Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/19—Hydroxy compounds containing aromatic rings
  • C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/181—Acids containing aromatic rings
  • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/78—Preparation processes
  • C08G63/79—Interfacial processes, i.e. processes involving a reaction at the interface of two non-miscible liquids
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
  • C09D167/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl - and the hydroxy groups directly linked to aromatic rings

Definitions

• 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.
• Patent Document 1 describes a film-forming resin mainly composed of a polyester composed of a residue of a divalent carboxylic acid having a biphenyl structure, a diphenyl ether structure and a cyclohexane structure, and a residue of a dihydric phenol.
• Patent Document 2 100 parts by mass of a polymer resin composition in which 95 to 5% by mass of the polyarylate component (A) and 5 to 95% by mass of the polycarbonate component (B) are combined to make 100% by mass, describes a resin composition comprising 0.01 to 1 part by mass of a silicone compound (C) having a glycidyl group with a specific structure.
• a molded article using this composition has both heat resistance and transparency, and is said to be suitable for automotive lamp peripheral parts, lighting fixture reflectors, and the like.
• the polymers are molded and processed into a desired shape, or dissolved in a solvent and applied onto a substrate to form a coating film.
• the functionality and mechanical properties of the polymer itself are improved, or the polymer is mixed with a functional material and applied.
• compatibility between the polymer and the functional material is important. It is important not to spoil it. Also, if a coating film with a small haze is obtained, it can be easily applied as an optical film or the like.
• the present invention provides a coating resin composition capable of realizing excellent film formability and capable of forming a coating film having excellent abrasion resistance, and a main component or binder of this coating resin composition.
• An object of the present invention is to provide a suitable polymer and a suitable production method thereof.
• Another object of the present invention is to provide a coating film which is excellent in film-forming properties when formed and itself is excellent in wear resistance, and a method for producing the same.
• the total content of the structural unit represented by the formula (IA) and the structural unit represented by the formula (IB) is 10% by mass or more
• the formula (II) A resin composition for coating, wherein the content of the represented structural unit is 10% by mass or more.
• R 1 represents an unsubstituted chain branched alkyl group having 4 or more carbon atoms.
• R2 represents a hydrogen atom, a linear alkyl group, or an aryl group.
• R3 represents a hydrogen atom , an alkyl group, or an aryl group.
• R 1 and R 2 do not combine to form a ring structure.
• the sum of the number of carbon atoms of R 1 and the number of carbon atoms of two R 3 is 6 or more.
• R4 represents a hydrogen atom, a linear alkyl group, or an aryl group.
• n is an integer from 2 to 20;
• R5 represents a hydrogen atom, an alkyl group, or an aryl group.
• R5 represents a hydrogen atom, an alkyl group, or an aryl group.
• Rc represents an alkyl group, an aryl group, or a halogen atom
• r is an integer of 0-4.
• R 2 is a hydrogen atom or an unsubstituted hydrocarbon group
• the content of the structural unit represented by the above formula (IA) in the polymer is 10% by mass or more.
• R c and r have the same definitions as R c and r in formula (II) above.
• R 3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, at least one of the two R 3 is an alkyl group having 1 to 4 carbon atoms
• -B represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least one of the two R 5 is an alkyl group having 1 to 4 carbon atoms
• ⁇ 1> to ⁇ 5> The coating resin composition according to any one of the above.
• ⁇ 7> The resin composition for coating according to any one of ⁇ 1> to ⁇ 6>, wherein R 1 has 5 or more carbon atoms.
• ⁇ 8> The resin composition for coating according to any one of ⁇ 1> to ⁇ 6>, wherein n is an integer of 4 to 20.
• n is an integer of 4 to 20.
• It contains a functional material composed of an aromatic ring-containing compound containing a benzene ring, and the mass ratio of the content of the polymer to the content of the functional material is the polymer/functional material 90:10 to 50: 50, the coating resin composition according to any one of ⁇ 1> to ⁇ 9>.
• R 1 represents an unsubstituted chain branched alkyl group having 4 or more carbon atoms.
• R2 represents a hydrogen atom, a linear alkyl group, or an aryl group.
• R3 represents a hydrogen atom , an alkyl group, or an aryl group.
• R 1 and R 2 do not combine to form a ring structure.
• the sum of the number of carbon atoms of R 1 and the number of carbon atoms of two R 3 is 6 or more.
• R4 represents a hydrogen atom, a linear alkyl group, or an aryl group.
• n is an integer from 2 to 20;
• R5 represents a hydrogen atom, an alkyl group, or an aryl group.
• R5 represents a hydrogen atom, an alkyl group, or an aryl group.
• Rc represents an alkyl group, an aryl group, or a halogen atom
• r is an integer of 0-4.
• R 1 represents an unsubstituted chain branched alkyl group having 4 or more carbon atoms.
• R2 represents a hydrogen atom, a linear alkyl group, or an aryl group.
• R3 represents a hydrogen atom , an alkyl group, or an aryl group.
• R 1 and R 2 do not combine to form a ring structure.
• the sum of the number of carbon atoms of R 1 and the number of carbon atoms of two R 3 is 6 or more. There are no substituents other than R3 on the two benzene rings shown in the formula.
• R4 represents a hydrogen atom, a linear alkyl group, or an aryl group.
• n is an integer from 2 to 20;
• R5 represents a hydrogen atom, an alkyl group, or an aryl group. There are no substituents other than R5 on the two benzene rings shown in the formula.
• ⁇ 13> A coating film containing the polymer according to ⁇ 11>.
• ⁇ 14> A method for forming a coating film, comprising coating a substrate with the coating resin composition according to any one of ⁇ 1> to ⁇ 10>.
• the coating resin composition of the present invention achieves excellent film formability and enables the formation of coating films with excellent abrasion resistance.
• the polymer of the present invention is suitable as a main component or binder of the resin composition for coating. According to the method for producing a polymer of the present invention, it is possible to efficiently obtain a polymer having a suitable molecular weight as a constituent polymer of a coating film.
• the coating film of the present invention is excellent in film formability and abrasion resistance. According to the method of forming a coating film of the present invention, it is possible to obtain a coating film that is excellent in wear resistance while achieving excellent film-forming properties.
• a numerical range represented using “-” means a range including the numerical values described before and after "-” as lower and upper limits.
• substituents, linking groups, etc. for which substitution or non-substitution is not specified clearly mean that the group may have an appropriate substituent. Therefore, in this specification, even when simply described as “- group” (eg, "alkyl group”), this "- group” (eg, "alkyl group”) does not have a substituent.
• substituents, linking groups, etc. for which substitution or non-substitution is not specified clearly mean that the group may have an appropriate substituent. Therefore, in this specification, even when simply described as “- group” (eg, "alkyl group”), this "- group” (eg, "alkyl group”) does not have a substituent.
• embodiments having further substituents eg, "substituted alkyl group" are also included.
• substituents include those selected from substituents T described later.
• substituents T when there are a plurality of substituents, etc., or when a plurality of substituents, etc. are specified simultaneously or alternatively, it means that the respective substituents, etc. may be the same or different. Further, even if not otherwise specified, when a plurality of substituents and the like are adjacent to each other, they may be connected to each other or condensed to form a ring. In this specification, when a polymer has a plurality of constituents with the same designation (indicated by the same general formula), each constituent may be the same or different.
• the coating resin composition of the present invention comprises at least one of a structural unit represented by the following formula (IA) and a structural unit represented by the following formula (IB), and a structural unit represented by the following formula (II). including polymers having structural units with This polymer may be hereinafter simply referred to as "the above polymer”.
• R 1 represents an unsubstituted chain branched alkyl group having 4 or more carbon atoms (the chain branched alkyl group of R 1 does not have a substituent).
• the number of carbon atoms in R 1 is preferably 4-20, more preferably 4-15, even more preferably 4-10, and particularly preferably 4-8. It is also preferred that R 1 has 5 or more carbon atoms. Therefore, the carbon number of R 1 is preferably 5 to 20, preferably 6 to 15, preferably 6 to 10, and more preferably 7 to 8.
• R 1 Preferred specific examples of R 1 include 1-methylpropyl group, 2-methylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, 1-methylbutyl group, 2- methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 4-methylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1,3-dimethylpentyl group, 1,4-dimethylpentyl group, 2, 4,4-trimethylpentyl group, 1-ethylheptyl group, 2-ethylheptyl group, 3-methylhexyl
• R 1 includes 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1-ethylbutyl group, 1-ethylpentyl group and 1-ethylhexyl group.
• 1-ethylheptyl group and 2,4,4-trimethylpentyl group are preferred, and 2-methylpropyl group, 1-ethylbutyl group, 1-ethylpentyl group, 2,4,4-trimethylpentyl group and 1-ethylheptyl groups are more preferred.
• R2 represents a hydrogen atom, a linear alkyl group, or an aryl group.
• the straight-chain alkyl group that can be used as R 2 preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
• a straight-chain alkyl group that can be used as R 2 is preferably a methyl group or an ethyl group, more preferably a methyl group.
• the number of carbon atoms in the aryl group that can be used as R 2 is preferably 6-26, more preferably 6-20, even more preferably 6-15, particularly preferably 6-12, and most preferably 6-10.
• R2 is preferably a hydrogen atom or a methyl group.
• R3 represents a hydrogen atom , an alkyl group, or an aryl group.
• Alkyl groups that can be used as R 3 may be any of linear, branched and cyclic alkyl groups.
• the number of carbon atoms in the alkyl group that can be used as R 3 is preferably 1-10, more preferably 1-6, and still more preferably 1-4.
• the alkyl group that can be used as R 3 is preferably a methyl group or an ethyl group, more preferably a methyl group.
• the aryl group that can be used as R3 has the same meaning as the aryl group that can be used as R2 , and the preferred forms are also the same.
• R3 is preferably a hydrogen atom or a methyl group.
• R 1 and R 2 do not combine to form a ring structure.
• the total number of carbon atoms of R 1 and two R 3 is 6 or more, preferably 6-20, more preferably 6-16, still more preferably 6-13. If the sum of the number of carbon atoms in R 1 and the number of carbon atoms in two R 3 is 5 or less, the polymer tends to be less soluble in solvents and less compatible with functional materials.
• R 4 represents a hydrogen atom, a linear alkyl group, or an aryl group.
• the straight-chain alkyl group that can be used as R4 has the same meaning as the straight-chain alkyl group that can be used as R2 , and the preferred forms are also the same.
• the aryl group that can be used as R4 has the same definition as the aryl group that can be used as R2 , and the preferred forms are also the same.
• R5 represents a hydrogen atom, an alkyl group, or an aryl group.
• the alkyl group or aryl group that can be used as R5 has the same meaning as the alkyl group or aryl group that can be used as R3 , and the preferred forms are also the same.
• R5 is preferably a hydrogen atom or a methyl group.
• n is an integer from 2 to 20. When n is 1 or less, the solubility of the polymer in a solvent decreases, or the compatibility with a functional material decreases, making it difficult to form a coating film and exhibit functions.
• n is preferably 3-20, more preferably 4-20, still more preferably 4-15, particularly preferably 5-13, most preferably 6-10.
• R c represents an alkyl group, an aryl group, or a halogen atom
• r is an integer of 0-4.
• the alkyl group and aryl group that can be used as Rc are synonymous with the alkyl group and aryl group that can be used as R3 , respectively, and the preferred forms are also the same.
• r is preferably 0 or 2, more preferably 0.
• the total content of the structural unit represented by the formula (IA) and the structural unit represented by the formula (IB) is 10% by mass or more, and ) is 10% by mass or more.
• the total content of the structural unit represented by the formula (IA) and the structural unit represented by the formula (IB) is preferably 20% by mass or more, more preferably is 25% by mass or more, more preferably 30% by mass or more. Further, in the polymer, the total content of the structural unit represented by the formula (IA) and the structural unit represented by the formula (IB) is usually 70% by mass or less, It is also preferably 65% by mass or less.
• the content of the structural unit represented by formula (II) in the polymer is preferably 20% by mass or more, more preferably 25% by mass or more, and still more preferably 30% by mass or more. In addition, the content of the structural unit represented by the formula (II) in the polymer is usually 60% by mass or less, preferably 50% by mass or less.
• R 2 is preferably a hydrogen atom, an unsubstituted linear alkyl group, or an unsubstituted aryl group. That is, it is preferable that R 1 and R 2 as a whole consist only of carbon atoms and hydrogen atoms.
• the content of the structural unit represented by formula (IA) in the polymer is preferably 20% by mass or more, more preferably 25% by mass or more, and still more preferably 30% by mass. % by mass or more. This content is usually 70% by mass or less, preferably 65% by mass or less.
• the content of the structural unit represented by the formula (II) in the polymer is 10% by mass or more.
• the content of the structural unit represented by the following formula (II-1) is more preferably 20% by mass or more, more preferably 25% by mass or more, and still more preferably 30% by mass or more. be.
• the content of the structural unit represented by the following formula (II-1) in the polymer is usually 60% by mass or less, preferably 50% by mass or less.
• R c and r have the same meanings as R c and r in formula (II) above, and preferred forms are also the same.
• 4,4'-biphenyldicarboxylic acid is a preferred example of the dicarboxylic acid that provides the structural unit represented by formula (II-1) above.
• the remainder excluding the structural units represented by the formulas (IA), (IB) and (II) is represented by, for example, the following formula (IC) It can contain at least one structural unit.
• R c and r have the same meanings as R c and r in formula (II), and preferred forms are also the same.
• W 1 represents an oxygen atom, a sulfur atom, or a hydrocarbon group having 1 to 15 carbon atoms.
• the structural unit represented by the above formula (IC) is a structural unit different from the structural units represented by the above formulas (IA) and (IB). That is, in the present invention, even if the structure is included in the structural unit represented by the above formula (IC), any one of the above formulas (IA) and (IB) Those also included in the structural unit represented are not represented by the structural unit represented by the above formula (IC), but are represented by any of the above formulas (IA) and (IB).
• hydrocarbon group having 1 to 15 carbon atoms that can be used as W 1 is a structural unit that As the hydrocarbon group having 1 to 15 carbon atoms that can be used as W 1 , a hydrocarbon group having 1 to 12 carbon atoms is preferable, and a hydrocarbon group having 1 to 10 carbon atoms is more preferable.
• 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 , 1,1-bis(3-methyl-4-hydroxyphenyl)methane, 4,4′
• the content of the structural unit represented by the above formula (IC) is preferably 0 to 40% by mass, more preferably 0 to 30% by mass, and still more preferably 0 to 20% by mass in the polymer.
• the remainder of the polymer excluding the structural units represented by the formulas (IA), (IB), (II) and (IC), contains, for example, dicarboxylic acid as described below. It is also preferred to contain a structural unit derived from an acid.
• 4,4′-diphenyl ether dicarboxylic acid 4,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid and the like.
• structural units derived from the above dicarboxylic acids structural units derived from 4,4'-diphenyletherdicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and terephthalic acid are preferable from the viewpoint of further increasing the abrasion resistance of the photosensitive layer.
• the content of the structural unit derived from the dicarboxylic acid other than the structural unit represented by the formula (II-1) is preferably 10 to 60% by mass, more preferably 20 to 50% by mass, still more preferably 20 to 50% by mass, in the polymer. is 30 to 50% by mass.
• the above polymer preferably has a terminal structure represented by the following formula (IV-1) or (IV-2).
• R a and R b represent monovalent organic groups.
• R a is bonded to the oxygen atom shown in formula (IV-1) through the carbon atom in R a
• R b is bound through the carbon atom in R b . It is bonded to the carbonyl group shown in formula (IV-2).
• R a and R b preferably have no fluorine atoms. * indicates the binding site. Note that * indicates a binding site also in the following formulas.
• the monovalent organic group that can be used as R a and R b is preferably an alkyl group or an aryl group.
• Alkyl groups that can be used as R a and R b may be linear or branched, and the number of carbon atoms (the number of carbon atoms including substituents when having substituents) is preferably 1 to 13, and 1 to 8. is more preferable, 1 to 6 is also preferable, and 1 to 3 is also preferable.
• R a and R b are alkyl groups, the number of carbon atoms is preferably as small as possible from the viewpoint of abrasion resistance.
• the aryl group that can be used as R a and R b has preferably 6 to 30 carbon atoms (the number of carbon atoms including the substituents when having substituents), more preferably 6 to 25, and still more preferably 6 to 20. 6 to 15 are particularly preferred, and 6 to 12 are most preferred.
• the aryl group that can be used as R a and R b is preferably a phenyl group.
• the terminal structure represented by the above formula (IV-1) is preferably represented by the following formula (IV-1-1).
• R d is 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 alkylcarbonyl oxy group) or a halogen atom, and s is an integer of 0-5.
• Rd is preferably an alkyl group, an alkoxy group, an alkoxycarbonyl group or an acyloxy group, more preferably an alkyl group or an alkoxy group, and even more preferably an alkyl group.
• the alkyl group that can be used as R d may be any of linear, branched and cyclic alkyl groups.
• the number of carbon atoms in the alkyl group that can be used as R d (the number of carbon atoms including the substituents, if any) is preferably 1-10, more preferably 1-6, and still more preferably 1-4.
• the alkyl group that can be used as R d is preferably a methyl group or a t-butyl group, more preferably a methyl group.
• s is preferably 2 or 3, more preferably 3.
• the number of carbon atoms in the aryl group that can be used as R d is preferably 6 to 26, more preferably 6 to 20, still more preferably 6 to 15, and particularly preferably 6-12, most preferably 6-10.
• Preferable specific examples of the aryl group that can be used as R d include a phenyl group, a 4-methoxyphenyl group, a 4-acetoxyphenyl group, a 1-naphthyl group and a 2-naphthyl group.
• the number of carbon atoms in the alkoxy group, alkoxycarbonyl group and acyloxy group that can be used as R d is preferably 1 to 10, more preferably 1 to 4, 1 or 2 is more preferred.
• This preferable number of carbon atoms is the number of carbon atoms excluding the carbon atoms forming the carbonyl group in each group for the alkoxycarbonyl group and the acyloxy group.
• the aryl group in the aryloxy group and aryloxycarbonyl group that can be used as R d has preferably 6 to 30 carbon atoms (the number of carbon atoms including the substituents when having substituents), more preferably 6 to 25, and 6 ⁇ 20 is more preferred, 6-15 is particularly preferred, and 6-12 is most preferred.
• the aryl group that can be used as R d is preferably a phenyl group, a 4-methoxyphenyl group or a 4-acetoxyphenyl group, more preferably a phenyl group.
• s is preferably an integer of 0-3.
• Preferred terminal structures represented by the above formulas (IV-1) to (IV-1-1) include, for example, those represented by the following formulas.
• Examples of preferred terminal structures represented by the above formula (IV-2) include those represented by the following formula.
• Terminal structures other than the above formula (IV-1) or (IV-2) include those represented by the following formulas. *-H *-OH
• Terminal structures represented by *-H and *-OH are preferably not included, but if they are included, they are preferably 50 mol% or less, preferably 30 mol%, of all the terminal structures of the polymer. It is more preferably 10 mol % or less, more preferably 10 mol % or less.
• the end is represented as follows, for example.
• the end is represented as follows, for example.
• the end is represented as follows, for example.
• the end is represented as follows, for example.
• the total amount of terminal structures represented by the above formula (IV-1) or (IV-2) is preferably 50 to 100 mol%, and preferably 70 to 100 mol%. is more preferred, and 90 to 100 mol % is even more preferred.
• the terminal structure represented by the above formula (IV-1) or (IV-2) can be used as a terminal blocking agent in, for example, a solution polymerization method or an interfacial polymerization method. It can be introduced by using an acid chloride. Further, after obtaining a polymer having a phenolic hydroxyl group as a terminal structure, the phenolic hydroxyl group is acylated in a polymer reaction to induce a terminal structure represented by the above formula (IV-2). can also
• the weight average molecular weight of the polymer is preferably 50,000 to 250,000, more preferably 80,000 to 180,000, still more preferably 100,000 to 150,000.
• the molecular weight of a polymer means weight average molecular weight unless otherwise specified.
• the weight average molecular weight can be determined as a polystyrene-equivalent molecular weight by gel permeation chromatography (GPC). Tetrahydrofuran can be preferably used as the eluent because of the solvent solubility of the polymer of the present invention.
• the preferred weight-average molecular weight range is based on the polystyrene-equivalent weight-average molecular weight when tetrahydrofuran is used as an eluent.
• Substituent T includes the following. alkyl groups (preferably alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl groups (preferably alkenyl groups having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.), alkynyl groups (preferably alkynyl groups having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl etc.), cycloalkyl groups (preferably cycloalkyl groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), aryl groups (
• the method for producing the polymer comprises at least one of a monomer giving a structural unit represented by the above formula (IA) and a monomer giving a structural unit represented by the above formula (IB); ) and, if necessary, other monomers are polycondensed by a conventional method.
• the method for producing the polymer is not particularly limited. Examples thereof include an interfacial polymerization method and a solution polymerization method, and the interfacial polymerization method is preferred.
• the interfacial polymerization method is a polymerization method for obtaining a polyester by mixing a dihydric carboxylic acid halide dissolved in an organic solvent immiscible with water and a dihydric phenol dissolved in an alkaline aqueous solution.
• Documents relating to the interfacial polymerization method include W. M. Eareckson, J. Poly.
• the interfacial polymerization method has a faster reaction than the solution polymerization method, hydrolysis of the acid halide can be suppressed, and as a result, a resin having a high molecular weight can be obtained.
• an alkaline aqueous solution of dihydric phenol is prepared as the aqueous phase, and then a polymerization catalyst is added.
• a divalent carboxylic acid halide is dissolved in a solvent that is not miscible with water and dissolves the polymer.
• a desired polymer solution can be obtained by carrying out the polymerization reaction with stirring for 8 hours. Not all of the divalent carboxylic acid halide may dissolve in the organic phase.
• Method A In the method for producing the polymer described above, Method A below may be used. In particular, this method is effective when the divalent carboxylic acid halide does not dissolve or has low solubility in the solvent of the organic layer.
• Method A As an aqueous phase, an alkaline aqueous solution of dihydric phenol is prepared, and then a polymerization catalyst is added. At this time, the dihydric phenol or its phenoxide may not be completely dissolved in the alkaline aqueous solution of the dihydric phenol.
• an organic phase only an organic solvent that is incompatible with water and dissolves the polymer is mixed with the alkaline solution and suspended by stirring.
• a solid divalent carboxylic acid halide such as powder is added thereto to carry out a polymerization reaction.
• This approach has three advantages. The first point is that the dihydric carboxylic acid halide is not made into a solution or a solvent suspension in advance, so that hydrolysis can be suppressed until it is mixed with the aqueous alkali solution of dihydric phenol. The second point is that since the solvent suspension is not handled, it is possible to avoid the troublesome operation of transferring the solvent suspension in order to mix it with the alkaline aqueous solution. In order to avoid handling the divalent carboxylic acid halide as a solvent suspension, it is conceivable to dilute it with a large amount of solvent to form a solution.
• Method A in which a solid divalent carboxylic acid halide is added, has the third advantage that there is no need to completely dissolve the divalent carboxylic acid halide itself, so the amount of organic solvent used can be reduced. As a result, production efficiency can be increased and organic solvents can be saved.
• the polymerization catalyst may be added in advance to the aqueous layer or to the organic layer.
• Alkali used in preparing the dihydric phenol aqueous solution include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like.
• the amount of alkali to be used is generally 2 to 5 times the number of moles of dihydric phenol, that is, 1 to 2.5 equivalents to hydroxyl groups.
• Method B In the method for producing the polymer of the present invention, method B below may be used.
• Method B For the organic layer, an organic solvent that is not miscible with water and dissolves the polymer and a divalent carboxylic acid halide are mixed and stirred to obtain a suspension.
• an alkaline aqueous solution of dihydric phenol is prepared as an aqueous phase in another container, and then a polymerization catalyst is added. The resulting aqueous layer is added to the above suspension to carry out a polymerization reaction.
• the reproducibility of the polymerization process may be improved by making the divalent carboxylic acid halide into an organic solvent suspension in advance by the method B described above.
• Method B includes a liquid transfer step of the solvent suspension. Therefore, the complexity of the operation is reduced, and there is less concern about hydrolysis of the divalent carboxylic acid halide in the liquid transfer step.
• Method C In the production method of the present invention, method C below may be used.
• Method C As a method of the general interfacial polymerization method described above, as described above, an alkaline aqueous solution of dihydric phenol is prepared as the aqueous phase, and then a polymerization catalyst is added. On the other hand, a solution or solvent suspension of divalent carboxylic acid halide is prepared as an organic phase, added to the above alkaline solution, and polymerized.
• a terminal blocking agent may be used during the polymerization from the viewpoint of controlling the molecular weight of the polymer. Also from the viewpoint of controlling the properties of the polymer, it is preferable that the terminal of the polymer is capped with a monohydric phenol, a monohydric acid chloride, a monohydric alcohol, a monohydric carboxylic acid, or the like.
• Monohydric phenols used as such terminal blocking agents include phenol, o-cresol, m-cresol, p-cresol, p-tert-butylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol.
• Examples of monovalent acid chlorides used as terminal blockers include benzoyl chloride, methanesulfonyl chloride, phenyl chlorocarbonate, acetyl chloride and lauroyl chloride.
• Examples of monohydric alcohols used as end blocking agents include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, pentanol, hexanol, dodecyl alcohol, stearyl alcohol, benzyl alcohol, and phenethyl alcohol. be done.
• Examples of monovalent carboxylic acids used as terminal blocking agents include acetic acid, propionic acid, octanoic acid, cyclohexanecarboxylic acid, benzoic acid, toluic acid, phenylacetic acid, p-tert-butylbenzoic acid, p-methoxyphenylacetic acid, and the like. mentioned. Among them, it is preferable to end-cap with monohydric phenol or monohydric acid chloride, such as p-tert-butylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, benzoyl chloride, or acetyl It is more preferably capped with chloride.
• Polymerization catalysts for interfacial polymerization include quaternary ammonium salts such as tributylbenzylammonium halide, tetrabutylammonium halide, trimethylbenzylammonium halide and triethylbenzylammonium halide, and tributylbenzylphosphonium halide, tetrabutylphosphonium halide and trimethylbenzylphosphonium.
• quaternary phosphonium salts such as halides and triethylbenzylphosphonium halides; Among them, those selected from tributylbenzylammonium halide, tetrabutylammonium halide, tributylbenzylphosphonium halide, and tetrabutylphosphonium halide are preferable in terms of facilitating polymerization.
• Organic phase solvents in interfacial polymerization include dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, o-dichlorobenzene, Chlorinated solvents such as m-dichlorobenzene and p-dichlorobenzene, aromatic hydrocarbons such as toluene, benzene, xylene and anisole can be used, and tetrahydrofuran and the like can also be used. Among them, dichloromethane and o-dichlorobenzene are preferable as the organic solvent for the organic layer.
• the divalent carboxylic acid halide does not dissolve or has low solubility in the organic solvent of the organic layer, other organic solvents can be used.
• the organic solvent for the organic layer is preferably one that does not dissolve in water. Part or all of the organic layer can be replaced with an organic solvent that is also water soluble for the purpose of controlling and obtaining the desired molecular weight polymer.
• organic solvents effective for improving the solubility of the divalent carboxylic acid halide in the organic layer include tetrahydrofuran, N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), Dimethylsulfoxide (DMSO), 1,4-dioxane, 1,3-dioxolane.
• a higher polymer concentration relative to the organic solvent in the organic layer is preferable from the viewpoint of productivity.
• the amount of polymer relative to the amount of liquid in 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.
• 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.
• Acetic acid is added to the polymer solution obtained after polymerization, and after the polymerization is completed, the polymer solution is washed with water while being repeatedly stirred, and sodium ions, potassium ions, lithium ions, chloride ions, and Remove ionic components such as polymerization catalysts.
• the water used for washing may be acidic or basic, and washing is repeated until the washing waste water becomes neutral.
• the solid content concentration of the polymer solution is preferably 7% by mass or less.
• the volume of the poor solvent is preferably at least three times the volume of the polymer solution. Poor solvents include methanol, ethanol, isopropyl alcohol, acetone, acetonitrile, hexane and the like.
• the immersion time in the poor solvent after the precipitation treatment in the poor solvent is 1 minute or longer.
• the immersion time is preferably 3 minutes or longer. Removal of less than 3 minutes may result in insufficient removal of residual monomer and impurities from the polymer.
• the above procedure of dissolving the obtained polymer in a solvent again and adding it to a poor solvent for precipitation may be repeated.
• Impurities that are insoluble in tetrahydrofuran or dichloromethane may be produced during the production of the polymer of the present invention.
• One reason for this is considered to be the use of 4,4'-biphenyldicarbonyl chloride or the like in introducing the structural unit represented by the above formula (II-1). That is, 4,4'-biphenyldicarboxylic acid or 4-(4-carboxyphenyl)-benzoic acid chloride, which are impurities that may be contained in 4,4'-biphenyldicarbonyl chloride, are brought into the production process of the polymer.
• the polymer or coating film of the invention does not contain such insoluble impurities.
• Methods for obtaining a polymer free of insoluble impurities include, for example, a method in which a solution containing both the polymer and insoluble impurities is treated with various adsorbents to remove the insoluble impurities.
• 4,4'-biphenyldicarboxylic acid or 4,4'-biphenyldicarboxylic acid containing a small amount of 4-(4-carboxyphenyl)-benzoic acid chloride as impurities is used. Preference is given to using carbonyl chloride.
• the content of 4,4'-biphenyldicarboxylic acid and 4-(4-carboxyphenyl)-benzoic acid chloride is preferably 5% by mass or less, and 1% by mass or less. More preferably, 0.5% by mass or less is even more preferable.
• the coating resin composition of the present invention usually contains a solvent in addition to the above polymer.
• the polymer obtained as described above has high solubility in general-purpose solvents or mixed solvents thereof. That is, solvents used alone or in combination include dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, o -, chlorinated solvents such as m-dichlorobenzene, aromatic hydrocarbons such as toluene, benzene, xylene, N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), 1,4- dioxane, tetrahydrofuran, and the like. These solvents can be used alone or as a mixed solvent.
• the coating resin composition of the present invention also preferably contains a functional material in order to impart desired functionality to the coating film of the present invention to be obtained.
• the functions imparted to the coating film of the present invention are not limited to specific functions.
• the mass ratio of each content of the polymer and the functional material can be 90:10 to 50:50, and can be 80:20 to 50:50. preferable.
• the functional material is not particularly limited, and an aromatic ring-containing compound containing a benzene ring is preferable from the viewpoint of further enhancing compatibility and interaction with the polymer.
• This aromatic ring-containing compound containing a benzene ring preferably has 2 to 15 benzene rings, more preferably 3 to 12 benzene rings, and still more preferably 4 to 10 benzene rings.
• the aromatic ring-containing compound containing a benzene ring preferably has a molecular weight of 200 to 2,000, more preferably 250 to 1,500, and even more preferably 300 to 1,000.
• the above aromatic ring-containing compound containing a benzene ring is preferably a compound represented by the following formula (V).
• X represents an oxygen atom, a sulfur atom, an optionally substituted hydrocarbon group, or an optionally substituted imino group.
• n1 represents an integer of 0-4.
• R represents a monovalent organic group or hydroxyl group.
• the hydrocarbon group that may have a substituent that can be taken as X is preferably a hydrocarbon group containing an aromatic ring having 6 to 35 carbon atoms, and a hydrocarbon group containing an aromatic ring having 6 to 25 carbon atoms.
• a hydrogen group is more preferred.
• n1 is preferably an integer of 0 to 2, more preferably 0 or 1.
• a preferred monovalent organic group that can be used as R is a linear alkyl group.
• the aromatic compound represented by the above formula (V) contains a plurality of benzene rings, contains hetero atoms such as oxygen atoms, sulfur atoms, nitrogen atoms, etc.
• the aromatic compounds represented by the above formula (V) Since the mass ratio of the benzene rings in is large and the rigidity is high, the compatibility and interaction between the polymer and the functional material are enhanced, and the mechanical properties of the resulting coating film can be further improved. In addition, an effect of suppressing the moisture permeability of the coating film by causing densification of the coating film is also expected.
• the molecular weight of the aromatic compound represented by the above formula (V) is preferably 200-2000, more preferably 250-1500, even more preferably 300-1000.
• the number of benzene rings in the above formula (V) is preferably 2-15, more preferably 3-12, even more preferably 4-10.
• the aromatic compound represented by formula (V) above preferably has at least one of an oxygen atom and a nitrogen atom.
• At least one of a structural unit represented by the following formula (IA) and a structural unit represented by the following formula (IB), and the following formula (II-2) It is suitable as a method for producing a polymer having the structural unit represented by A step of mixing with '-biphenyldicarbonyl chloride.
• the production method of the present invention more preferably includes the step of adding solid 4,4′-biphenyldicarbonyl chloride to a mixture containing an alkaline aqueous solution of dihydric phenol and an organic solvent while stirring.
• solid 4,4'-biphenyldicarbonyl chloride means solid 4,4'-biphenyldicarbonyl chloride itself, not in a state (solution or slurry) mixed with an organic solvent.
• the polymer comprises at least one structural unit represented by the following formula (IA) and a structural unit represented by the following formula (IB), and a structural unit represented by the following formula (II-2). and the total content of each structural unit represented by the formula (IA) and the structural unit represented by the formula (IB) is 10% by mass or more, and the formula (II- The content of the structural unit represented by 2) is 10% by mass or more.
• R 1 represents an unsubstituted chain branched alkyl group having 4 or more carbon atoms.
• R2 represents a hydrogen atom, a linear alkyl group, or an aryl group.
• R3 represents a hydrogen atom , an alkyl group, or an aryl group.
• R 1 and R 2 do not combine to form a ring structure.
• the sum of the number of carbon atoms of R 1 and the number of carbon atoms of two R 3 is 6 or more.
• R4 represents a hydrogen atom, a linear alkyl group, or an aryl group.
• n is an integer from 2 to 20;
• R5 represents a hydrogen atom, an alkyl group, or an aryl group. There are no substituents other than R5 on the two benzene rings shown in the formula.
• the manufacturing method of the present invention is performed, for example, by method A described above.
• the advantages of Method A are as described above.
• a structural unit represented by the above formula (IA) or (IB) is provided as the dihydric phenol component. It is preferred to use at least one compound of the formula.
• R 1 represents an unsubstituted chain branched alkyl group having 4 or more carbon atoms.
• R2 represents a hydrogen atom, a linear alkyl group, or an aryl group.
• R3 represents a hydrogen atom , an alkyl group, or an aryl group.
• R 1 and R 2 do not combine to form a ring structure.
• the sum of the number of carbon atoms of R 1 and the number of carbon atoms of two R 3 is 6 or more. There are no substituents other than R3 on the two benzene rings shown in the formula.
• R4 represents a hydrogen atom, a linear alkyl group, or an aryl group.
• n is an integer from 2 to 20;
• R5 represents a hydrogen atom, an alkyl group, or an aryl group. There are no substituents other than R5 on the two benzene rings shown in the formula.
• the solid 4,4'-biphenyldicarbonyl chloride preferably does not contain an organic solvent.
• 4,4'-biphenyldicarbonyl chloride may contain an organic solvent
• the content of the organic solvent with respect to the total amount of solid 4,4'-biphenyldicarbonyl chloride and the organic solvent is preferably 20% by mass or less, and 10% by mass. % by mass or less is more preferable, and 5% by mass or less is even more preferable.
• R a is the same monovalent organic group as R a in formula (IV-1) above, and the preferred forms are also the same.
• Examples of the compound represented by H—O—R a include monohydric phenols and monohydric alcohols used in the method for producing the polymer.
• the ratio of the total terminal structure derived from the compound represented by H—O—R a is preferably all the terminal structures of the polymer. Among them, the proportion occupied by the total terminal structure derived from the compound represented by the above formula (IV-1) is the same.
• R b is the same monovalent organic group as R b in formula (IV-2) above, and the preferred forms are also the same.
• Examples of the compound represented by the above formula include monoacid chlorides used in the method for producing the above polymer.
• 4,4'-biphenyldicarbonyl chloride may be used together with the monovalent carboxylic acid used in the above polymer production method.
• the ratio of the total terminal structure derived from the above compound is preferably represented by the above formula (IV-2) among all the terminal structures of the polymer. is the same as the proportion of the total terminal structure derived from the compound to be determined.
• a monomer that provides at least one of the above formulas (IC), (II), (II-1) and the dicarboxylic acid unit-derived structural unit used in the above polymer production method is may be used.
• Structural units derived from the above formulas (IA), (IB), (II), (II-1), (IC) and the above dicarboxylic acid units in the polymer obtained by the production method of the present invention The content is preferably the same as the content of these structural units in the polymer.
• the weight average molecular weight of the polymer obtained by the production method of the present invention is preferably the same as the weight average molecular weight of the above polymer.
• the polymerization catalyst and organic solvent used in the production method of the present invention are the same as the polymerization catalyst and organic solvent used in the above-described polymer production method, and the preferred polymerization catalyst and organic solvent are also the same. .
• the reason why the desired polymer can be obtained without being affected by hydrolysis in spite of the addition of 4,4′-biphenyldicarbonyl chloride as a solid is due to the dihydric phenol phenoxide and 4 ,4'-biphenyldicarbonyl chloride reacts very quickly, and therefore, even when the solid surface of 4,4'-biphenyldicarbonyl chloride is in direct contact with the alkaline aqueous solution, the desired polymerization reaction is presumed to be dominant. From the viewpoint of further suppressing hydrolysis of 4,4'-biphenyldicarbonyl chloride, it is preferable to reduce the amount of alkali used when preparing an alkaline aqueous solution of dihydric phenol.
• the post-treatment in the above polymer production method may be performed.
• the coating film of the present invention may be composed of the polymer of the present invention, and may contain other components in addition to the polymer of the present invention. Other components include, for example, the functional materials described above.
• the coating film of the present invention has excellent film formability when formed, and the coating film itself has excellent heat resistance and abrasion resistance.
• Examples of coating films combined with functional materials include, for example, low moisture permeability films as described in JP-A-2016-69468. That is, by adding a phenolic compound as a functional material to the polymer, the polymer and the functional material exhibit high compatibility, and the moisture permeability can be effectively suppressed.
• Another example of a composite coating film containing a functional material is a charge transport layer of an electrophotographic photoreceptor.
• the charge-transporting layer contains the polymer as a binder and a charge-transporting material, and the binder is required to have high compatibility with the charge-transporting material.
• the coating film of the present invention as a charge-transporting layer containing the above polymer and an aromatic compound as a charge-transporting material, a charge-transporting layer having excellent abrasion resistance can be obtained.
• the coating film of the present invention can also be preferably applied as, for example, a metal wire coating film, a polarizing plate protective film for display devices, and the like.
• the coating film of the present invention can also be used with other layers arranged thereon.
• the durability can be further improved by forming a protective layer in contact with the coating film of the present invention.
• the method for forming the coating film of the present invention is not particularly limited as long as it can form a film containing the above polymer.
• it can be formed by applying the coating resin composition of the present invention onto a substrate and drying the coating film.
• any method that can be normally employed in the coating and drying of the coating liquid can be appropriately applied.
• the base material is not particularly limited, and a wide range of materials, members, etc. having surfaces to be coated can be applied.
• Me represents a methyl group.
• the polymer was precipitated by pouring it into methanol (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.). The precipitated polymer was filtered and dried at 50°C. This polymer was re-dissolved in 900 mL of tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and poured into methanol to precipitate the polymer. The precipitated polymer was filtered, washed with methanol, and dried at 50° C. to obtain 17.5 g of white polymer (1).
• the weight average molecular weight (Mw) of the polymer was 130,000 as determined by gel permeation chromatography (GPC, using tetrahydrofuran as an eluent) as a polystyrene equivalent molecular weight.
• GPC gel permeation chromatography
• Example 2 Preparation of polymer (2)- A white polymer (2) composed of the structural units shown in Table 1 was prepared according to Example 1 according to the following scheme.
• Example 3> Preparation of polymer (3)- A white polymer (3) composed of the structural units shown in Table 1 was prepared according to Example 1 according to the following scheme.
• Example 5 Preparation of polymer (5)- A white polymer (5) composed of the structural units shown in Table 1 was prepared according to Example 1 according to the following scheme.
• Example 6> Preparation of polymer (6)- A white polymer (6) composed of structural units shown in Table 1 was prepared according to Example 1 according to the following scheme.
• Example 7 Preparation of polymer (7)- A white polymer (9) composed of the structural units shown in Table 2 was prepared according to Example 1 according to the following scheme.
• Example 8> Preparation of polymer (8)- A white polymer (10) composed of structural units shown in Table 2 was prepared according to Example 1 according to the following scheme.
• Example 9 Preparation of polymer (9)- A white polymer (11) composed of the structural units shown in Table 2 was prepared according to Example 1 according to the following scheme.
• a white comparative polymer (12) composed of the structural units shown in Table 5 was prepared as structure I-14 of JP-A-2005-156605. Synthesis conditions for I-14 were not disclosed, so the synthesis conditions were the same as in Example 1.
• Table 5 shows the weight-average molecular weight of Comparative Polymer (12) determined in the same manner as in Example 1 and the calculated structural unit content.
• the ratio (molar ratio) of the structural units derived from terephthalic acid chloride and isophthalic acid chloride in the comparative polymer (12) was 1:1.
• a white comparative polymer (15) composed of the structural units shown in Table 6 was prepared according to Example 5 of Japanese Patent No. 6455025.
• Table 6 shows the weight-average molecular weight of Comparative Polymer (14) determined in the same manner as in Example 1 and the calculated structural unit content.
• the ratio (molar ratio) of the structural units derived from terephthalic acid chloride and isophthalic acid chloride in the comparative polymer (14) was 1:1.
• evaluation sample (1) 1.2 g of each of the polymers (1) to (9) and comparative polymers (1) to (15) prepared above, and 18 g of tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a solvent are mixed, and each polymer is Each coating liquid was prepared. Each coating liquid was dropped onto a petri dish and dried to obtain a cast film having a thickness of 10 to 50 ⁇ m corresponding to each polymer as a coating film. This cast film was peeled off from the petri dish and used as an evaluation sample.
• Weight loss by abrasion is less than 7 mg
• B: Weight loss by abrasion is 7 mg or more and less than 8 mg
• C: Weight loss by abrasion is 8 mg or more and less than 10 mg
• D: Weight loss by abrasion is 10 mg or more and less than 13 mg
• E: Weight loss by abrasion is 13 mg or more
• evaluation sample (2) 800 mg each of polymers (1) to (9) prepared above and comparative polymers (2) to (15), 4,4′-( ⁇ -methylbenzylidene)bisphenol as an aromatic ring-containing compound (functional material) 400 mg (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 18 g of tetrahydrofuran (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) as a solvent were mixed to prepare each coating liquid corresponding to each polymer. Each coating liquid was dropped onto a petri dish to obtain a cast film having a thickness of 10 to 50 ⁇ m corresponding to each polymer as a coating film. This cast film was peeled off from the petri dish and used as an evaluation sample.
• ⁇ Heat resistance evaluation> The cast film containing the functional material prepared in preparation (2) of the evaluation sample was placed in a blower constant temperature thermostat set at 170° C. and heat-treated for 15 minutes in an air atmosphere. After that, cloudiness and coloration of each cast film, or bleeding of the functional material was visually observed. Visually check whether fogging is promoted after heating compared to before heating, whether coloring is promoted after heating compared to before heating, and whether bleeding of the functional material is observed. evaluated. The results are shown in Tables 1-6. -Evaluation criteria for heat resistance- OK: No haze was promoted after heating and no coloration was promoted. No bleeding of the functional material was observed. NG: After heating, fogging was clearly accelerated, coloration was accelerated, or bleeding of the functional material was observed.
• the wear resistance of each photoreceptor was evaluated based on the wear loss obtained. The results are shown in Tables 1-6. Evaluation samples formed from polymers (1) to (9) were used as evaluation samples for wear resistance test (2) in Examples 1 to 9, respectively, and comparative polymers (2) to (15) were formed. Evaluation samples are used as evaluation samples for wear resistance test (2) of Comparative Examples 1 to 15, respectively. The abrasion resistance of each evaluation sample was evaluated according to the same evaluation criteria as those in the abrasion resistance test (1). The results are shown in Tables 1-6.
• Comparative polymers (1)-(7) and (13)-(15) do not have any of the structural units represented by formulas (IA) and (IB) above.
• the content of the structural unit represented by the above formula (II) is less than 10% by mass.
• Comparative polymers (8) to (12) do not have structural units represented by formula (II) above.
• the content of the structural unit represented by the formula (IB) in the comparative polymer (8) is less than 10% by mass.
• Comparative polymer (1) did not have solubility in tetrahydrofuran and could not be formed into a film.
• Each cast film formed from each comparative polymer other than Comparative Polymer (1) was inferior in abrasion resistance.
• many of the comparative polymers tended to be inferior in heat resistance in coexistence with the functional material.
• each cast film formed from the polymer specified in the present invention was excellent in abrasion resistance, and excellent in film formability even when a large amount of functional material was coexisted. Furthermore, the heat resistance of the cast films of Examples 1 to 5 and 8 was also excellent.

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