alkyl group has no substituent). R 1 The number of carbon atoms in R is preferably 4 to 20, more preferably 4 to 15, further preferably 4 to 10, and particularly preferably 4 to 8. 1 The number of carbon atoms in R is preferably 5 or more. 1 The number of carbon atoms in the moiety is preferably 5 to 20, more preferably 6 to 15, more preferably 6 to 10, and even more preferably 7 to 8.

[0110] As R 1Preferred specific examples include 1-methylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 4-methylpentyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 2,4,4-trimethylpentyl, 1-ethylheptyl, 2-ethylheptyl, 3-methylhexyl, and 11-methyldodecyl.

[0111] Among them, as R 1 , preferably 1-methylpropyl, 1-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylhexyl, 1-ethylheptyl, 2,4,4-trimethylpentyl, more preferably 1-ethylbutyl, 1-ethylpentyl, 2,4,4-trimethylpentyl, 1-ethylheptyl.

[0112] R 2 represents a hydrogen atom, a straight-chain alkyl group or an aryl group,

[0113] Can be used as R 2 The number of carbon atoms of the linear alkyl group is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4. 2 The straight-chain alkyl group is preferably a methyl group or an ethyl group, more preferably a methyl group.

[0114] Can be used as R 2 The number of carbon atoms of the aryl group is preferably 6 to 26, more preferably 6 to 20, further preferably 6 to 15, particularly preferably 6 to 12, and most preferably 6 to 10. 2 Preferred specific examples of the aryl group include phenyl, 4-methoxyphenyl, 4-acetoxyphenyl, 1-naphthyl, and 2-naphthyl.

[0115] R 2 Preferred is a hydrogen atom or a methyl group.

[0116] R 3 represents a hydrogen atom, an alkyl group or an aryl group,

[0117] Can be used as R 3 The alkyl group can be any of a straight chain, a branched chain, and a cyclic alkyl group. 3 The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4. 3 The alkyl group is preferably a methyl group or an ethyl group, more preferably a methyl group.

[0118] Can be used as R3 The meanings of the aryl groups are respectively the same as those of the aryl groups which can be used as R 2 The same is true for the aryl group and the preferred aspects are also the same.

[0119] R 3 Preferred is a hydrogen atom or a methyl group.

[0120] In the above formula (IA), R 1 and R 2 bonded without forming a ring structure. 1 The number of carbon atoms and 2 R 3 The total number of carbon atoms is 6 or more, preferably 6-20, more preferably 6-16, and even more preferably 6-13.

[0121] [Chemical Formula 17]

[0122]

[0123] In the above formula (IB), R 4 represents a hydrogen atom, a straight-chain alkyl group or an aryl group.

[0124] Can be used as R 4 The meaning of the straight chain alkyl group is the same as that of the straight chain alkyl group which can be used as R 2 The straight-chain alkyl groups are the same as those in the preceding group, and the preferred manner is also the same.

[0125] Can be used as R 4 The meaning of aryl is the same as that of R 2 The same is true for the aryl group and the preferred aspects are also the same.

[0126] R 5 represents a hydrogen atom, an alkyl group or an aryl group, and can be R 5 The meanings of the alkyl or aryl groups are respectively the same as those of the groups that can be used as R 3 The alkyl or aryl groups are the same and the preferred aspects are also the same.

[0127] R 5 Preferred is a hydrogen atom or a methyl group.

[0128] n is an integer of 2 to 20, preferably 3 to 20, more preferably 4 to 20, further preferably 4 to 15, particularly preferably 5 to 13, and most preferably 6 to 10.

[0129] When the polymer has the structural unit represented by the formula (IA), R 2 It is preferably a hydrogen atom, an unsubstituted linear alkyl group or an unsubstituted aryl group. 1 and R 2 The entire structure is preferably composed only of carbon atoms and hydrogen atoms.

[0130] Specific examples of the structural unit represented by the above formula (IA) are shown below, but the present invention is not to be construed as being limited to the following specific examples. In the following formulae, Me represents a methyl group.

[0131] [Chemical Formula 18]

[0132]

[0133] Specific examples of the structural unit represented by the above formula (IB) are shown below, but the present invention is not to be construed as being limited to the following specific examples.

[0134] [Chemical Formula 19]

[0135]

[0136] [Chemical Formula 20]

[0137]

[0138] The polymer may contain, in addition to the structural units represented by each of the formulae (I), (IA), (IB), and (II), a structural unit represented by the following formula (IV), for example. The structural unit represented by the following formula (IV) is not incorporated into the polymer as a structural unit represented by the formula (II).

[0139] [Chemical Formula 21]

[0140]

[0141] In formula (IV), R c represents an alkyl group, an aryl group or a halogen atom, and r is an integer of 0 to 4.

[0142] Can be used as R c The meanings of the alkyl and aryl groups are respectively the same as those of the groups that can be used as R 3 The alkyl and aryl groups are the same and the preferred aspects are also the same.

[0143] r is preferably 0-3.

[0144] Specific examples of the structural unit represented by the above formula (IV) are shown below, but the present invention is not to be construed as being limited to the following specific examples.

[0145] [Chemical Formula 22]

[0146]

[0147] The polymer may contain at least one structural unit represented by the following formula (IC), for example, in the remainder other than the structural units represented by the formulas (I), (IA), (IB), (II), and (IV).

[0148] [Chemical Formula 23]

[0149]

[0150] In the above formula (IC), R c and r have the same meanings as R in the above formula (IV) c and r are the same, and the preferred embodiment is also the same. 1 represents an oxygen atom, a sulfur atom, or a hydrocarbon group having 1 to 15 carbon atoms. The structural unit represented by formula (IC) is a structural unit different from the structural units represented by each of formulas (IA) and (IB). That is, in the present invention, a structural unit included in the structural unit represented by formula (IC) and a structural unit also included in the structural unit represented by any of formulas (IA) and (IB) are to be interpreted as the structural unit represented by any of formulas (IA) and (IB) above, not the structural unit represented by formula (IC).

[0151] As can be adopted as W 1 The hydrocarbon group has 1 to 15 carbon atoms, preferably has 1 to 12 carbon atoms, and more preferably has 1 to 10 carbon atoms.

[0152] Examples of the divalent phenol compound into which the structural unit represented by the formula (IC) is introduced 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), 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, and 1,1-bis(4-hydroxyphenyl)-1-phenylethane. phenyl)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-propylene)-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-di-sec-butyl-4-hydroxyphenyl)methane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(2-hydroxy-3,5-di-tert-butylphenyl)ethane, bis(3-nonyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, bis(2-hydroxy-3,5-di-tert-butyl-6-methylphenyl)methane, 1,1-bis(3-phenyl-4-hydroxyphenyl)-1-phenylethane, bis(3-fluoro-4-hydroxyphenyl)methane, 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, (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'-tetramethyl-4,4'-biphenol Tert-butyl-4,4'-biphenol, bis(4-hydroxyphenyl)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-di-tert-butyl-4-hydroxyphenyl)-1-phenylethane, 1,1-bis(2-methyl-4-hydroxy-5-cyclohexylphenyl)-2-methylpropane, 1,1-bis(2-hydroxy-3,5-di-tert-butylphenyl) ethane, isatinyl bisphenol, isatin biscresol, 2,2',3,3',5,5'-hexamethyl-4,4'-biphenol, bis(2-hydroxyphenyl)methane, 2,4'-methylene bisphenol, 1,2-bis(4-hydroxyphenyl)ethane, 2-(4-hydroxyphenyl)-2-(2-hydroxyphenyl)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-di-tert-butyl-4-hydroxyphenyl)ethane, bis(2-hydroxy-3,5-di-tert-butylphenyl)methane, 2,2-bis(3-phenylvinyl-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'-tetra-tert-butyl-2,2'-biphenol, 2,2'-diallyl-4,4'-biphenol, 1,1- Bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5,5-tetramethyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,4-trimethyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3-dimethyl-5-ethyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclopentane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane, 1,1-bis(3,5-diphenyl-4-hydroxyphenyl)-3,3,5-trimethyl-cyclopentane Hexane, 1,1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane, 1,1-bis(3-phenyl-4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane, 1,1-bis(3,5-dichloro-4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane, 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-trimethyl-cyclohexane, bis(4-hydroxyphenyl)sulfone, bis(2-hydroxyphenyl)sulfone, bis(3,5-dimethyl- 4-hydroxyphenyl)sulfone group, bis(3,5-diethyl-4-hydroxyphenyl)sulfone group, bis(3-methyl-4-hydroxyphenyl)sulfone group, bis(3-ethyl-4-hydroxyphenyl)sulfone group, bis(4-hydroxyphenyl)sulfide group, bis(3,5-dimethyl-4-hydroxyphenyl)sulfide group, bis(3,5-diethyl-4-hydroxyphenyl)sulfide group, bis(3-methyl-4-hydroxyphenyl)sulfide group, bis(3-ethyl-4-hydroxyphenyl)sulfide group, 2,4-dihydroxydiphenylsulfone, 4,4'-(α-methylbenzylidene)bisphenol, 1,1-bis(4-hydroxy-3-methylphenyl)-ethane, bisphenol E, etc. That is, the structural unit represented by the formula (IC) is a structural unit that can be derived from the above-mentioned dihydric phenol compound.

[0153] Among the above divalent phenol compounds, 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.

[0154] In the polymer, the content of the structural unit represented by the 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.

[0155] The polymer also preferably contains, in addition to the structural units represented by the above formulae (I), (IA), (IB), (II), (IV), and (IC), for example, a structural unit derived from a dicarboxylic acid as described below.

[0156] 4,4'-Diphenyletherdicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, Adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, etc.

[0157] Among the structural units derived from the above-mentioned dicarboxylic acids, structural units derived from 4,4′-diphenyl ether dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, and terephthalic acid are preferred from the viewpoint of further improving the abrasion resistance of the coating film.

[0158] Examples of terminal structures other than the above-mentioned formula (III-A) or (III-B) include terminal structures represented by the following formulas.

[0159] *-H

[0160] *-OH

[0161] When the polymer of the present invention has the structural unit represented by the above formula (I) as an end structure other than the above formula (III-A) or (III-B), the end thereof is represented, for example, as follows.

[0162] [Chemical Formula 24]

[0163]

[0164] When the polymer of the present invention has the structural unit represented by the above formula (IA) as an end structure other than the above formula (III-A) or (III-B), the end thereof is represented, for example, as follows.

[0165] [Chemical Formula 25]

[0166]

[0167] When the polymer of the present invention has the structural unit represented by the above formula (IB) as an end structure other than the above formula (III-A) or (III-B), the end thereof is represented, for example, as follows.

[0168] [Chemical Formula 26]

[0169]

[0170] When the polymer of the present invention has the structural unit represented by the above formula (IC) as an end structure other than the above formula (III-A) or (III-B), the end thereof is represented, for example, as follows.

[0171] [Chemical Formula 27]

[0172]

[0173] When the polymer of the present invention has the structural unit represented by the above formula (II) as an end structure other than the above formula (III-A) or (III-B), the end thereof is represented, for example, as follows.

[0174] [Chemical Formula 28]

[0175]

[0176] The terminal structures represented by *-H and *-OH are preferably not included. However, if included, the content is preferably 0 to 50 mol%, more preferably 0 to 30 mol%, and even more preferably 0 to 10 mol% of all the terminal structures in the polymer.

[0177] The weight average molecular weight of the polymer is preferably 50,000 to 250,000, more preferably 80,000 to 180,000, and even more preferably 100,000 to 150,000.

[0178] In the present invention, the molecular weight of a polymer refers to a weight average molecular weight unless otherwise specified. The weight average molecular weight can be determined as a molecular weight based on polystyrene conversion using gel permeation chromatography (GPC). Due to the solvent solubility of the polymer of the present invention, tetrahydrofuran can preferably be used as an eluent. The range of the above-mentioned preferred weight average molecular weight is based on the weight average molecular weight based on polystyrene conversion when tetrahydrofuran is used as an eluent.

[0179] As the substituent T, the following substituents can be mentioned.

[0180] Alkyl (preferably an alkyl group having 1 to 20 carbon atoms, for example, methyl, ethyl, isopropyl, tert-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl (preferably an alkenyl group having 2 to 20 carbon atoms, for example, vinyl, allyl, oleyl, etc.), alkynyl (preferably an alkynyl group having 2 to 20 carbon atoms, for example, ethynyl, butadiynyl, phenylethynyl, etc.), cycloalkyl (preferably a cycloalkyl group having 3 to 20 carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), aryl (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 The heterocyclic group may be a 5- or 6-membered heterocyclic group having at least one oxygen atom, sulfur atom or nitrogen atom. The heterocyclic group may include an aromatic heterocyclic group and an aliphatic heterocyclic group. For example, tetrahydropyranyl, tetrahydrofuranyl, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, etc.), alkoxy (preferably an alkoxy having 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropoxy, benzyloxy, etc.), aryloxy (preferably an aryl having 6 to 26 carbon atoms, such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), heterocyclooxy (a group in which an -O- group is bonded to the above heterocyclic group), alkoxycarbonyl (preferably an alkoxy having 2 to 3 carbon atoms ... alkyloxycarbonyl (preferably an alkyloxycarbonyl group having 0 to 20 carbon atoms, for example, an ethoxycarbonyl group, a 2-ethylhexyloxycarbonyl group, etc.), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 6 to 26 carbon atoms, for example, a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 3-methylphenoxycarbonyl group, a 4-methoxyphenoxycarbonyl group, etc.), an amino group (preferably an amino group having 0 to 20 carbon atoms, an alkylamino group, an arylamino group, for example, an amino group (-NH2), N,N-dimethylamino group, N,N-diethylamino group, N-ethylamino group, anilino group, etc.), a sulfamoyl group (preferably a sulfamoyl group having 0 to 20 carbon atoms, for example, N,N-dimethylsulfamoyl group, N-phenylsulfamoyl group, etc.), an acyl group (preferably an alkylcarbonyl group, an alkenylcarbonyl group, an alkynylcarbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, preferably a an acyl group having 1 to 20 atoms, for example, acetyl, propionyl, butyryl, octanoyl, hexadecanoyl, acryloyl, methacryloyl, crotonyl, benzoyl, naphthoyl, nicotinoyl, etc.; an acyloxy group (including an alkylcarbonyloxy group, an alkenylcarbonyloxy group, an alkynylcarbonyloxy group, an arylcarbonyloxy group, and a heterocycliccarbonyloxy group, preferably an acyloxy group having 1 to 20 carbon atoms, for example, acetyloxy, propionyloxy, butyryl, octanoyl, hexadecanoyl, acryloyl, methacryloyl, crotonyloxy, benzoyloxy, naphthoyloxy, nicotinoyl, etc.); an aroyloxy group (preferably an aroyloxy group having 7 to 23 carbon atoms, for example, benzoyloxy, etc.); a carbamoyl group (preferably a carbamoyl group having 1 to 20 carbon atoms, for example, N,

[0065] Examples of the present invention include N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.), acylamino (preferably acylamino having 1 to 20 carbon atoms, for example, acetylamino, benzylamino, etc.), alkylthio (preferably alkylthio having 1 to 20 carbon atoms, for example, methylthio, ethylthio, isopropylthio, benzylthio, etc.), arylthio (preferably arylthio having 6 to 26 carbon atoms, for example, phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio, etc.), heterocyclic thio (a group in which -S- is bonded to the above heterocyclic group), alkylsulfonyl (preferably alkylthio having 1 to 20 carbon atoms, for example, methylthio, ethylthio, isopropylthio, benzylthio, etc.), alkylsulfonyl groups, for example, methylsulfonyl and ethylsulfonyl groups), arylsulfonyl groups (preferably arylsulfonyl groups having 6 to 22 carbon atoms, for example, phenylsulfonyl groups), alkylsilyl groups (preferably alkylsilyl groups having 1 to 20 carbon atoms, for example, monomethylsilyl, dimethylsilyl, trimethylsilyl and triethylsilyl groups), arylsilyl groups (preferably arylsilyl groups having 6 to 42 carbon atoms, for example, triphenylsilyl groups), phosphoryl groups (preferably phosphate groups having 0 to 20 carbon atoms, for example, -OP(=O)(R, P ) 2), phosphono group (preferably a phosphono group having 0 to 20 carbon atoms, for example, -P(=O)(R P ) 2), phosphinyl group (preferably a phosphinyl group having 0 to 20 carbon atoms, for example, -P(R P ) 2), sulfo group (sulfonic acid group), carboxyl group, hydroxyl group, sulfanyl group, cyano group, halogen atom (such as fluorine atom, chlorine atom, bromine atom, iodine atom, etc.). R P is a hydrogen atom or a substituent (preferably a group selected from substituent T).

[0181] Furthermore, each group exemplified in these substituents T may further have the above-mentioned substituent T as a substituent.

[0182] The polymer can be obtained by polycondensing a monomer providing the structural unit represented by the formula (I), a monomer providing the structural unit represented by the formula (II), and other monomers as needed, by a conventional method.

[0183] The manufacturing method of the above-mentioned polymer is not particularly limited. As an example, interfacial polymerization, solution polymerization, etc. can be enumerated, preferably interfacial polymerization. Interfacial polymerization is a polymerization method for obtaining polyester by mixing a dibasic carboxylic acid halide dissolved in a water-incompatible organic solvent and a dihydric phenol dissolved in an alkaline aqueous solution. As documents relevant to interfacial polymerization, WMEARECKSON, J.Poly.Sci., XL399, 1959 and Special Publication No. 40-1959 Communiqué can be enumerated. Compared with solution polymerization, the reaction of interfacial polymerization is faster, so the hydrolysis of the acyl halide can be suppressed, and as a result, a high molecular weight resin can be obtained.

[0184] More specifically, an alkaline aqueous solution of a dihydric phenol is prepared as the aqueous phase, followed by the addition of a polymerization catalyst. Meanwhile, as the organic phase, a dicarboxylic acid halide is dissolved in a water-immiscible solvent that dissolves the polymer. This solution is then mixed with the alkaline solution and subjected to polymerization while preferably stirring at a temperature below 50°C for 1 to 8 hours, thereby obtaining the desired polymer solution. The organic phase does not necessarily need to dissolve all of the dicarboxylic acid halide.

[0185] In the method for producing the polymer of the present invention, the following method A can be used. When the dibasic carboxylic acid halide is insoluble or has low solubility in the solvent of the organic layer, the following method is particularly effective.

[0186] Method A

[0187] An alkaline aqueous solution of dihydric phenol is prepared as the aqueous phase, and then a polymerization catalyst is added. In this process, the dihydric phenol or its phenoxide may not be completely dissolved in the alkaline aqueous solution of dihydric phenol.

[0188] Alternatively, as an organic phase, an organic solvent that is incompatible with water and dissolves the polymer is mixed into the alkaline solution and the mixture is suspended by stirring.

[0189] Adding solid 4,4'-biphenyldicarboxylic acid chloride in the form of powder or the like to the reaction mixture allows for polymerization. This method has three advantages.

[0190] The first point is that since 4,4'-biphenyl dicarboxylic acid chloride is not prepared as a solution or solvent suspension, hydrolysis can be suppressed during the period leading up to mixing with the alkaline aqueous solution of the dihydric phenol. The second point is that since the solvent suspension is not handled, the complicated operation of pipetting the solvent suspension for mixing with the alkaline aqueous solution can be avoided. To avoid using 4,4'-biphenyl dicarboxylic acid chloride as a solvent suspension, it is conceivable to dilute it with a large amount of solvent to form a solution. In contrast, the third advantage of Method A, which adds solid 4,4'-biphenyl dicarboxylic acid chloride, is that since it does not need to be completely dissolved, the amount of organic solvent used can be reduced, resulting in improved production efficiency and a reduction in organic solvent.

[0191] Furthermore, the polymerization catalyst may be added to the aqueous layer in advance, or may be added to the organic layer.

[0192] Examples of the base used in preparing the aqueous dihydric phenol solution include sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. The amount of the base used is generally 2 to 5 times the number of moles of the dihydric phenol, that is, 1 to 2.5 equivalents to the hydroxyl group.

[0193] In the method for producing the polymer of the present invention, the following method B can be used.

[0194] Method B

[0195] As the organic phase, a water-immiscible organic solvent that dissolves the polymer is mixed with 4,4'-biphenyldicarboxylic acid chloride and stirred to form a suspension. Separately, an alkaline aqueous solution of a dihydric phenol is prepared in a separate container as the aqueous phase, followed by the addition of a polymerization catalyst. The resulting aqueous layer is added to the suspension to initiate a polymerization reaction.

[0196] In some cases, the reproducibility of the polymerization process can be improved by preliminarily preparing 4,4'-biphenyldicarboxylic acid chloride as a suspension in an organic solvent using Method B. Furthermore, compared to the reverse step of adding a suspension of 4,4'-biphenyldicarboxylic acid chloride to an alkaline aqueous solution of a dihydric phenol, Method B does not involve the step of transferring the suspension, thus reducing operational complexity and the likelihood of hydrolysis of 4,4'-biphenyldicarboxylic acid chloride during the transfer step.

[0197] In the production method of the present invention, the following method C can be used.

[0198] Method C

[0199] The general interfacial polymerization method is as described above. An alkaline aqueous solution of a dihydric phenol is prepared as the aqueous phase, followed by the addition of a polymerization catalyst. Meanwhile, a solution or solvent suspension of 4,4'-biphenyldicarboxylic acid chloride is prepared as the organic phase and added to the alkaline solution to initiate the polymerization reaction.

[0200] In interfacial polymerization, an end-capping agent may be used during polymerization from the perspective of controlling the molecular weight of the polymer. Furthermore, from the perspective of controlling the properties of the polymer, it is also preferred to cap the ends of the polymer with monophenols, monoacid chlorides, monoalcohols, monocarboxylic acids, or the like. Examples of the monohydric phenols used as such end-capping 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, 2-phenyl-2-(4-hydroxyphenyl)propane (sometimes referred to as "p-(α-cumyl)phenol"), 2-phenyl-2-(2-hydroxyphenyl)propane, and 2-phenyl-2-(3-hydroxyphenyl)propane. Examples of the monohydric acid chlorides used as end-capping agents include benzoyl chloride, methanesulfonyl chloride, phenyl chlorocarbonate, acetyl chloride, and lauroyl chloride. Examples of the monohydric alcohol used as the end-capping agent include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, pentanol, hexanol, dodecanol, stearyl alcohol, benzyl alcohol, and phenylethyl alcohol. Examples of the monocarboxylic acid used as the end-capping agent include acetic acid, propionic acid, octanoic acid, cyclohexanecarboxylic acid, benzoic acid, methylbenzoic acid, phenylacetic acid, p-tert-butylbenzoic acid, and p-methoxyphenylacetic acid.

[0201] Among these, the terminal is preferably blocked with a monohydric phenol or a monohydric acid chloride, and more preferably blocked with p-tert-butylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, benzoyl chloride, or acetyl chloride.

[0202] 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 tributylbenzylammonium halide, tetrabutylphosphonium halide, trimethylbenzylammonium halide, and triethylbenzylammonium halide. Among these, compounds selected from tributylbenzylammonium halide, tetrabutylammonium halide, tributylbenzylammonium halide, and tetrabutylphosphonium halide are preferred from the viewpoint of easily accelerating polymerization.

[0203] As the solvent 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, aromatic hydrocarbons such as toluene, benzene, xylene, and anisole can be used. Tetrahydrofuran can also be used. Among them, dichloromethane and o-dichlorobenzene are preferred as organic solvents for the organic layer.

[0204] When the dibasic carboxylic acid halide is insoluble or has low solubility in the organic solvent of the organic layer, other organic solvents may be used. The organic solvent of the organic layer is preferably an organic solvent that is insoluble in water. However, in order to improve the solubility of the dibasic carboxylic acid halide in the organic layer, or to increase the efficiency of the polymerization reaction and suppress the hydrolysis of the dibasic carboxylic acid halide to obtain a polymer of a desired molecular weight, a portion or all of the organic layer may be replaced with an organic solvent that is also soluble in water.

[0205] Examples of organic solvents effective for improving the solubility of the dicarboxylic acid halide in the organic layer include tetrahydrofuran, N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), 1,4-dioxane, and 1,3-dioxolane.

[0206] From the perspective of productivity, the polymer concentration relative to the organic solvent in the organic layer is preferably as high as possible. 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 amount 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.

[0207] After polymerization is completed by adding acetic acid to the resulting polymer solution, the polymer solution is repeatedly stirred and washed with water to remove ionic components such as sodium ions, potassium ions, lithium ions, chloride ions, and the polymerization catalyst. The water used for washing can be acidic or alkaline, and washing is repeated until the wastewater is neutral.

[0208] The resulting polymer solution is added dropwise to a poor solvent to precipitate the polymer as a solid component. The solid content concentration of the polymer solution is preferably 7% by mass or less. Furthermore, the volume of the poor solvent is preferably at least 3 times the volume of the polymer solution. Examples of the poor solvent include methanol, ethanol, isopropyl alcohol, acetone, acetonitrile, and hexane.

[0209] By adding the polymer solution to a poor solvent, the residual monomers and impurities derived from alkali and polymerization catalysts contained in the polymer can be reduced. In order to reduce the content of residual monomers and impurities, it is particularly preferred that the immersion time in the poor solvent after the poor solvent is subjected to the precipitation treatment is set to more than 1 minute. In addition, when using trimethylbenzyl ammonium halide, triethylbenzyl ammonium halide, etc. with relatively low polymerization activity as a polymerization catalyst, it is preferred that the immersion time is set to more than 3 minutes. When taking out when not yet reaching 3 minutes, it is possible that the removal of the residual monomers and impurities in the polymer is insufficient. In order to reduce residual monomers and impurities, the obtained polymer can be repeatedly dissolved in a solvent again and added to the poor solvent and the above-mentioned operation of precipitation.

[0210] During the production of the aforementioned polymers, impurities insoluble in tetrahydrofuran or dichloromethane may sometimes be generated. One possible reason for this is that 4,4'-biphenyldicarboxylic acid chloride is used to introduce the structural unit represented by formula (II). Specifically, this is believed to be due to the introduction of 4,4'-biphenyldicarboxylic acid or 4-(4-carbonylphenyl)-benzoyl chloride, potentially impurities contained in 4,4'-biphenyldicarboxylic acid, into the polymer production process, resulting in the formation of an acid anhydride compound as an insoluble impurity, as shown in the following scheme.

[0211] This is also considered to be because 4,4′-biphenyldicarboxylic acid or 4-(4-carbonylphenyl)-benzoyl chloride is generated in the polymerization reaction of the production process and then forms an acid anhydride compound as shown in the following scheme.

[0212] [Chemical Formula 29]

[0213]

[0214] Depending on the application of the polymer or coating film of the present invention, it is preferred that the polymer or coating film of the present invention does not contain such insoluble impurities. As a method for obtaining a polymer free of insoluble impurities, for example, a method of removing the insoluble impurities by treating a solution containing both the polymer and the insoluble impurities with various adsorbents can be cited.

[0215] Furthermore, for the purpose of suppressing the generation of insoluble impurities, it is preferred to use 4,4'-biphenyldicarboxylic acid chloride, which has a low content of 4,4'-biphenyldicarboxylic acid or 4-(4-carbonylphenyl)-benzoic acid chloride, as the impurity. The content of 4,4'-biphenyldicarboxylic acid and 4-(4-carbonylphenyl)-benzoic acid chloride in 4,4'-biphenyldicarboxylic 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, respectively.

[0216] The coating resin composition of the present invention generally contains a solvent in addition to the above-mentioned polymer. The polymer obtained by the above method has high solubility in a general solvent or a mixed solvent thereof. That is, as a solvent used alone or in combination, 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, aromatic hydrocarbons such as toluene, benzene, and xylene, N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), 1,4-dioxane, tetrahydrofuran, etc. can be cited.

[0217] In order to impart desired functionality to the resulting coating film of the present invention, the coating resin composition of the present invention also preferably contains a functional material. The function 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 set to 90:10 to 50:50, and preferably 80:20 to 50:50.

[0218] The functional material is not particularly limited. From the perspective of further improving compatibility and interaction with the polymer, an aromatic ring-containing compound containing a benzene ring is preferred. The aromatic ring-containing compound containing a benzene ring preferably has 2 to 15 benzene rings, more preferably 3 to 12 benzene rings, and even more preferably 4 to 10 benzene rings. Furthermore, the molecular weight of the aromatic ring-containing compound containing a benzene ring is preferably 200 to 2000, more preferably 250 to 1500, and even more preferably 300 to 1000.

[0219] The aromatic ring-containing compound including a benzene ring is preferably a compound represented by the following formula (V).

[0220] [Chemical formula 30]

[0221]

[0222] In the formula, X represents an oxygen atom, a sulfur atom, a hydrocarbon group which may have a substituent, or an imino group which may have a substituent. n1 represents an integer from 0 to 4. R represents a monovalent organic group or a hydroxyl group.

[0223] The hydrocarbon group that may have a substituent that can be used as X is preferably a hydrocarbon group containing an aromatic ring and having 6 to 35 carbon atoms, and more preferably a hydrocarbon group containing an aromatic ring and having 6 to 25 carbon atoms. Preferably, n1 is an integer of 0 to 2, and more preferably, n1 is 0 or 1. A preferred monovalent organic group that can be used as R is a linear alkyl group.

[0224] Since the aromatic compound represented by formula (V) contains multiple benzene rings and heteroatoms such as oxygen, sulfur, and nitrogen atoms, and the benzene rings in the aromatic compound represented by formula (V) have a high mass ratio and are rigid, the compatibility and interaction between the polymer and the functional material can be improved, further enhancing the mechanical properties of the resulting coating film. Furthermore, the densification of the coating film can be expected to suppress the moisture permeability of the coating film.

[0225] The molecular weight of the aromatic compound represented by the formula (V) is preferably 200 to 2000, more preferably 250 to 1500, and even more preferably 300 to 1000.

[0226] The number of benzene rings in the above formula (V) is preferably 2-15, more preferably 3-12, and even more preferably 4-10.

[0227] The aromatic compound represented by the formula (V) preferably has at least one of an oxygen atom and a nitrogen atom.

[0228] [Method for producing polymer]

[0229] Preferred embodiments of the method for producing a polymer of the present invention will be described.

[0230] In the interfacial polymerization of a dihydric carboxylic acid halide and a dihydric phenol, it is generally considered preferable to add the dihydric carboxylic acid halide to the alkaline aqueous solution of the dihydric phenol as a solution or slurry mixed with an organic solvent, as described above, from the perspective of preventing hydrolysis of the dihydric carboxylic acid halide and improving the reproducibility of the polymerization reaction. On the other hand, the present inventors have conducted extensive research and discovered that even when a solid such as a powder of 4,4'-biphenyldicarboxylic acid chloride is directly added to a mixture comprising an alkaline aqueous solution of the dihydric phenol, a polymerization catalyst, and an organic solvent for the organic layer, a polymer having a desired molecular weight can be effectively obtained.

[0231] The method for producing a polymer of the present invention is suitable as a method for producing a polymer having a structural unit represented by the following formula (II) (hereinafter also referred to as the "production method of the present invention"), and includes a step of mixing a mixture of an alkaline aqueous solution containing a dihydric phenol and an organic solvent with solid 4,4'-biphenyldicarboxylic acid chloride. The production method of the present invention more preferably includes a step of adding solid 4,4'-biphenyldicarboxylic acid chloride while stirring the mixture of an alkaline aqueous solution containing a dihydric phenol and an organic solvent. In the present invention, "solid 4,4'-biphenyldicarboxylic acid chloride" refers to solid 4,4'-biphenyldicarboxylic acid chloride itself, rather than a state mixed with an organic solvent (solution or slurry).

[0232] [Chemical Formula 31]

[0233]

[0234] The production method of the present invention can be carried out, for example, by the above-mentioned method A. The advantages of method A are as described above.

[0235] In the production method (method A) of the present invention, from the viewpoint of improving the properties of the obtained polymer, it is preferred to use, as the dihydric phenol component, a compound represented by the following formula that provides the structural unit represented by the above-mentioned formula (I).

[0236] [Chemical Formula 32]

[0237]

[0238] From the perspective of workability during production, solid 4,4'-biphenyldicarboxylic acid chloride preferably does not contain an organic solvent. Even if 4,4'-biphenyldicarboxylic acid chloride may contain an organic solvent, the content of the organic solvent relative to the total amount of solid 4,4'-biphenyldicarboxylic acid chloride and the organic solvent is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0239] In the interfacial polymerization of the production method of the present invention, it is preferred to use a compound represented by the following formula together with a dihydric phenol from the viewpoint of improving the properties of the obtained polymer and further controlling the molecular weight during polymerization.

[0240] HOR a

[0241] Where R a is the same as R in the above formula (III-A) a The same monovalent organic group has the same preferred aspects.

[0242] As mentioned above HOR a Examples of the compound represented by include monohydric phenols and monohydric alcohols used in the above-mentioned method for producing the polymer.

[0243] Regarding all the terminal structures of the polymer obtained by the production method of the present invention, those derived from the HOR a The ratio of the total terminal structures of the compounds represented by formula (III-A) is preferably the same as the ratio of the total terminal structures derived from the compounds represented by formula (III-A) in all terminal structures of the polymer.

[0244] Furthermore, it is also preferable to use a compound represented by the following formula together with 4,4'-biphenyldicarboxylic acid chloride.

[0245] [Chemical Formula 33]

[0246]

[0247] Where R b is the same as R in the above formula (III-B) b The same monovalent organic group has the same preferred aspects.

[0248] Examples of the compound represented by the above formula include monobasic acid chlorides used in the above-mentioned method for producing the polymer.

[0249] In the production method of the present invention, the monocarboxylic acid used in the production method of the above-mentioned polymer can be used together with 4,4'-biphenyldicarboxylic acid chloride.

[0250] The ratio of the total of terminal structures derived from the above-mentioned compound in all terminal structures of the polymer obtained by the production method of the present invention is preferably the same as the ratio of the total of terminal structures derived from the compound represented by formula (III-B) in all terminal structures of the above-mentioned polymer.

[0251] In the production method of the present invention, a monomer comprising at least one of the above-mentioned formulas (IA), (IB), (IV), and (IC) and the structural units derived from the above-mentioned dicarboxylic acid units used in the production method of the above-mentioned polymer can be used. The content of the above-mentioned formulas (II), (I), (IA), (IB), (IV), and (IC) and the structural units derived from the above-mentioned dicarboxylic acid units 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 also preferably the same as the weight-average molecular weight of the above-mentioned polymer.

[0252] The polymerization catalyst and organic solvent used in the production method of the present invention are the same as those used in the above-mentioned production method of the polymer, and preferred polymerization catalysts and organic solvents are also the same.

[0253] The reason why the desired polymer solution is obtained despite the low solvent solubility of 4,4'-biphenyl dicarboxylic acid chloride is believed to be that the added solid 4,4'-biphenyl dicarboxylic acid chloride is gradually consumed, starting with the components dissolved in the organic layer. As a result, some or all of the 4,4'-biphenyl dicarboxylic acid chloride dissolves and the polymerization reaction proceeds. Furthermore, the reason why the desired polymer is obtained despite the addition of solid 4,4'-biphenyl dicarboxylic acid chloride is believed to be that the reaction between the phenoxide of the dihydric phenol and 4,4'-biphenyl dicarboxylic acid chloride is very rapid. Therefore, even when the solid surface of 4,4'-biphenyl dicarboxylic acid chloride directly contacts the alkaline aqueous solution, the desired polymerization reaction proceeds. To further suppress the hydrolysis of 4,4'-biphenyl dicarboxylic acid chloride, it is preferable to reduce the amount of base used when preparing the alkaline aqueous solution of the dihydric phenol.

[0254] In the production method of the present invention, post-treatment in the above-mentioned production method of the polymer may be performed.

[0255] [Coating]

[0256] 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 when formed, and the coating film itself has excellent heat resistance and abrasion resistance.

[0257] Examples of coating films composited with functional materials include low moisture permeability films described in Japanese Patent Application Laid-Open No. 2016-69468. Specifically, by adding a phenol compound as a functional material to a polymer, the polymer and the functional material exhibit high compatibility, effectively suppressing moisture permeability.

[0258] Another example of a composite coating film containing a functional material is the charge transport layer of an electrophotographic photoreceptor. Specifically, the charge transport layer comprises the aforementioned polymer as a binder and a charge transport material, and high compatibility between the binder and the charge transport material is required. By using the coating film of the present invention as a charge transport layer comprising the aforementioned polymer and an aromatic compound as a charge transport material, a charge transport layer with excellent friction resistance can be achieved.

[0259] The coating film of the present invention can also be suitably used as, for example, a metal wire coating film, a polarizing plate protective film for display devices, and the like.

[0260] The coating film of the present invention can also be used with other layers disposed thereon. For example, by forming a protective layer in contact with the coating film of the present invention, the durability can be further improved.

[0261] The method for forming the coating of the present invention is not particularly limited as long as it can form a film containing the above-mentioned polymer. For example, it can be formed by applying the coating resin composition of the present invention on a substrate and drying the coating. The coating method and the drying method themselves can be appropriately applied to the method commonly used in the coating and drying of the coating solution. The substrate is not particularly limited and can be widely used for materials, parts, etc. having a surface to be coated.

[0262] Example

[0263] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In the structural formula shown below, Me represents a methyl group.

[0264] [Preparation of polymer constituting the coating composition]

[0265] <Example 1>

[0266] - Preparation of polymer (1) -

[0267] Polymer (1) was prepared according to the following scheme.

[0268] [Chemical Formula 34]

[0269]

[0270] In a reaction vessel equipped with a stirrer, 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 dithionite (manufactured by FUJIFILM Wako Pure Chemical Corporation), and 230 mL of water were added to prepare a suspension. While stirring the suspension at 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 under a nitrogen atmosphere for 30 minutes to prepare a solution (slightly turbid) in which the solid substance was substantially dissolved. 210 mL of o-dichlorobenzene (manufactured by FUJIFILM Wako Pure Chemical Corporation) was added to the aqueous solution, and after stirring for 30 minutes under a nitrogen atmosphere, 12.0000 g of powdered 4,4'-biphenyl dicarboxylic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. After the addition was completed, the temperature was set to 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 water layer was removed. After washing with a dilute acetic acid solution and ion exchange water, the polymer was precipitated by adding it to methanol (manufactured by FUJIFILM Wako Pure Chemical Corporation). The precipitated polymer was filtered and dried at 50°C. The polymer was dissolved again in 900 mL of tetrahydrofuran (manufactured by FUJIFILM Wako Pure Chemical Corporation) and added to methanol to precipitate the polymer. The precipitated polymer was filtered out, washed with methanol, and then dried at 50° C. to obtain 17.8 g of a white polymer (1).

[0271] The weight average molecular weight (Mw) of the polymer (1) as a molecular weight in terms of polystyrene was determined by gel permeation chromatography (GPC, using tetrahydrofuran as an eluent) to be 120,000.

[0272] Confirmed to be based on 1Based on the calculation of the unit molar ratio of each structure by H NMR, polymer (1) was 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'-biphenyldicarboxylic acid chloride, and 1% by mass of terminal structures derived from 2,3,5-trimethylphenol.

[0273] In the above method, 4,4'-biphenyldicarboxylic acid chloride powder was added, which corresponds to method A.

[0274] <Example 2>

[0275] - Preparation of polymer (2) -

[0276] According to the following scheme, a white polymer (2) was prepared.

[0277] [Chemical Formula 35]

[0278]

[0279] In a reaction vessel equipped with a stirring device, 260 mL of methylene chloride (manufactured by FUJIFILM Wako Pure Chemical Corporation) was added to 43.0952 g of 2,2-bis(4-hydroxyphenyl)-4-methylpentane (manufactured by Honshu Chemical Industry Co., Ltd.) and 33.0645 g of triethylamine (manufactured by FUJIFILM Wako Pure Chemical Corporation) to prepare a solution. At a temperature of 5°C, 45.0000 g of powdered 4,4'-biphenyldicarboxylic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added while stirring the solution. After the addition was completed, the temperature was raised to 30°C and the reaction was allowed to proceed by stirring for 4 hours under a nitrogen atmosphere. The solution after polymerization was diluted with 3000 mL of tetrahydrofuran and poured into methanol to precipitate a polymer. The precipitated polymer was filtered, washed with methanol, and then dried at 50°C. The polymer was dissolved again in 3000 mL of tetrahydrofuran and poured into methanol to precipitate a polymer. The precipitated polymer was filtered, washed with methanol, and then dried at 50° C. to obtain 68.9 g of a white polymer.

[0280] The above method is a solution polymerization method, not an interfacial polymerization method, and therefore does not correspond to any of Method A, Method B, and Method C.

[0281] In a reaction vessel equipped with a stirring device, 10.0000 g of the polymer and 1.2941 g of triethylamine were added with 110 mL of methylene chloride to prepare a solution. At a temperature of 5°C, 1.7121 g of benzoyl chloride (manufactured by FUJIFILM Wako Pure Chemical Corporation) was added while stirring the solution. After the addition was completed, the temperature was raised to 30°C and the reaction was allowed to proceed by stirring for 4 hours under a nitrogen atmosphere. The solution after polymerization was diluted with 400 mL of tetrahydrofuran and poured into methanol to precipitate a polymer. The precipitated polymer was filtered, washed with methanol, and then dried at 50°C. The polymer was dissolved in 400 mL of tetrahydrofuran again and poured into methanol to precipitate a polymer. The precipitated polymer was filtered, washed with methanol, and then dried at 50°C to obtain 8.7 g of a white polymer (2). The weight average molecular weight of the polymer (1) determined in the same manner as in Example 1 and the calculated content of the structural units are shown in Table 1.

[0282] <Example 3>

[0283] - Preparation of polymer (3) -

[0284] According to the following protocol and in accordance with Example 2, a white polymer (3) consisting of the structural units shown in Table 1 was prepared.

[0285] [Chemical Formula 36]

[0286]

[0287] Table 1 shows the weight average molecular weight of the polymer (3) determined in the same manner as in Example 1 and the calculated content of the structural unit.

[0288] <Example 4>

[0289] - Preparation of polymer (4) -

[0290] A white polymer (4) composed of the structural units shown in Table 1 was prepared according to the following scheme.

[0291] [Chemical Formula 37]

[0292]

[0293] In a reaction vessel equipped with a stirrer, 11.4493 g of 2,2-bis(4-hydroxyphenyl)-4-methylpentane (manufactured by Honshu Chemical Industry Co., Ltd.), 0.1930 g of p-tert-butylphenol (manufactured by FUJIFILM Wako Pure Chemical Corporation), 0.0572 g of sodium dithionite (manufactured by FUJIFILM Wako Pure Chemical Corporation), and 230 mL of water were added to prepare a suspension. While stirring the suspension at 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 under a nitrogen atmosphere for 30 minutes to prepare a solution (slightly turbid) in which the solid substance was substantially dissolved. To the aqueous solution was added 12.0000 g of 4,4'-biphenyl dicarboxylic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 210 mL of a mixed solution of methylene chloride (manufactured by FUJIFILM Wako Pure Chemical Corporation) (in a slurry state in Example 4). After the addition was completed, the temperature was set to room temperature (20°C) and the reaction was allowed to proceed by stirring for 4 hours under a nitrogen atmosphere. The polymerized solution was diluted with 300 mL of methylene chloride to remove the water layer. After washing with a dilute acetic acid solution and ion exchange water, the polymer was precipitated by adding it to methanol (manufactured by FUJIFILM Wako Pure Chemical Corporation). The precipitated polymer was filtered and dried at 50°C. The polymer was dissolved again in 900 mL of tetrahydrofuran (manufactured by FUJIFILM Wako Pure Chemical Corporation) and added to methanol to precipitate the polymer. The precipitated polymer was filtered, washed with methanol, and dried at 50° C. to obtain 14.0 g of a white polymer (4). The weight average molecular weight of the polymer (4) determined in the same manner as in Example 1 and the calculated content of the structural units are shown in Table 1.

[0294] In this method, 4,4'-biphenyldicarboxylic acid chloride is added as a mixed solution (slurry) with methylene chloride, corresponding to Method C. The slurry mixture contains a precipitate of 4,4'-biphenyldicarboxylic acid chloride, and adding this mixture requires a complex process of adding all of the 4,4'-biphenyldicarboxylic acid chloride, including the precipitate, to the alkaline solution. Method C is considered significantly less efficient than Method A, particularly when producing polymers on a 1 kg or 1 ton scale.

[0295] <Example 5>

[0296] - Preparation of polymer (5) -

[0297] A white polymer (5) composed of the structural units shown in Table 1 was prepared according to the following scheme.

[0298] [Chemical Formula 38]

[0299]

[0300] In a reaction vessel equipped with a stirrer, 34.3484 g of 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 0.5270 g of 2,3,5-trimethylphenol, 0.1717 g of sodium dithionite, and 690 mL of water were added to form a suspension. While stirring the suspension at room temperature (20°C), 14.5000 g of sodium hydroxide, 0.5955 g of benzyltributylammonium chloride, and 460 mL of water were added. The mixture was stirred under a nitrogen atmosphere for 30 minutes to form a solution in which the solids were largely dissolved (slightly turbid). 630 mL of o-dichlorobenzene was added to this aqueous solution, and after stirring under a nitrogen atmosphere for 30 minutes, 36.0000 g of powdered 4,4'-biphenyldicarboxylic acid chloride was added. After the additions were completed, the mixture was stirred under a nitrogen atmosphere at room temperature (20°C) for 4 hours to allow the reaction to proceed. The solution after polymerization was diluted with 900 mL of o-dichlorobenzene, and the aqueous layer was removed. After washing with a dilute acetic acid solution and ion exchange water, the solution was poured into methanol to precipitate a polymer. The precipitated polymer was filtered and dried at 50°C. The polymer was dissolved again in 2700 mL of tetrahydrofuran and poured into methanol to precipitate a polymer. The precipitated polymer was filtered, washed with methanol, and dried at 50°C to obtain 55.3 g of a white polymer (5).

[0301] The weight average molecular weight of polymer (5) determined in the same manner as in Example 1 and the calculated content of the structural unit are shown in Table 1. The terminal structure of polymer (5) is mainly derived from the terminal structure A of 2,3,5-trimethylphenol, but 1 HNMR also confirmed a portion of the terminal structure B and terminal structure C. 1By H NMR, the terminal structure B and the terminal structure C were estimated to be approximately 2 mol % each relative to 100 mol % of the terminal structure A.

[0302] In the above method, 4,4'-biphenyldicarboxylic acid chloride powder was added, which corresponds to method A.

[0303] Comparative Example 1

[0304] -Preparation of Comparative Polymer (1)-

[0305] A white comparative polymer (1) composed of the structural units shown in Table 2 was prepared into a polymer equivalent to Resin-2 of Japanese Patent No. 6500996 according to the following scheme. Since the synthesis conditions of Resin-2 are not disclosed, the synthesis conditions follow those of Example 1. However, the resulting polymer does not have sufficient solubility in tetrahydrofuran, so film formation for preparing evaluation samples was originally impossible. The weight average molecular weight of the comparative polymer (1) determined in the same manner as in Example 1 and the calculated content of the structural units are shown in Table 2. The weight average molecular weight of the soluble component in tetrahydrofuran was measured.

[0306] [Chemical Formula 39]

[0307]

[0308] Comparative Example 2

[0309] -Preparation of Comparative Polymer (2)-

[0310] According to the following scheme and in accordance with Synthesis Example 17 of JP-A-2017-215584, a white comparative polymer (2) composed of the structural units shown in Table 2 was prepared. In Synthesis Example 17 described in Table 1 of JP-A-2017-215584, although the structure represented by the general formula (I) is I-1 / I-24 (90 / 10), since the specific structure of I-24 is not disclosed, the comparative polymer (2) was prepared as I-1 / I-4 (90 / 10). The weight average molecular weight of the comparative polymer (2) determined in the same manner as in Example 1 and the calculated content of the structural units are shown in Table 2.

[0311] [Chemical Formula 40]

[0312]

[0313] Comparative Example 3

[0314] -Preparation of Comparative Polymer (3)-

[0315] According to the following scheme and in accordance with Example 3 of Japanese Patent No. 4927690, a white comparative polymer (3) composed of the structural units shown in Table 2 was prepared. The weight average molecular weight of the comparative polymer (3) determined in the same manner as in Example 1 and the calculated content of the structural units are shown in Table 2.

[0316] [Chemical Formula 41]

[0317]

[0318] <Comparative Example 4>

[0319] -Preparation of Comparative Polymer (4)-

[0320] According to the following scheme and in accordance with Example 4 of Japanese Patent No. 4927690, a white comparative polymer (4) composed of the structural units shown in Table 2 was prepared. The weight average molecular weight of the comparative polymer (4) determined in the same manner as in Example 1 and the calculated content of the structural units are shown in Table 2.

[0321] [Chemical Formula 42]

[0322]

[0323] <Comparative Example 5>

[0324] -Preparation of Comparative Polymer (5)-

[0325] According to the following scheme and in accordance with Example 5 of Japanese Patent No. 4927690, a white comparative polymer (5) composed of the structural units shown in Table 3 was prepared. The weight average molecular weight of the comparative polymer (5) determined in the same manner as in Example 1 and the calculated content of the structural units are shown in Table 3.

[0326] [Chemical Formula 43]

[0327]

[0328] <Comparative Example 6>

[0329] -Preparation of Comparative Polymer (6)-

[0330] According to the following scheme and in accordance with Example 6 of Japanese Patent No. 4927690, a white comparative polymer (6) composed of the structural units shown in Table 3 was prepared. The weight average molecular weight of the comparative polymer (6) determined in the same manner as in Example 1 and the calculated content of the structural units are shown in Table 3.

[0331] [Chemical Formula 44]

[0332]

[0333] <Comparative Example 7>

[0334] -Preparation of Comparative Polymer (7)-

[0335] According to the following scheme and in accordance with Example 1 of Japanese Patent No. 5117006, a white comparative polymer (7) composed of the structural units shown in Table 3 was prepared. The weight average molecular weight of the comparative polymer (7) determined in the same manner as in Example 1 and the calculated content of the structural units are shown in Table 3.

[0336] [Chemical Formula 45]

[0337]

[0338] <Comparative Example 8>

[0339] -Preparation of Comparative Polymer (8)-

[0340] According to the following scheme and in accordance with Production Example 14 of Japanese Patent No. 5481829, a white comparative polymer (8) composed of the structural units shown in Table 4 was prepared. The weight average molecular weight of the comparative polymer (8) determined in the same manner as in Example 1 and the calculated content of the structural units are shown in Table 4.

[0341] [Chemical Formula 46]

[0342]

[0343] <Comparative Example 9>

[0344] -Preparation of Comparative Polymer (9)-

[0345] According to the following scheme and in accordance with Production Example 3 of Japanese Patent No. 4246621, a white comparative polymer (9) composed of the structural units shown in Table 4 was prepared. The weight average molecular weight of the comparative polymer (9) determined in the same manner as in Example 1 and the calculated content of the structural units are shown in Table 4.

[0346] [Chemical Formula 47]

[0347]

[0348] <Comparative Example 10>

[0349] -Preparation of Comparative Polymer (10)-

[0350] According to the following scheme and in accordance with Comparative Production Example 1 of Japanese Patent No. 4246621, a white comparative polymer (10) composed of the structural units shown in Table 4 was prepared. The weight average molecular weight of the comparative polymer (10) determined in the same manner as in Example 1 and the calculated content of the structural units are shown in Table 4.

[0351] [Chemical Formula 48]

[0352]

[0353] <Comparative Example 11>

[0354] -Preparation of Comparative Polymer (11)-

[0355] A white comparative polymer (11) composed of the structural units shown in Table 4 was prepared according to the following scheme to have the structure of I-15 described in JP-A-2005-156605. Since the synthesis conditions of I-15 are not disclosed, the synthesis conditions were those of Example 1. The weight-average molecular weight of the comparative polymer (11) and the calculated content of the structural units, determined in the same manner as in Example 1, are shown in Table 4. The ratio (molar ratio) of the structural units derived from terephthaloyl chloride and isophthaloyl chloride in the comparative polymer (11) was 1:1.

[0356] [Chemical Formula 49]

[0357]

[0358] <Comparative Example 12>

[0359] -Preparation of Comparative Polymer (12)-

[0360] A white comparative polymer (12) composed of the structural units shown in Table 4 was prepared according to the following scheme to have the structure of I-14 described in JP-A-2005-156605. Since the synthesis conditions of I-14 are not disclosed, the synthesis conditions were those of Example 1. The weight-average molecular weight of the comparative polymer (12) and the calculated content of the structural units, determined in the same manner as in Example 1, are shown in Table 4. The ratio (molar ratio) of the structural units derived from terephthaloyl chloride and isophthaloyl chloride in the comparative polymer (12) was 1:1.

[0361] [Chemical Formula 50]

[0362]

[0363] <Comparative Example 13>

[0364] -Preparation of Comparative Polymer (13)-

[0365] According to the following scheme and in accordance with Synthesis Example 12 of JP-A-2017-151425, a white comparative polymer (13) composed of the structural units shown in Table 5 was prepared. 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 are shown in Table 5.

[0366] [Chemical Formula 51]

[0367]

[0368] <Comparative Example 14>

[0369] -Preparation of Comparative Polymer (14)-

[0370] According to the following scheme and in accordance with Example 5 of Japanese Patent No. 6455025, a white comparative polymer (14) composed of the structural units shown in Table 5 was prepared. 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 are shown in Table 5. The ratio (molar ratio) of the structural units derived from terephthaloyl chloride and isophthaloyl chloride in the comparative polymer (14) was 1:1.

[0371] [Chemical Formula 52]

[0372]

[0373] <Comparative Example 15>

[0374] -Preparation of Comparative Polymer (15)-

[0375] According to the following scheme and in accordance with Example 5 of Japanese Patent No. 6815025, a white comparative polymer (15) composed of the structural units shown in Table 5 was prepared. The weight average molecular weight of the comparative polymer (15) determined in the same manner as in Example 1 and the calculated content of the structural units are shown in Table 5. The ratio (molar ratio) of the structural units derived from terephthaloyl chloride and isophthaloyl chloride in the comparative polymer (15) was 1:1.

[0376] [Chemical Formula 53]

[0377]

[0378] <Comparative Example 16>

[0379] -Preparation of Comparative Polymer (16)-

[0380] A white comparative polymer (16) composed of the structural units shown in Table 6 was prepared according to the following scheme as a polymer equivalent to Resin-11 of Japanese Patent No. 6500996. Since the synthesis conditions of Resin-11 are not disclosed, the synthesis conditions were the same as in Example 1. The weight average molecular weight of the comparative polymer (16) determined in the same manner as in Example 1 and the calculated content of the structural units are shown in Table 6.

[0381] [Chemical Formula 54]

[0382]

[0383] [Preparation of evaluation samples (1)]

[0384] 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 coating solutions corresponding to the respective polymers. Each coating solution was dropwise added to a Petri dish and dried to obtain a cast film having a film thickness of 10 to 50 μm corresponding to the respective polymer as a coating film. The cast film was peeled from the Petri dish and used as an evaluation sample.

[0385] <Friction resistance test (1)>

[0386] Each cast film produced in the preparation of evaluation samples (1) was attached to S-36 (manufactured by Taber) to prepare an evaluation sample for abrasion resistance test.

[0387] Each evaluation sample produced was mounted on a rotary wear tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.) and rotated 2000 times using a grinding wheel CS-10 (manufactured by Taber Co.) under conditions of a load of 500 gf and a rotation speed of 60 rpm, and a wear evaluation test was performed. The mass change of the sample before and after the wear evaluation test, i.e., the wear loss (mg / 2000 rotations), was measured. Based on the obtained wear loss, the friction resistance of each evaluation sample was evaluated according to the following standards. The results are shown in Tables 1 to 5. In addition, the evaluation samples formed by polymers (1) to (5) were used as evaluation samples for the friction resistance test (1) of Examples 1 to 5, respectively, and the evaluation samples formed by comparative polymers (2) to (16) were used as evaluation samples for the friction resistance test (1) of Comparative Examples 2 to 16, respectively.

[0388] -Evaluation criteria for friction resistance-

[0389] A: Wear loss is less than 7mg

[0390] B: Wear loss is 7 mg or more and less than 8 mg

[0391] C: Wear loss is 8 mg or more and less than 10 mg

[0392] D: Wear loss is 10 mg or more and less than 13 mg

[0393] E: Wear loss is more than 13 mg

[0394] [Preparation of evaluation samples (2)]

[0395] 800 mg of 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-containing compound (functional material), and 18 g of tetrahydrofuran (manufactured by FUJIFILM Wako Pure Chemical Corporation) as a solvent were mixed to prepare coating solutions corresponding to the respective polymers. Each coating solution was dropwise added to a Petri dish to obtain a cast film having a film thickness of 10 to 50 μm corresponding to the respective polymer as a coating film. The cast film was peeled from the Petri dish and used as an evaluation sample.

[0396] <Film Formability (Compatibility) Evaluation>

[0397] For each polymer, the cast films containing no functional material produced in the evaluation sample preparation (1) and the cast films containing the functional material produced in the evaluation sample preparation (2) were visually observed for fogging (for example, in the case of using polymer (1), the cast films containing polymer (1) and no functional material and the cast films containing polymer (1) and the functional material were visually observed for fogging or wrinkling). Thus, the film-forming properties based on the compatibility between each polymer and the functional material were evaluated. The results are shown in Tables 1 to 6.

[0398] -Evaluation criteria for film forming properties-

[0399] OK: The cast film containing the functional material showed the same degree of transparency as the cast film containing no functional material.

[0400] NG: The cast film containing the functional material showed more obvious fogging or wrinkling than the cast film not containing the functional material.

[0401] Heat resistance evaluation

[0402] The cast films containing the functional material produced in Preparation of Evaluation Samples (2) were placed in a constant-temperature thermostat set at 170°C and heated in an air atmosphere for 15 minutes. Each cast film was then visually observed for fogging, coloration, or leakage of the functional material. Heating accelerated fogging, accelerated coloration, or observed leakage of the functional material compared to before heating. The results are shown in Tables 1 to 5.

[0403] -Evaluation criteria for heat resistance-

[0404] OK: After heating, fogging and coloring were not accelerated. No leakage of the functional material was observed.

[0405] NG: After heating, fogging is significantly accelerated, coloring is accelerated, or leakage of the functional material is observed.

[0406] <Friction resistance test (2)>

[0407] Each cast film produced in the production of evaluation samples (2) was attached to S-36 (manufactured by Taber) to prepare an evaluation sample for abrasion resistance test.

[0408] Each evaluation sample produced was installed in a rotary wear tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.) and rotated 2000 times using a grinding wheel CS-10 (manufactured by Taber Co., Ltd.) under the conditions of a load of 500 gf and a rotation speed of 60 rpm to implement a wear evaluation test. The mass change of the sample before and after the wear evaluation test, i.e., the wear loss (mg / 2000 rotations), was measured. Based on the obtained wear loss, the friction resistance of each evaluation sample was evaluated according to the following standards. The results are shown in Tables 1 to 5. In addition, the evaluation samples formed by polymers (1) to (5) were used as evaluation samples for the friction resistance test (2) of Examples 1 to 5, respectively, and the evaluation samples formed by comparative polymers (2) to (16) were used as evaluation samples for the friction resistance test (2) of Comparative Examples 2 to 16, respectively. The friction resistance of each evaluation sample was evaluated according to the following standards. The results are shown in Tables 1 to 5.

[0409] -Evaluation criteria for friction resistance-

[0410] A: Wear loss is less than 7mg

[0411] B: Wear loss is 7 mg or more and less than 8 mg

[0412] C: Wear loss is 8 mg or more and less than 10 mg

[0413] D: Wear loss is 10 mg or more and less than 13 mg

[0414] E: Wear loss is more than 13 mg

[0415] [Table 1]

[0416]

[0417] (*) represents the content in each polymer, and the unit is mass %. The same applies to Tables 2 to 5.

[0418] [Table 2]

[0419]

[0420] [Table 3]

[0421]

[0422] [Table 4]

[0423]

[0424] [Table 5]

[0425]

[0426] [Table 6]

[0427]

[0428] Comparative polymers (1) to (7) and (13) do not have the structural unit represented by the above-mentioned formula (I). In addition, in comparative polymer (2), the content of the structural unit represented by the above-mentioned formula (II) is less than 10% by mass. Comparative polymers (8) to (12) do not have any of the structural units represented by the above-mentioned formulas (I) and (II). Comparative polymers (14) and (15) do not have the structural unit represented by the above-mentioned formula (II). In addition, the terminal structure of comparative polymers (1), (3) to (6), (11) and (12) may be any of the above-mentioned formulas (III-A) and (III-B). In addition, comparative polymer (16) has any of the structural units represented by the above-mentioned formulas (I) and (II), but the terminal structure may be any of the above-mentioned formulas (III-A) and (III-B).

[0429] Since comparative polymer (1) is not soluble in tetrahydrofuran, films of comparative polymer (1) could not be produced. Cast films produced from comparative polymers other than comparative polymer (1) exhibited poor abrasion resistance. Furthermore, each comparative polymer exhibited poor film-forming properties or heat resistance when coexisted with a functional material.

[0430] In contrast, each cast film produced from the polymer specified in the present invention has excellent friction resistance and is excellent in both film formability and heat resistance even when coexisting with a functional material.

[0431] The present invention has been described together with its embodiments, but unless otherwise specified, the present invention is not intended to be limited to any of the details described, and should be interpreted broadly within the scope of the invention as shown in the appended claims.

[0432] This application claims priority based on Japanese Patent Application No. 2021-082815 filed in Japan on May 14, 2021, the contents of which are incorporated herein by reference as a part of the description in this specification.

Claims

1. A coating resin composition comprising a polymer having 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), In the polymer, the content of the structural unit represented by the formula (I) is 10% by mass or more, and the content of the structural unit represented by the formula (II) is 10% by mass or more, [Chemical Formula 1] In the formula, Me represents a methyl group, [Chemical Formula 2] [Chemical Formula 3] *-OR a (III-A) Where R a and R b represents a monovalent organic group, in formula (III-A), R a By R a The carbon atom in the formula (III-A) is bonded to the oxygen atom shown in the formula (III-B). b By R b The carbon atom in is bonded to the carbonyl group represented by formula (III-B), and * indicates a bonding site.

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

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

4. The coating resin composition according to claim 1 or 2, wherein The terminal structure represented by the formula (III-A) in the polymer is represented by the following formula (III-A-1), [Chemical Formula 4] Where R d represents an alkyl group, an aryl group or a halogen atom, s is an integer of 0 to 5, and * represents a bonding site. The coating resin composition according to claim 1 or 2, comprising a solvent.

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

50.

7. A polymer comprising 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), In the polymer, the content of the structural unit represented by the formula (I) is 10% by mass or more, and the content of the structural unit represented by the formula (II) is 10% by mass or more, [Chemical Formula 5] In the formula, Me represents a methyl group, [Chemical Formula 6] [Chemical Formula 7] *-OR a (III-A) Where R a and R b represents a monovalent organic group, in formula (III-A), R a By R a The carbon atom in the formula (III-A) is bonded to the oxygen atom shown in the formula (III-B). b By R b The carbon atom in is bonded to the carbonyl group represented by formula (III-B), and * indicates a bonding site.

8. A method for producing a polymer having a structural unit represented by the following formula (II), the method comprising the following steps: A mixture of an alkaline aqueous solution containing a dihydric phenol and an organic solvent and solid 4,4'-biphenyl dicarboxylic acid chloride are mixed. [Chemical Formula 8] in, The polymer is the polymer according to claim 7.

9. A coating film comprising the polymer according to claim 7.

10. A method for forming a coating film, comprising the following steps: A substrate is coated with the coating resin composition according to any one of claims 1 to 6.

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