JP2016180034A - Method for producing polyester resin and electrophotographic photoreceptor prepared therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polyester resin which can achieve a high molecular weight while comprising an easily-oxidizable divalent phenol, a poorly-reactive divalent alcohol or others and provide a photoreceptor having excellent electric characteristics and durability.SOLUTION: A method for producing a polyester resin, in which at least one ester oligomer is used as a raw material in the production of a polyester resin. An electrophotographic photoreceptor has at least a photosensitive layer on a conductive support, and comprises a polyester resin produced by the production method.SELECTED DRAWING: None

Description

  The present invention is a method for producing a polyester resin, specifically, a method for producing a polyester resin by interfacial polymerization using an oligomer obtained by solution polymerization or melt polymerization, and further an electron using a polyester obtained by using the polyester resin. The present invention relates to a photoconductor.

  A polyester resin is known as one of engineering plastics that are excellent in mechanical strength and amorphous. Regarding the structure of this polyester resin, various structures have been proposed for the properties required so far. In recent years, there has been an increasing demand for coating film resins having excellent transparency and wear resistance in the electrical and electronic fields. Among them, in the electrophotographic field, polyester resins having various structures are used as binder resins for organic photoreceptors. The use of is being considered.

  The electrophotographic photosensitive member is repeatedly used in an electrophotographic process, that is, a cycle such as charging, exposure, development, transfer, cleaning, and static elimination, and is deteriorated by various stresses during that time. Such deterioration includes, for example, strongly oxidative ozone generated from a corona charger normally used as a charger, chemical damage caused by NOx to the photosensitive layer, and carrier (current) generated by image exposure. There are chemical and electrical degradation such as flowing inside, electrical damage due to charging for transferring toner to paper, and decomposing the photosensitive layer composition by static elimination light or external light. Since these deteriorations cause the life of the electrophotographic photosensitive member, the photosensitive layer is required to have durability against these deteriorations.

  As a development of the polyester resin on the electrophotographic photoreceptor, a commercially available polyester resin “U-polymer” is used as a binder resin for the photosensitive layer, so that a polycarbonate resin used in many electrophotographic photoreceptors can be obtained. It has been reported that the sensitivity is improved as compared with the case of using (see Patent Document 1). However, the coating solution prepared by dissolving this polyester resin has low stability, and it may be difficult to produce the coating. To solve this problem, a polyester resin using a divalent phenol component having a specific structure is used as a binder resin, so that the stability of a coating solution used for producing an electrophotographic photoreceptor is improved, and the electrophotographic photoreceptor machine is used. Improvement in mechanical strength and wear resistance has been reported (see Patent Documents 2 to 5).

  The polyester used in these electrophotographic photoreceptors is generally produced by interfacial polymerization using a phase transfer catalyst by mixing a two-phase system of an organic layer and an aqueous layer. The interfacial polymerization method is advantageous in that since divalent phenol is dissolved in an alkaline aqueous solution, it is possible to use divalent phenol which is difficult to dissolve in an organic solvent, and a high molecular weight polyester resin can be obtained. On the other hand, since a highly alkaline aqueous solution is used, a dihydric aliphatic alcohol having low reactivity cannot be used. Dihydric phenol is easily oxidized, and is used because it is hydrolyzed when a dihydric phenol having an ester bond is used as a monomer. There are drawbacks such as inability to do so, and the structure of the resulting polymer is limited. For example, in Patent Document 6 and Patent Document 7, polyesters into which bivalent phenols such as biphenol and resorcinol which are easily oxidized are introduced are obtained by interfacial polymerization using a large amount of antioxidants. On the other hand, it is possible to introduce aliphatic alcohol or dihydric phenol which is easily oxidized into the polyester resin by the melt polymerization method.

JP-A-56-135844 Japanese Patent Laid-Open No. 3-6567 JP-A-9-22126 JP-A-9-319129 JP 2006-290959 A JP 2008-214541 A JP 2010-83986 A

  However, in the techniques described in Patent Document 6 and Patent Document 7, since a large amount of antioxidant is used, the antioxidant remains in the obtained resin, and characteristics such as electrical characteristics may deteriorate. In melt polymerization, if the viscosity at the time of melting is too high, it becomes difficult to handle, so the viscosity average molecular weight of the polyester usually obtained is around 20,000, and the durability may be insufficient. Especially in the field of electrophotography, high-life and high-speed high-end models that can print 100,000 sheets or more have recently appeared, and high mechanical strength is required, so high-molecular weight polyester resins are required.

  An object of the present invention is to provide a method for producing a polyester resin capable of increasing the molecular weight while containing a dihydric phenol that is easily oxidized, a dihydric alcohol having poor reactivity, a dihydric phenol having an ester bond, and the like. An object of the present invention is to obtain a photoreceptor excellent in electrical characteristics and durability by using a polyester resin obtained from the polyester resin production method as a binder resin for an electrophotographic photoreceptor.

  As a result of intensive studies on the production of a polyester resin that can solve the above-mentioned problems, the present inventors have produced an ester oligomer by solution polymerization or melt polymerization at the first stage, and then at the first stage at the second stage. By using the ester oligomer obtained in step 1 as a raw material and producing a polyester resin by interfacial polymerization, etc., dihydric phenols that are easily oxidized, dihydric alcohols with poor reactivity, dihydric phenols with ester bonds, etc. are introduced. The present inventors have found that a high molecular weight polyester resin can be obtained, and have found that the obtained polyester resin can improve the characteristics of an electrophotographic photosensitive member, leading to the present invention. That is, the gist of the present invention resides in the following <1> to <9>.

<1> A method for producing a polyester resin, the method comprising producing at least one ester oligomer as a raw material.
<2> The method for producing a polyester resin according to <1>, wherein the ester oligomer is obtained by a solution polymerization method or a melt polymerization method.
<3> The method for producing a polyester resin according to <1> or <2>, wherein polymerization is performed by an interfacial polymerization method using at least one ester oligomer as a raw material.

<4> The method for producing a polyester resin according to any one of <1> to <1>, wherein at least two kinds of dicarboxylic acid chlorides are used.
<5> The method for producing a polyester resin according to any one of <1> to <4>, wherein at least two kinds of dihydric phenols or dihydric alcohols are used.
<6> The polyester production method according to any one of <1> to <5>, wherein the polyester resin is polymerized so that a viscosity average molecular weight is 15,000 to 100,000.

<7> A method for producing a polyester polycarbonate resin, characterized in that at least one type of carbonate oligomer or polycarbonate resin produced by a melt polymerization method is used as a raw material and polymerized by an interfacial polymerization method. Method.
<8> The method for producing a polyester polycarbonate resin according to <7>, wherein polymerization is performed such that the viscosity average molecular weight of the polyester polycarbonate resin is 30,000 to 150,000.

  <9> An electrophotographic photoreceptor having at least a photosensitive layer on a conductive support, wherein the photosensitive layer is produced by the production method according to any one of <1> to <8>. An electrophotographic photoreceptor comprising a resin.

  According to the present invention, it is possible to produce a high molecular weight polyester resin containing a dihydric phenol that is easily oxidized, a dihydric alcohol having poor reactivity, a dihydric phenol having an ester bond, and the like. By using a polyester resin obtained from a polyester resin production method as a binder resin for an electrophotographic photoreceptor, a photoreceptor excellent in electrical characteristics and durability can be obtained.

1 is a conceptual diagram illustrating an embodiment of an image forming apparatus using an electrophotographic photosensitive member of the present invention.

Hereinafter, modes for carrying out the present invention (hereinafter, embodiments of the present invention) will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the invention.
The method for producing the polyester resin of the present invention is a method for obtaining a polyester resin by using at least one ester oligomer, carbonate oligomer or polycarbonate resin as a raw material. Below, an example of the manufacturing method of a polyester resin is demonstrated.

  In the present invention, the ester means an ester bond composed of a carboxylic acid residue and a phenol residue or an alcohol residue, and the carbonate means a carbonate bond composed of a phenol residue and a carbonyl group. The ester oligomer indicates a product obtained by reacting a divalent carboxylic acid with a dihydric phenol and / or a dihydric alcohol, and there is no clear boundary line with the polymer, but one or several structural units are removed. In the present invention, for example, compounds having a viscosity average molecular weight (Mv) of about 800 to 20,000 can be mentioned. In addition, even when a viscosity average molecular weight exceeds the said range, if it is a manufacturing method of an equivalent effect, it does not exceed the range of this invention. In the present invention, phenol means an aromatic alcohol, and alcohol means an alkyl alcohol.

≪Method for producing ester oligomer≫
Examples of the method for producing the ester oligomer include solution polymerization, melt polymerization, and interfacial polymerization. Among these, solution polymerization and melt polymerization are preferable from the viewpoints of antioxidation of bisphenol, reactivity of dihydric alcohol, stability of ester bond in the monomer, and the like. Furthermore, solution polymerization is particularly preferred from the standpoint of production.

When using the dihydric phenol which has an ester bond, it is preferable to use at the time of ester oligomer manufacture. In the general interfacial polymerization method for producing polyester for electrophotographic photoreceptors, when an alkali salt divalent phenol is dissolved in an aqueous layer, it is quickly ester-bonded by a nucleophilic agent such as hydroxide ion. Is hydrolyzed and polymerization does not proceed. Therefore, by introducing a dihydric phenol having an ester bond into the ester oligomer by a solution polymerization method or a melt polymerization method, it becomes difficult to dissolve in an aqueous solution and can be used for the following polyester production without hydrolysis. It becomes.

  When using the dihydric phenol which is easily oxidized, it is preferable to use it at the time of ester oligomer manufacture. Divalent phenols that are easily oxidized are particularly easily oxidized when they become anions. Therefore, in the interfacial polymerization method, the strong alkali aqueous solution becomes an anion and is rapidly oxidized to prevent the polymerization from proceeding. Therefore, by introducing a dihydric phenol that is easily oxidized into an ester oligomer in advance by a solution polymerization method or a melt polymerization method that does not form an anion, it can be used for the following polyester production.

  In the case of production by a solution polymerization method, for example, the polymerization can be carried out by dissolving a dihydric phenol compound and / or a dihydric alcohol compound and a dicarboxylic acid chloride compound in a solvent and adding a base such as triethylamine. The polymerization temperature is preferably in the range of −10 ° C. to 40 ° C., and the polymerization time is preferably in the range of 0.5 hour to 10 hours from the viewpoint of productivity. After completion of the polymerization, the oligomer dissolved in the organic phase is washed and recovered to obtain the target oligomer. Moreover, you may use the oligomer solution wash | cleaned without collect | recovering as it is for the following polyester polymerization.

Examples of the base used in the solution polymerization method include triethylamine, tripropylamine, tributylamine, N, N-diisopropylethylamine, N, N-dipropylethylamine, N, N-diethylmethylamine, N, N-dimethylethylamine. N, N-dimethylbutylamine, N, N-dimethylisopropylamine, N, N-diethylisopropylamine, N, N, N ′, N′-tetramethyldiethylamine, 1,4-diazabicyclo [2,2,2] Examples include tertiary amines such as octane, pyridines such as pyridine and 4-methylpyridine, and organic bases such as 1,8-diazabicyclo [5.4.0] -7-undecene. Further, there is no particular limitation as long as it is a base such as phosphazene base and inorganic base used for esterification. Among these bases, triethylamine, N, N-dipropylethylamine, N, N-diethylmethylamine, and pyridine are preferable from the viewpoint of the reactivity of the esterification reaction and availability, and the acid chloride is inhibited from being decomposed or washed. Triethylamine is particularly preferable from the viewpoint of ease of removal. The amount of the base used is preferably in the range of 1.01 to 2 equivalents of the carboxylic acid chloride group contained in the reaction system.

Examples of the solvent include halogenated hydrocarbon compounds such as dichloromethane, chloroform, 1,2-dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene and dichlorobenzene, aromatic hydrocarbon compounds such as toluene, anisole and xylene, cyclohexane, methylcyclohexane and the like. Hydrocarbon compounds, ether compounds such as tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 1,3-dioxolane, ester compounds such as ethyl acetate, methyl benzoate, benzyl acetate, N, N-dimethylformamide, N, N- Examples thereof include amide compounds such as dimethylacetamide. Pyridine may be used as a base and a solvent. Among these, dichloromethane, chloroform, 1,2-dichloroethane, tetrahydrofuran, N, N-dimethylformamide, and pyridine are preferable from the viewpoints of solubility of monomers and oligomers to be formed and reactivity of esterification reaction. Further, dichloromethane is particularly preferable from the viewpoint of washing efficiency and electrical characteristics.

When oligomers are produced by the solution polymerization method, the ratio of dihydric phenol and / or dihydric alcohol to dicarboxylic acid chloride is not particularly limited, but one of them must be excessive for use in the production of polyester shown below. There is. Since the phenol end is higher in the air and in the solution than the carboxylic acid chloride end, the dihydric phenol and / or the dihydric alcohol is preferably used in excess of the dicarboxylic acid chloride. When the dihydric phenol and / or dihydric alcohol is more than the dicarboxylic acid chloride, the ratio of dihydric phenol and / or dihydric alcohol: dicarboxylic acid chloride is 10: 1 to 1.1: in molar ratio. 1 is preferable.

  In the case of using a dihydric alcohol for the production of an ester oligomer, if the alcohol is at the end of the oligomer, the hydroxyl group reactivity is low, so that it may not be used in the polyester production method shown below. Therefore, in order to introduce a divalent alcohol residue into the structure of the ester oligomer, it is necessary to copolymerize with a divalent phenol. As this copolymerization method, a dihydric alcohol and a dicarboxylic acid chloride are reacted in advance, and then a divalent phenol is added and reacted to obtain a copolymer oligomer having a terminal hydroxyl group. The ratio of the dihydric alcohol to the dicarboxylic acid chloride is preferably 1:10 to 1: 1.1 in molar ratio and excessive use of the dicarboxylic acid chloride.

  In addition, in the production of ester oligomers, when using a dihydric phenol having poor solubility in a solvent, it may precipitate when reacting with a divalent carboxylic acid chloride, resulting in clouding of the reaction solution or inhibition of oligomerization. . Therefore, when dihydric phenol having poor solubility is introduced into the ester oligomer, it is preferable to use a copolymer with divalent phenol and / or dihydric alcohol having good solubility. In order to further improve the solubility, it is more preferable to react a dihydric phenol and / or dihydric alcohol and a divalent dicarboxylic acid chloride, which have good solubility in advance, and then add and react a dihydric phenol having poor solubility. . Examples of the poorly soluble monomer include rigid aromatic compounds such as hydroquinone, 4,4′-biphenol, and 4-hydroxyphenyl 4-hydroxybenzoate.

  For the production of the ester oligomer, a molecular weight regulator can be used. Or it is also possible to use it at the time of polyester manufacture shown below. Examples of the molecular weight regulator include phenol, o, m, p-cresol, o, m, p-ethylphenol, o, m, p-propylphenol, o, m, p- (tert-butyl) phenol, and pentyl. Alkylphenols such as phenol, hexylphenol, octylphenol, nonylphenol, 2,6-dimethylphenol derivatives, 2-methylphenol derivatives; monofunctional phenols such as o, m, p-phenylphenol; acetic acid chloride, butyric acid chloride, octyl Examples thereof include monofunctional acid halides such as acid chloride, benzoyl chloride, benzenesulfonyl chloride, benzenesulfinyl chloride, sulfinyl chloride, benzenephosphonyl chloride and substituted products thereof. In addition, monofunctional alcohols such as methanol, ethanol, propanol and the like, and monofunctional alcohols having acrylics such as 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy methacrylate, 1H, 1H, 2H, 2H- Examples thereof include monofunctional alcohols having perfluoroalkyl such as tridecafluoro-1-n-octanol, 1H, 1H, 2H, 2H-heptadecafluoro-1-decanol, and monofunctional alcohols having siloxane. Among these molecular weight regulators, o, m, p- (tert-butyl) phenol, 2,6-dimethylphenol derivatives, 2-methylphenol derivatives are preferred because of their high molecular weight controllability and solution stability. It is. Particularly preferred are p- (tert-butyl) phenol, 2,3,6-trimethylphenol, and 2,3,5-trimethylphenol.

  The viscosity average molecular weight (Mv) of the ester oligomer is usually 800 or more. Moreover, it is 20,000 or less normally, Preferably it is 15,000 or less. When the viscosity average molecular weight is less than 800, it may be dissolved in an alkaline aqueous solution at the time of producing a polyester by the interfacial polymerization described below and the ester bond may be decomposed. If it exceeds 20,000, it may be difficult to adjust the viscosity-average molecular weight as intended during the production of the polyester as shown below, and the production efficiency is reduced.

In order not to oxidize the dihydric phenol, an antioxidant can be added during the polymerization reaction or in the cleaning liquid. Examples of the antioxidant include sodium sulfite, hydrosulfite (sodium hyposulfite), sulfur dioxide, potassium sulfite, sodium hydrogen sulfite and the like. Among these, hydrosulfite is particularly preferable from the viewpoint of the antioxidant effect and reduction of environmental load. The amount of the antioxidant used is usually 0.01% by mass or more based on the total dihydric phenol, and preferably 0.1% by mass or more from the viewpoint of antioxidant. Usually, it is 10.0 mass% or less, and 5 mass% or less is preferable from a viewpoint of an electrical property.

  As the washing method after polymerization of the ester oligomer, any method can be used as long as the effects of the present invention are not significantly impaired. For example, a solution of the ester oligomer is an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide; hydrochloric acid, An aqueous solution of acid such as nitric acid and phosphoric acid; a method of separating by standing separation, centrifugation, etc. after washing with water or the like. The ester oligomer after washing is precipitated in water, alcohol or other organic solvent in which the ester oligomer is insoluble, or the solvent of the ester oligomer is distilled off in warm water or in a dispersion medium in which the polyester resin is insoluble, or heated and reduced in pressure. For example, the solvent may be removed by distilling off the solvent, and when the slurry is taken out, the solid can be taken out by a centrifuge or a filter. Further, the ester oligomer may not be taken out after washing, and may be used as it is for the production of the following polyester resin as a solution.

  When the ester oligomer is taken out, it is usually dried at a temperature not higher than the decomposition temperature of the ester oligomer, but can be preferably dried at 20 ° C. or higher and not higher than the melting temperature of the ester oligomer. At this time, it is preferable to dry under reduced pressure. Preferably, the drying time is longer than the time until the purity of impurities such as the residual solvent becomes below a certain level. Specifically, the residual solvent is usually 1000 ppm or lower, preferably 300 ppm or lower, more preferably 100 ppm or lower. dry.

  Since the base used in the production of the ester oligomer may adversely affect the polyester production shown below, such as reaction inhibition and decomposition of dicarboxylic acid chloride, the residual amount of the base is usually 50,000 ppm or less, preferably 10 1,000 ppm or less, more preferably 5,000 ppm or less.

≪Method for producing carbonate oligomer and polycarbonate resin≫
The carbonate oligomer or polycarbonate resin used in the present invention is produced by melt polymerization. Since the carbonate oligomer or polycarbonate produced by melt polymerization has many phenol ends, it can react with a carboxylic acid chloride during the production of the polyester shown below, and a copolymer can be easily obtained. The amount of OH groups present at the ends of the carbonate oligomer and the polycarbonate is usually 30 μeq / g or more, preferably 50 μeq / g or more. If the amount of terminal OH groups does not exceed the above range, there is a possibility that the copolymer will not be obtained due to insufficient reaction during the production of the following polyester resin.

≪Polyester production method≫
When producing a polyester resin using at least one of the ester oligomer, carbonate oligomer and polycarbonate resin, a solution polymerization method or an interfacial polymerization method is preferred. In particular, the interfacial polymerization method is particularly preferable from the viewpoint of the ease of adjusting the molecular weight of the produced polyester resin and the electrical characteristics.

In the case of production by the interfacial polymerization method, for example, an alkaline aqueous solution and a halogenated hydrocarbon or aromatic hydrocarbon solution in which the ester oligomer and the aromatic dicarboxylic acid chloride compound are dissolved are mixed. In this case, a quaternary ammonium salt or a quaternary phosphonium salt can be present as a catalyst. The polymerization temperature is preferably in the range of 0 ° C. to 40 ° C., and the polymerization time is preferably in the range of 2 hours to 20 hours from the viewpoint of productivity. After the completion of the polymerization, the water phase and the organic phase are separated, and the polymer dissolved in the organic phase is washed and recovered by a known method to obtain the intended resin. In the production by interfacial polymerization, if necessary, it is also possible to add a dihydric phenol separately to the alkaline aqueous solution.

Examples of the alkali component used in the interfacial polymerization method include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. As the usage-amount of an alkali component, the range of 1.01 times equivalent-3 times equivalent of the phenolic hydroxyl group contained in a reaction system is preferable.
Examples of the halogenated hydrocarbon include dichloromethane, chloroform, 1,2-dichloroethane, trichloroethane, tetrachloroethane, dichlorobenzene, and the like. Examples of the aromatic hydrocarbon include toluene, xylene, benzene and the like.

  Examples of the quaternary ammonium salt or quaternary phosphonium salt used as the catalyst include, for example, salts of tertiary alkylamines such as tributylamine and trioctylamine such as hydrochloric acid, bromic acid and iodic acid; benzyltriethylammonium chloride, benzyltrimethylammonium Examples include chloride, benzyltributylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, trioctylmethylammonium chloride, tetrabutylphosphonium bromide, triethyloctadecylphosphonium bromide, N-laurylpyridinium chloride, laurylpicolinium chloride It is done.

  In the interfacial polymerization method, a molecular weight regulator can be used. Examples of the molecular weight regulator include phenol, o, m, p-cresol, o, m, p-ethylphenol, o, m, p-propylphenol, o, m, p- (tert-butyl) phenol, and pentyl. Alkylphenols such as phenol, hexylphenol, octylphenol, nonylphenol, 2,6-dimethylphenol derivatives, 2-methylphenol derivatives; monofunctional phenols such as o, m, p-phenylphenol; acetic acid chloride, butyric acid chloride, octyl Examples thereof include monofunctional acid halides such as acid chloride, benzoyl chloride, benzenesulfonyl chloride, benzenesulfinyl chloride, sulfinyl chloride, benzenephosphonyl chloride and substituted products thereof. Among these molecular weight regulators, o, m, p- (tert-butyl) phenol, 2,6-dimethylphenol derivatives, 2-methylphenol derivatives are preferred because of their high molecular weight controllability and solution stability. It is. Particularly preferred are p- (tert-butyl) phenol, 2,3,6-trimethylphenol, and 2,3,5-trimethylphenol.

  In order not to oxidize the dihydric phenol in the alkaline solution, an antioxidant can be added. Examples of the antioxidant include sodium sulfite, hydrosulfite (sodium hyposulfite), sulfur dioxide, potassium sulfite, sodium hydrogen sulfite and the like. Among these, hydrosulfite is particularly preferable from the viewpoint of the antioxidant effect and reduction of environmental load. As the usage-amount of antioxidant, 0.01 mass% or more and 10.0 mass% or less are preferable with respect to all the bivalent phenols. More preferably, it is 0.1 mass% or more and 5 mass% or less. If the content is too small, the antioxidant effect may be insufficient. If the content is too large, it may remain in the polyester and adversely affect electrical characteristics.

As the purification method after polymerization of the polyester resin, any method can be used as long as the effects of the present invention are not significantly impaired. For example, the polyester resin solution is an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide; hydrochloric acid, An aqueous solution of acid such as nitric acid and phosphoric acid; a method of separating by standing separation, centrifugation, etc. after washing with water or the like.
Other purification methods include, for example, a method in which the produced polyester resin solution is precipitated in a solvent in which the polyester resin is insoluble, a method in which the polyester resin solution is dispersed in warm water, and the solvent is distilled off, or polyester You may refine | purify by the method etc. which distribute | circulate the resin solution to an adsorption column etc.

  The polyester resin after purification is precipitated in water, alcohol or other organic solvent in which the polyester resin is insoluble, or the solvent of the polyester resin is distilled off in warm water or in a dispersion medium in which the polyester resin is insoluble, or heating and decompression are performed. For example, the solvent may be removed by distilling off the solvent, and when the slurry is taken out, the solid can be taken out by a centrifuge or a filter. The obtained polyester resin is usually dried at a temperature equal to or lower than the decomposition temperature of the polyester resin, but can be preferably dried at 20 ° C. or higher and below the melting temperature of the resin. At this time, it is preferable to dry under reduced pressure.

Preferably, the drying time is longer than the time until the purity of impurities such as the residual solvent becomes below a certain level. Specifically, the residual solvent is usually 1000 ppm or lower, preferably 300 ppm or lower, more preferably 100 ppm or lower. dry.
In addition, the conditions equivalent to the said polyester manufacture can be applied for manufacture of the polyester polycarbonate resin in this invention.

≪Polyester resin≫
The structure of the polyester resin produced according to the present invention is not particularly limited, but a polyester resin having the following structure is preferable from the viewpoint of solubility, mechanical properties, electrical characteristics, and the like. When at least two types of dicarboxylic acid chlorides are used, or when at least two types of dihydric phenols or dihydric alcohols are used, the above method for producing a polyester resin is effective. The types referred to here are distinguished by molecular structure, and positional isomers, stereoisomers and the like are also distinguished to be one type.

(Divalent carboxylic acid residue)
The polyester resin preferably has at least one divalent carboxylic acid residue represented by the following formulas (1) to (4).

In formula (1), each R ¹ independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a halogenated alkyl group, a halogen group, or a benzyl group, and n is 0 to 0. It is an integer of 4. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, an isobutyl group, and a cyclohexyl group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a cyclohexoxy group. Examples of the halogenated alkyl group include a chloromethyl group and a fluorinated alkyl group. Examples of the halogen group include a fluorine group, a chloro group, and a bromo group. From the viewpoint of wear resistance, an alkyl group having 1 to 6 carbon atoms and an alkoxyl group having 1 to 6 carbon atoms are preferable, and a methyl group and an ethyl group are particularly preferable. Each n is independently an integer of 0 to 4, and preferably n = 0 from the viewpoint of manufacturing simplicity. Specific examples of the divalent carboxylic acid compound derived from the divalent carboxylic acid residue represented by the formula (1) include orthophthalic acid, isophthalic acid, terephthalic acid and the like. Among these, isophthalic acid and terephthalic acid are particularly preferable from the viewpoint of wear resistance.

In formula (2), R ² and R ³ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a halogenated alkyl group, a halogen group, or a benzyl group, m, l is an integer of 0 to 4, and X represents a single bond or an oxygen atom. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, an isobutyl group, and a cyclohexyl group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a cyclohexoxy group. Examples of the halogenated alkyl group include a chloromethyl group and a fluorinated alkyl group. Examples of the halogen group include a fluorine group, a chloro group, and a bromo group. From the viewpoint of wear resistance, an alkyl group having 1 to 6 carbon atoms and an alkoxyl group having 1 to 6 carbon atoms are preferable, and a methyl group and an ethyl group are particularly preferable. m and l are each independently an integer of 0 to 4, and preferably m = 1 from the viewpoint of simplicity in production.

Specific examples of the divalent carboxylic acid compound that derives the divalent carboxylic acid residue represented by the formula (2) include, for example, diphenyl ether-2,2′-dicarboxylic acid, diphenyl ether-2,4′-dicarboxylic acid, Examples include diphenyl ether-4,4′-dicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 2,2′-diphenyldicarboxylic acid, 2,4′-diphenyldicarboxylic acid, and the like. Among these, diphenyl ether-4,4′-dicarboxylic acid and 4,4′-diphenyldicarboxylic acid are particularly preferable from the viewpoints of production convenience and wear resistance.

In formula (3), R ⁴ each independently represents an alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, an isobutyl group, and a cyclohexyl group. From the viewpoint of wear resistance, an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group and an ethyl group are particularly preferable. Each p is independently an integer of 0 to 10, and preferably p = 0 from the viewpoint of ease of production.

Specific examples of the divalent carboxylic acid compound that derives the divalent carboxylic acid residue represented by the formula (3) include, for example, trans-1,4-cyclohexanedicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid, trans-1,3-cyclohexanedicarboxylic acid, cis-1
, 3-cyclohexanedicarboxylic acid and the like. Among these, from the viewpoint of simplicity in production and wear resistance, trans-1,4-cyclohexanedicarboxylic acid, cis-1,
4-cyclohexanedicarboxylic acid is particularly preferred.

  In formula (4), Y represents a single bond, an alkylene group having 1 to 14 carbon atoms, a p-phenylene group, an m-phenylene group, or a 4,4′-biphenyl group. Specific examples of the alkylene group include a methylene group, ethylene group, propylene group, butylene group, 2,2-dimethylpropylene group, cyclohexylene group, and cyclohexanedimethyl group. Specific examples of the divalent carboxylic acid compound derived from the divalent carboxylic acid residue represented by the formula (4) include malonic acid, succinic acid, 2,2-dimethylsuccinic acid, glutamic acid, azelaic acid, 1, Examples thereof include 3-adamantane dicarboxylic acid, sebacic acid, 1,10-decanedicarboxylic acid, 1,4-phenylenediacetic acid and the like.

If necessary, the above dicarboxylic acid residues can be used in combination. In particular, when the polyester resin contains the dicarboxylic acid residue of the formulas (3) and (4), the dicarboxylic acid residue of the above formulas (1) and (2) and Copolymerization is preferred.
(Divalent phenol residue, divalent aliphatic alcohol residue)
The polyester resin preferably has at least one dihydric phenol and / or dihydric alcohol represented by the following formulas (5) to (12).

In formula (5), R ⁵ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a halogenated alkyl group, a halogen group, or a benzyl group, and q is 0 to 0. It is an integer of 4. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, an isobutyl group, and a cyclohexyl group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a cyclohexoxy group. Examples of the halogenated alkyl group include a chloromethyl group and a fluorinated alkyl group. Examples of the halogen group include a fluorine group, a chloro group, and a bromo group. From the viewpoint of wear resistance, an alkyl group having 1 to 6 carbon atoms and an alkoxyl group having 1 to 6 carbon atoms are preferable, and a methyl group and an ethyl group are particularly preferable. Each q is independently an integer of 0 to 4, and preferably, n = 0 and 1 from the viewpoint of simplicity in production.

  Specific examples of the dihydric phenol compound for deriving the dihydric phenol residue represented by the formula (5) include, for example, hydroquinone, methylhydroquinone, bromohydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, resorcinol, 2- Examples include methylresorcinol, 5-methylresorcinol, 5-bromoresorcinol, catechol, and 4-methylcatechol. Among these, hydroquinone, methylhydroquinone, and resorcinol are particularly preferable from the viewpoints of production convenience and wear resistance.

In formula (6), each R ⁶ independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a halogenated alkyl group, a halogen group, or a benzyl group, and r is 0 to It is an integer of 6. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, an isobutyl group, and a cyclohexyl group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a cyclohexoxy group. Examples of the halogenated alkyl group include a chloromethyl group and a fluorinated alkyl group. Examples of the halogen group include a fluorine group, a chloro group, and a bromo group. From the viewpoint of wear resistance, an alkyl group having 1 to 6 carbon atoms and an alkoxyl group having 1 to 6 carbon atoms are preferable, and a methyl group and an ethyl group are particularly preferable. Each n is independently an integer of 0 to 4, and preferably n = 0 from the viewpoint of manufacturing simplicity.

  Specific examples of the dihydric phenol compound for deriving the dihydric phenol residue represented by the formula (6) include 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1 , 6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and the like. Among these, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene are particularly preferable from the viewpoints of manufacturing simplicity, solubility, and abrasion resistance. .

In formula (7), Ar ¹ and Ar ² are each independently a p-phenylene group, m-phenylene group, divalent naphthalene group, or divalent biphenyl group, Z is an alkylene group having 1 to 10 carbon atoms, A p-phenylene group or the following formula (12) is represented, and s is an integer of 0 or 1.

Wherein ^{(12), R} 15 ~R ¹⁸ independently represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms.
Specific examples of the alkylene group in the formula (7) include a methylene group, an ethylene group, a propylene group, a butylene group, a 2,2-dimethylpropylene group, a cyclohexylene group, and a cyclohexanedimethyl group. From the viewpoints of solubility and wear resistance, an alkyl group having 1 to 8 carbon atoms is preferable, and an ethylene group, a cyclohexylene group, and a cyclohexanedimethyl group are particularly preferable.

Specific examples of the alkyl group in formula (12) include a methyl group, an ethyl group, a til group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, an isobutyl group, and a cyclohexyl group. A methyl group is preferred from the viewpoint of solubility, abrasion resistance, and ease of production.
Specific examples of the dihydric phenol compound for deriving the dihydric phenol residue represented by the formula (7) are shown below.

  In formula (8), W is a single bond, an alkylene group having 1 to 16 carbon atoms, a perfluoroalkylene group having 3 to 10 carbon atoms, an m-phenylene group, a p-phenylene group, a divalent biphenyl group, or 2 Represents a divalent naphthalene group. Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a cyclohexylene group, and an octylene group. Specific examples of the perfluoroalkylene group include a hexafluoro-1,3-propylene group, an octafluoro-1,4-butylene group, a dodecafluoro-1,6-hexylene group, and a hexadecafluoro-1,8-octylene group. Etc. From the viewpoint of solubility and wear resistance, an alkylene group having 1 to 6 carbon atoms and a perfluoroalkylene group having 3 to 8 carbon atoms are preferable.

  Specific examples of the dihydric alcohol compound derived from the dihydric alcohol residue represented by the formula (8) include, for example, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentane. Diol, 1,3-cyclopentanedimethanol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,16 -Hexadecanediol, 1,4-benzenedimethanol, 4,4'-biphenyldimethanol, 2,2,3,3,4,4-hexafluoro-1,5-pentanediol, 2,2,3,3 , 4,4,5,5,6,6,7,7-dodecafluoro-1,8-octanediol, 1H, 1H, 10H, 10H-hexadecafluor 1,10-decanediol, and the like. Among these, ethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,8-octanediol, 1,4-benzene from the viewpoint of ease of production, solubility, and abrasion resistance Dimethanol and 4,4′-biphenyldimethanol are particularly preferred.

In the formula (9), R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxyl group having 1 to 10 carbon atoms, and t and u are each an integer of 0 to 10. . A represents a single bond, —CR ⁹ R ¹⁰ —. R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a group that forms a ring in which R ⁹ and R ¹⁰ may be bonded to each other. v is an integer of 0 or 1. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, an isobutyl group, and a cyclohexyl group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a cyclohexoxy group. From the viewpoint of wear resistance, an alkyl group having 1 to 6 carbon atoms and an alkoxyl group having 1 to 6 carbon atoms are preferable, and a methyl group and an ethyl group are particularly preferable. t and u are each independently an integer of 0 to 10, and preferably t = u = 0 from the viewpoint of ease of production.

  Specific examples of the dihydric alcohol compound for deriving the dihydric alcohol residue represented by the formula (9) include 1,4-cyclohexanediol, 2,2-bis (4-hydroxycyclohexyl) propane, 4, 4-bicyclohexanol etc. are mentioned.

  Specific examples of the dihydric alcohol compound that induces the dihydric alcohol residue represented by the formula (10) include isomannide, isosorbide, and the like.

In formula (11), R ^{11 to} R ¹⁴ each independently represents a hydrogen atom or a methyl group. V represents a single bond, —CR ¹⁵ R ¹⁶ —, O, CO, or S. R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a methyl group, or an ethyl group, or R ¹⁵ and R ¹⁶ are a cyclopentyl group or a cyclohexylidene group formed by combining R ¹⁵ and R ^16. Represents.
Specific examples of the bisphenol residue of the polyester resin represented by the formula (11) include bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) methane, and bis- (3 5-dimethyl-4-hydroxyphenyl) methane, 1,1-bis- (4-hydroxyphenyl) ethane, 1,1-bis- (4-hydroxy-3-methylphenyl) ethane, 1,1-bis- ( 3,5-dimethyl-4-hydroxyphenyl) ethane, 1,1-bis- (4-hydroxyphenyl) propane, 1,1-bis- (4-hydroxy-3-methylphenyl) propane, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydrokey 3 Methylphenyl) propane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis- (4-hydroxyphenyl) cyclohexane, 1,1-bis- (4-hydrokey 3 -Methylphenyl) cyclohexane, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis- (4-hydroxyphenyl) -1-phenylethane, 4,4'-biphenol 3,3′-dimethyl-4,4′-biphenol, 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol, 4,4′-dihydroxydiphenyl ether, 3,3′-dimethyl- 4,4'-dihydroxydiphenyl ether, bis (4-hydroxyphenyl) sulfide, 4,4'-dihydroxybenzophenone, etc. The Among these, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) methane, bis- ( 3,5-dimethyl-4-hydroxyphenyl) methane, 1,1-bis- (4-hydroxyphenyl) ethane, 1,1-bis- (4-hydroxy-3-methylphenyl) ethane, 2,2-bis -(4-hydroxyphenyl) propane, 2,2-bis- (4-hydrokey 3-methylphenyl) propane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1- Bis- (4-hydroxyphenyl) cyclohexane, 4,4'-biphenol, 3,3'-dimethyl-4,4'-biphenol, 3,3 ', 5,5'-tetramethyl -4,4'-biphenol and 4,4'-dihydroxydiphenyl ether are preferred. Further, considering mechanical properties, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) methane, 1,1-bis- (4-hydroxyphenyl) ethane, 1,1- Bis- (4-hydroxy-3-methylphenyl) ethane, 2,2-bis- (4-hydrokey 3-methylphenyl) propane, 4,4'-biphenol, 3,3'-dimethyl-4,4'- Biphenol and 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol are more preferred.

In the case of producing the polyester resin of the present invention, when at least one dihydric phenol or dihydric alcohol of the above formulas (5) to (10) is used, from the viewpoint of solubility, molecular weight of the resin, and mechanical properties, It is preferable to copolymerize with the dihydric phenol of (11). The content of the formula (11) is not particularly defined, but is preferably 5 mol% or more of all dihydric phenols and dihydric alcohols, more preferably 30 mol% or more, and further preferably 50 mol% or more.
Since the base used at the time of the ester oligomer production may adversely affect the reaction of the polyester production shown below and the decomposition of dicarboxylic acid chloride, the residual amount of the base is usually 20,000 ppm or less, preferably It is 5,000 ppm or less, more preferably 1,000 ppm or less.
The total nitrogen amount (TN amount) contained in the ester oligomer is preferably 5,000 ppm or less, more preferably 2,500 ppm or less, and particularly preferably 1,000 ppm or less. When the total nitrogen amount exceeds 5,000 ppm, there is a possibility of adverse effects such as reaction inhibition and decomposition of dicarboxylic acid chromoids on the polyester production shown below.

≪Polyester polycarbonate resin≫
About the polyester site | part contained in polyester polycarbonate resin, the thing equivalent to the said polyester resin is preferable about dicarboxylic acid, dihydric phenol, and / or dihydric alcohol. Formula (13) is preferable for the carbonate oligomer and the polycarbonate resin.

In formula (13), R ^{19 to} R ²² each independently represents a hydrogen atom or a methyl group. Q represents a single bond, —CR ²³ R ²⁴ —, O, CO, or S. R ²³ and R ²⁴ each independently represent a hydrogen atom, a methyl group, or an ethyl group, or R ²² and R ²³ are a cyclopentyl group or a cyclohexyl group formed by combining R ²² and R ^23. A den group. From the viewpoint of wear resistance and production convenience, it is preferable that R ¹⁹ = R ²¹ = hydrogen atom, methyl group, and R ²⁰ = R ²² = hydrogen atom. R ²³ and R ²⁴ are each preferably a hydrogen atom or a methyl group.

≪Resin physical properties≫
From the viewpoint of mechanical strength, the viscosity average molecular weight (Mv) of the polyester resin and polyester polycarbonate resin produced by the production method of the present invention is usually 15,000 or more, preferably 20,000 or more. Moreover, from a viewpoint of applicability | paintability, it is 150,000 or less normally, Preferably it is 100,000 or less.

In addition, the amount of carboxylic acid chloride group present at the terminal of the polyester resin in the present invention is usually 0.1 μ equivalent / g or less, preferably 0.05 μ equivalent / g or less. When the amount of the terminal carboxylic acid chloride group exceeds the above range, the storage stability when the polyester resin is used as a coating solution for an electrophotographic photoreceptor tends to decrease.
The amount of OH groups present at the end of the polyester resin in the present invention is usually 100 μeq / g or less, preferably 50 μeq / g or less. If the amount of terminal OH groups exceeds the above range, the electrical characteristics when the polyester resin is used as an electrophotographic photoreceptor may be deteriorated.

The amount of the carboxylic acid group present at the terminal of the polyester resin in the present invention is usually 200 µequivalent / g or less, preferably 100 µequivalent / g or less. If the amount of the terminal carboxylic acid group exceeds the above range, the electrical characteristics when the polyester resin is used as an electrophotographic photoreceptor may be deteriorated.
The total nitrogen amount (TN amount) contained in the polyester resin is preferably 3,000 ppm or less, more preferably 1,000 ppm or less, and particularly preferably 500 ppm or less. If the total nitrogen amount exceeds 3,000 ppm, the electrical characteristics may deteriorate.

≪Coating solution for electrophotographic photosensitive member≫
The polyester resin of the present invention is suitably used for an electrophotographic photoreceptor coating solution. This coating solution for an electrophotographic photoreceptor is usually used for forming a photosensitive layer in an electrophotographic photoreceptor, and particularly preferably used for forming a charge transport layer when the photosensitive layer is a laminated photosensitive layer.
In the electrophotographic photosensitive member coating solution, the polyester resin is usually used as a binder resin. In the electrophotographic photosensitive member coating solution, in addition to the polyester resin, for example, a charge generating material, a charge transporting material, or the like Necessary materials are appropriately contained depending on the application of the coating solution for a photographic photoreceptor. Such a charge generating substance, a charge transporting substance, and the like can be the same as those described in the section of the electrophotographic photosensitive member described later.

  Moreover, it is also possible to mix and use the polyester resin manufactured from the manufacturing method by this invention, and other resin in the coating liquid for electrophotographic photoreceptors. Examples of the resin having another structure mixed here include vinyl polymers such as polymethyl methacrylate, polystyrene, and polyvinyl chloride or copolymers thereof; polycarbonate resins, polyester resins, polyester resins, polyester polycarbonate resins, polysulfones. Examples thereof include thermoplastic resins such as resins, phenoxy resins, epoxy resins, and silicone resins, and various thermosetting resins. Among these resins, polycarbonate resin or polyester resin is preferable.

  Specific examples of suitable structures of the resin having the other structure are shown below. These specific examples are shown for illustration, and any known binder resin may be mixed and used as long as it does not contradict the gist of the present invention.

≪Electrophotographic photoreceptor≫
The electrophotographic photosensitive member to which this embodiment is applied has a photosensitive layer provided on a conductive support, and the photosensitive layer contains the polyester resin. As a specific configuration of the photosensitive layer, for example, a laminate in which a charge generation layer mainly composed of a charge generation material and a charge transport layer mainly composed of a charge transport material and a binder resin are stacked on a conductive support. Type photoreceptor; a dispersion type (single layer type) photoreceptor having a photosensitive layer in which a charge generating substance is dispersed in a layer containing a charge transport substance and a binder resin on a conductive support. The polyester resin is usually used for a layer containing a charge transport material, and preferably used for a charge transport layer of a multilayer photoreceptor.

  As a specific configuration of the photosensitive layer used in the electrophotographic photosensitive member to which the exemplary embodiment is applied, for example, in the case of a laminated type photosensitive member, it contains a charge transport material and a binder resin, and maintains an electrostatic charge. A charge transport layer that transports charges generated by exposure, and a charge generation layer that contains a charge generation material and generates charge pairs by exposure. In addition, if necessary, for example, a charge blocking layer for blocking charge injection from the conductive support, a light diffusion layer for diffusing light such as laser light to prevent interference fringes, etc. There is. In the case of a dispersion type (single layer type) photoreceptor, a charge transfer material and a charge generation material are dispersed in a binder resin in the photosensitive layer.

<Conductive support>
There is no particular limitation on the conductive support, but for example, metal materials such as aluminum, aluminum alloy, stainless steel, copper, and nickel, and conductive powder such as metal, carbon, and tin oxide are added to impart conductivity. A resin material, a resin, glass, paper, or the like on which a conductive material such as aluminum, nickel, or ITO (indium tin oxide) is deposited or applied on the surface is mainly used. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio. As a form of the conductive support, a drum form, a sheet form, a belt form or the like is used. Furthermore, a conductive material having an appropriate resistance value may be used on a conductive support made of a metal material in order to control conductivity and surface properties and to cover defects.

Moreover, when using metal materials, such as an aluminum alloy, as an electroconductive support body, you may use, after giving an anodic oxide film. When an anodized film is applied, it is desirable to perform a sealing treatment by a known method.
The support surface may be smooth, or may be roughened by using a special cutting method or performing a polishing treatment. Further, it may be roughened by mixing particles having an appropriate particle diameter with the material constituting the support. In order to reduce the cost, it is possible to use the drawing tube as it is without performing the cutting process.

<Underlayer>
An undercoat layer may be provided between the conductive support and the photosensitive layer described later for improving adhesion and blocking properties. As the undercoat layer, a resin and a resin in which particles such as a metal oxide are dispersed are used. The undercoat layer may be a single layer or a plurality of layers. The undercoat layer may contain a known antioxidant, pigment particles, resin particles and the like. The film thickness is usually 0.01 μm or more, preferably 0.1 μm or more, from the viewpoint of improving the electrical characteristics, strong exposure characteristics, image characteristics, repeat characteristics, and coating properties during production of the electrophotographic photoreceptor. Usually, it is 30 μm or less, preferably 20 μm or less.

  Examples of metal oxide particles used for the undercoat layer include metal oxide particles containing one metal element such as titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, zinc oxide, iron oxide, calcium titanate, titanium Examples thereof include metal oxide particles containing a plurality of metal elements such as strontium acid and barium titanate. One kind of these particles may be used alone, or a plurality of kinds of particles may be mixed and used. Among these metal oxide particles, titanium oxide and aluminum oxide are preferable, and titanium oxide is particularly preferable. The surface of the titanium oxide particles may be treated with an inorganic substance such as tin oxide, aluminum oxide, antimony oxide, zirconium oxide, or silicon oxide, or an organic substance such as stearic acid, polyol, or silicon. As the crystal form of the titanium oxide particles, any of rutile, anatase, brookite, and amorphous can be used. Moreover, the thing of the several crystal state may be contained. From the viewpoint of characteristics and liquid stability, the average primary particle size is preferably 10 nm or more and 100 nm or less, particularly preferably 10 nm or more and 50 nm or less. This average primary particle size can be obtained from a TEM photograph or the like.

The undercoat layer is preferably formed in a form in which metal oxide particles are dispersed in a binder resin. The binder resin used for the undercoat layer is epoxy resin, polyethylene resin, polypropylene resin, acrylic resin, methacrylic resin, polyamide resin, vinyl chloride resin, vinyl acetate resin, phenol resin, polycarbonate resin, polyurethane resin, polyimide resin, chloride resin. Cellulose esters such as vinylidene resin, polyvinyl acetal resin, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol resin, polyurethane resin, polyacryl resin, polyacrylamide resin, polyvinyl pyrrolidone resin, polyvinyl pyridine resin, water-soluble polyester resin, nitrocellulose Resin, cellulose ether resin, casein, gelatin, polyglutamic acid, starch, starch acetate, amino starch, zirconium chelate compound, zirconium The organic zirconium compound alkoxide compounds, titanyl chelate compounds, organic titanyl compounds such as titanium alkoxide compounds include known binder resins such as a silane coupling agent. These may be used alone or in combination of two or more in any combination and ratio. Moreover, you may use with the hardening | curing form with the hardening | curing agent. Among these, alcohol-soluble copolymerized polyamides, modified polyamides, and the like are preferable because they exhibit good dispersibility and coatability.

  The use ratio of the inorganic particles to the binder resin used in the undercoat layer can be arbitrarily selected. From the viewpoint of the stability of the dispersion and the coating property, the binder resin is usually 10% by mass or more, It is preferable to use in the range of 500 mass% or less.

<Photosensitive layer>
As a type of the photosensitive layer, a charge generation material and a charge transport material are present in the same layer and are dispersed in a binder resin, a charge generation layer in which a charge generation material is dispersed in a binder resin, and a charge. A functional separation type (laminated type) composed of two layers of a charge transport layer in which a transport material is dispersed in a binder resin can be mentioned, but any type may be used.

  In addition, as the laminated photosensitive layer, a charge generation layer and a charge transport layer are laminated in this order from the conductive support side, and a charge transport layer and a charge generation layer are laminated in this order. There are reverse laminated type photosensitive layers, and any of them can be adopted, but a forward laminated type photosensitive layer capable of exhibiting the most balanced photoconductivity is preferable.

<Laminated photosensitive layer>
[Charge generation layer]
In the case of a laminated type photoreceptor (function separation type photoreceptor), the charge generation layer is formed by binding a charge generation material with a binder resin. The film thickness is usually 0.1 μm or more, preferably 0.15 μm or more, and usually 10 μm or less, preferably 0.6 μm or less.

  Examples of the charge generation material include inorganic photoconductive materials such as selenium and its alloys, cadmium sulfide, and organic photoconductive materials such as organic pigments, but organic photoconductive materials are preferred, especially organic pigments. Is preferred. Examples of organic pigments include phthalocyanine pigments, azo pigments, dithioketopyrrolopyrrole pigments, squalene (squarylium) pigments, quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, anthanthrone pigments, and benzimidazole pigments. . Among these, phthalocyanine pigments or azo pigments are particularly preferable. When organic pigments are used as the charge generating substance, usually, fine particles of these organic pigments are used in the form of a dispersion layer bound with various binder resins.

  When using a phthalocyanine pigment as a charge generation material, specifically, metal-free phthalocyanine, copper, indium, gallium, tin, titanium, zinc, vanadium, silicon, germanium, aluminum or other metal or oxide thereof, halide, water Those having crystal forms of coordinated phthalocyanines such as oxides and alkoxides, and phthalocyanine dimers using oxygen atoms as bridging atoms are used. In particular, titanyl phthalocyanines (also known as oxytitanium) such as X-type, τ-type metal-free phthalocyanine, A-type (also known as β-type), B-type (also known as α-type), and D-type (also known as Y-type), which are highly sensitive crystal types Phthalocyanine), vanadyl phthalocyanine, chloroindium phthalocyanine, hydroxyindium phthalocyanine, chlorogallium phthalocyanine such as type II, hydroxygallium phthalocyanine such as type V, μ-oxo-gallium phthalocyanine dimer such as type G and type I, type II, etc. The [mu] -oxo-aluminum phthalocyanine dimer is preferred.

  Among these phthalocyanines, A-type (also known as β-type), B-type (also known as α-type), and powder X-ray diffraction angle 2θ (± 0.2 °) are 27.1 ° or 27.3 °. D-type (Y-type) titanyl phthalocyanine, II-type chlorogallium phthalocyanine, V-type and 28.1 ° have the strongest peak, and 26.2 ° have a peak. Hydroxygallium phthalocyanine having a clear peak at 28.1 ° and a full width at half maximum W of 25.9 ° of 0.1 ° ≦ W ≦ 0.4 °, G-type μ-oxo -Gallium phthalocyanine dimer and the like are particularly preferable. Among these, D-type (Y-type) titanyl phthalocyanine is preferable because it exhibits good sensitivity.

  The phthalocyanine compound may be a single compound or several mixed or mixed crystal states. As the mixed state that can be put in the phthalocyanine compound or crystal state here, those obtained by mixing the respective constituent elements later may be used, or they may be mixed in the production / treatment process of the phthalocyanine compound such as synthesis, pigmentation, and crystallization. It may be the one that caused the condition. As such treatment, acid paste treatment, grinding treatment, solvent treatment and the like are known. In order to generate a mixed crystal state, as described in JP-A-10-48859, two types of crystals are mixed, mechanically ground and made amorphous, and then converted into a specific crystal state by solvent treatment. The method of doing is mentioned.

  The binder resin used for the charge generation layer includes polyvinyl butyral resin, polyvinyl formal resin, polyvinyl acetal resins such as partially acetalized polyvinyl butyral resin in which a part of butyral is modified with formal, acetal, etc., polyarylate resin, polycarbonate Resin, polyester resin, modified ether polyester resin, phenoxy resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polystyrene resin, acrylic resin, methacrylic resin, polyacrylamide resin, polyamide resin, polyvinyl pyridine resin, cellulose Resin, polyurethane resin, epoxy resin, silicone resin, polyvinyl alcohol resin, polyvinylpyrrolidone resin, casein, vinyl chloride-vinyl acetate copolymer, Vinyl chloride-vinyl acetate copolymers such as droxy-modified vinyl chloride-vinyl acetate copolymer, carboxyl-modified vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, styrene-butadiene copolymer Insulating resins such as polymers, vinylidene chloride-acrylonitrile copolymers, styrene-alkyd resins, silicon-alkyd resins, phenol-formaldehyde resins, and organic photoconductive materials such as poly-N-vinylcarbazole, polyvinylanthracene, and polyvinylperylene. Examples thereof include polymers. Any one of these binder resins may be used alone, or two or more thereof may be mixed and used in any combination.

  In the charge generation layer, the mixing ratio (mass) of the binder resin and the charge generation material is usually 10 parts by mass or more, preferably 30 parts by mass or more, and usually 1000 parts by mass with respect to 100 parts by mass of the binder resin. Part or less, preferably 500 parts by weight or less.

[Charge transport layer]
The charge transport layer of the multilayer photoreceptor contains a charge transport material and usually contains a binder resin and other components used as necessary. The charge transport layer may be composed of a single layer, or may be a stack of a plurality of layers having different constituent components or composition ratios. The film thickness is usually 5 μm to 50 μm, preferably 10 μm to 45 μm.

Examples of charge transport materials include aromatic nitro compounds such as 2,4,7-trinitrofluorenone, cyano compounds such as tetracyanoquinodimethane, electron withdrawing materials such as quinone compounds such as diphenoquinone, carbazole derivatives, indoles Derivatives, imidazole derivatives, oxazole derivatives, pyrazole derivatives, thiadiazole derivatives, heterocyclic compounds such as benzofuran derivatives, aniline derivatives, hydrazone derivatives, aromatic amine derivatives, stilbene derivatives, butadiene derivatives, enamine derivatives and multiple types of these compounds bind Or an electron donating substance such as a polymer having a group consisting of these compounds in the main chain or side chain. Among these, carbazole derivatives, aromatic amine derivatives, stilbene derivatives, butadiene derivatives, enamine derivatives, and those in which a plurality of these compounds are bonded are preferable. These charge transport materials may be used alone or in combination. Specific examples of suitable structures of the charge transport material are shown below.

The polyester resin is preferably used as a binder resin for a charge transport layer. The binder resin may be a mixture of the polyester resin and a resin having another structure. Examples of the other resin include those described in Resins having other structures mixed in the photosensitive layer.
The ratio of the polyester resin to the charge transport material is usually 30 to 200 parts by weight, preferably 40 to 150 parts by weight with respect to 100 parts by weight of the binder resin. The ratio of the entire binder resin and the charge transport material in the photosensitive layer is preferably 20 parts by mass or more with respect to 100 parts by mass of the binder resin. Especially, 30 mass parts or more are more preferable from a viewpoint of residual potential reduction, and 40 mass parts or more are still more preferable from a viewpoint of stability and charge mobility at the time of using repeatedly. On the other hand, from the viewpoint of thermal stability of the photosensitive layer, it is preferable to use the charge transport material in a ratio of usually 150 parts by mass or less. Especially, 110 mass parts or less are more preferable from a compatible viewpoint of charge transport material and binder resin.

  It should be noted that the charge transport layer has well-known plasticizers, antioxidants, ultraviolet absorbers, and electron withdrawing properties in order to improve film forming properties, flexibility, coating properties, stain resistance, gas resistance, light resistance, etc. You may contain additives, such as a compound, dye, a pigment, and a leveling agent. Examples of the antioxidant include hindered phenol compounds and hindered amine compounds. Examples of dyes and pigments include various pigment compounds and azo compounds.

<Single layer type photosensitive layer>
The single-layer type photosensitive layer is formed using a binder resin in order to ensure film strength, in the same manner as the charge transport layer of the multilayer photoconductor, in addition to the charge generation material and the charge transport material. Specifically, a charge generation material, a charge transport material, and various binder resins are dissolved or dispersed in a solvent to prepare a coating solution, and on a conductive support (or an undercoat layer when an undercoat layer is provided). It can be obtained by coating and drying.

The types of the charge transport material and the binder resin and the use ratios thereof are the same as those described for the charge transport layer of the multilayer photoreceptor. The charge generating material is further dispersed in the charge transport medium comprising these charge transport material and binder resin.
As the charge generation material, the same materials as those described for the charge generation layer of the multilayer photoreceptor can be used. However, in the case of a photosensitive layer of a single-layer type photoreceptor, it is necessary to sufficiently reduce the particle size of the charge generating material. Specifically, the range is usually 1 μm or less, preferably 0.5 μm or less.

If the amount of the charge generating material dispersed in the single-layer type photosensitive layer is too small, sufficient sensitivity cannot be obtained, but if it is too large, there are adverse effects such as a decrease in chargeability and a decrease in sensitivity. It is used in the range of usually 0.5% by mass or more, preferably 1% by mass or more, and usually 50% by mass or less, preferably 20% by mass or less based on the whole layer-type photosensitive layer.
In addition, the usage ratio of the binder resin and the charge generation material in the single-layer type photosensitive layer is such that the charge generation material is usually 0.1 parts by weight or more, preferably 1 part by weight or more, based on 100 parts by weight of the binder resin. 30 parts by mass or less, preferably 10 parts by mass or less.

  The film thickness of the single-layer type photosensitive layer is usually 5 μm or more, preferably 10 μm or more, and usually 100 μm or less, preferably 50 μm or less. Also in this case, a known plasticizer for improving film formability, flexibility, mechanical strength, an additive for suppressing residual potential, a dispersion aid for improving dispersion stability, and coating properties are provided. Leveling agents and surfactants for improvement, such as silicone oil, fluorine oil and other additives may be added.

<Other functional layers>
For the purpose of improving film forming properties, flexibility, coating properties, contamination resistance, gas resistance, light resistance, etc., in both the photosensitive layer and the layers constituting the photosensitive layer, both of the multilayer type photosensitive member and the single layer type photosensitive member. Additives such as well-known antioxidants, plasticizers, ultraviolet absorbers, electron-withdrawing compounds, leveling agents, and visible light shielding agents may be contained. Further, for the purpose of reducing the frictional resistance and wear on the surface of the photoconductor, and increasing the transfer efficiency of the toner from the photoconductor to the transfer belt and paper, etc., the surface layer is made of fluorine resin, silicon resin, polyethylene resin, or the like. Particles made of the above resin or inorganic compound particles may be contained in the surface layer. Alternatively, a layer containing these resins and particles may be newly formed as a surface layer. Further, if necessary, it may have a layer for improving electrical properties and mechanical properties, such as an intermediate layer such as a barrier layer, an adhesive layer and a blocking layer, and a transparent insulating layer.

<Method for forming each layer>
Each layer constituting these photoreceptors is formed by immersing, coating, spraying, nozzle coating, bar coating, roll coating, blade coating, etc., on a support, a coating solution obtained by dissolving or dispersing a substance to be contained in a solvent. In this method, the coating and drying steps are sequentially repeated for each layer.

  There are no particular restrictions on the solvent or dispersion medium used in the preparation of the coating solution, but specific examples include alcohols such as methanol, ethanol, propanol and 2-methoxyethanol, tetrahydrofuran, 1,4-dioxane, dimethoxyethane and the like. Ethers, esters such as methyl formate and ethyl acetate, ketones such as acetone, methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as benzene, toluene and xylene, dichloromethane, chloroform, 1,2-dichloroethane, 1,1, Chlorinated hydrocarbons such as 2-trichloroethane, 1,1,1-trichloroethane, tetrachloroethane, 1,2-dichloropropane, trichloroethylene, n-butylamine, isopropanolamine, diethylamine, triethanolamine, ethylenediamine , Nitrogen-containing compounds such as triethylenediamine, acetonitrile, N- methylpyrrolidone, N, N- dimethylformamide, aprotic polar solvents such as dimethyl sulfoxide and the like. Among these solvents, non-halogen solvents are preferable from the viewpoint of environmental considerations, and toluene, xylene, anisole, dimethoxyethane, tetrahydrofuran, and 1,4-dioxane are particularly preferable from the viewpoint of solubility. Any one of these may be used alone, or two or more of these may be used in combination.

The amount of the solvent or dispersion medium used is not particularly limited, but considering the purpose of each layer and the properties of the selected solvent / dispersion medium, it is appropriate so that the physical properties such as solid content concentration and viscosity of the coating liquid are within a desired range. It is preferable to adjust.
For example, in the case of a charge transport layer of a single layer type photoreceptor or a function separation type photoreceptor, the solid content concentration of the coating solution is usually 5% by mass or more, usually 5% by mass or more, preferably 10% by mass or more. The range is usually 40% by mass or less, preferably 35% by mass or less. Further, the viscosity of the coating solution is usually in the range of 10 cps or more, preferably 50 cps or more, and usually 500 cps or less, preferably 400 cps or less.

In the case of a charge generation layer of a multilayer photoreceptor, the solid content concentration of the coating solution is usually 0.1% by mass or more, preferably 1% by mass or more, and usually 15% by mass or less, preferably 10% by mass. % Or less. The viscosity of the coating solution is usually 0.01 cps or more, preferably 0.1 cps or more, and usually 20 cps or less, preferably 10 cps or less.
Examples of the coating method include a dip coating method, a spray coating method, a spinner coating method, a bead coating method, a wire bar coating method, a blade coating method, a roller coating method, an air knife coating method, and a curtain coating method. Other known coating methods can also be used.

  The coating solution is preferably dried by touching at room temperature, followed by heating or drying in a temperature range of usually 30 ° C. or more and 200 ° C. or less for 1 minute to 2 hours, while still or blowing. The heating temperature may be constant or the heating may be performed while changing the temperature during drying.

<Image forming apparatus>
Next, an embodiment of an image forming apparatus using the electrophotographic photosensitive member of the present invention (an image forming apparatus of the present invention) will be described with reference to FIG. However, the embodiment is not limited to the following description, and can be arbitrarily modified without departing from the gist of the present invention.

As shown in FIG. 1, the image forming apparatus includes an electrophotographic photosensitive member 1, a charging device 2, an exposure device 3, and a developing device 4, and further, a transfer device 5, a cleaning device 6 and a fixing device as necessary. A device 7 is provided.
The electrophotographic photoreceptor 1 is not particularly limited as long as it is the above-described electrophotographic photoreceptor of the present invention, but in FIG. 1, as an example, a drum in which the above-described photosensitive layer is formed on the surface of a cylindrical conductive support. The photoconductor is shown. A charging device 2, an exposure device 3, a developing device 4, a transfer device 5 and a cleaning device 6 are arranged along the outer peripheral surface of the electrophotographic photosensitive member 1.

  The charging device 2 charges the electrophotographic photosensitive member 1 and uniformly charges the surface of the electrophotographic photosensitive member 1 to a predetermined potential. Examples of the charging device include a corona charging device such as a corotron and a scorotron, a direct charging device (contact type charging device) that charges a direct charging member to which a voltage is applied by contacting the photosensitive member surface, and a contact type charging device such as a charging brush. Often used. Examples of direct charging means include contact chargers such as charging rollers and charging brushes. In FIG. 1, a roller-type charging device (charging roller) is shown as an example of the charging device 2. As the direct charging means, either charging with air discharge or injection charging without air discharge is possible. Moreover, as a voltage applied at the time of charging, it is possible to use only a direct current voltage or to superimpose an alternating current on a direct current.

  The type of the exposure apparatus 3 is not particularly limited as long as it can expose the electrophotographic photoreceptor 1 to form an electrostatic latent image on the photosensitive surface of the electrophotographic photoreceptor 1. Specific examples include halogen lamps, fluorescent lamps, lasers such as semiconductor lasers and He—Ne lasers, LEDs, and the like. Further, exposure may be performed by a photoreceptor internal exposure method. The light used for the exposure is arbitrary. For example, the exposure may be performed using monochromatic light with a wavelength of 780 nm, monochromatic light with a wavelength slightly shorter than 600 nm to 700 nm, or monochromatic light with a short wavelength of 380 nm to 500 nm. . Among these, it is preferable to use light having a short wavelength of 380 to 500 nm because the resolution becomes high. Among these, 405 nm monochromatic light is preferable.

  The type of the developing device 4 is not particularly limited, and an arbitrary device such as a dry development method such as cascade development, one-component insulating toner development, one-component conductive toner development, or two-component magnetic brush development, or a wet development method is used. be able to. In FIG. 1, the developing device 4 includes a developing tank 41, an agitator 42, a supply roller 43, a developing roller 44, and a regulating member 45, and has a configuration in which toner T is stored inside the developing tank 41. . Further, a replenishing device (not shown) for replenishing the toner T may be attached to the developing device 4 as necessary. The replenishing device is configured to be able to replenish toner T from a container such as a bottle or a cartridge.

  The type of the transfer device 5 is not particularly limited, and an apparatus using an arbitrary system such as an electrostatic transfer method such as corona transfer, roller transfer, or belt transfer, a pressure transfer method, or an adhesive transfer method can be used. . Here, it is assumed that the transfer device 5 includes a transfer charger, a transfer roller, a transfer belt, and the like that are disposed to face the electrophotographic photoreceptor 1. The transfer device 5 applies a predetermined voltage value (transfer voltage) having a polarity opposite to the charging potential of the toner T, and transfers the toner image formed on the electrophotographic photosensitive member 1 to a recording paper (paper, medium) P. Is.

  There is no restriction | limiting in particular about the cleaning apparatus 6, Arbitrary cleaning apparatuses, such as a brush cleaner, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, can be used. The cleaning device 6 is for scraping off residual toner adhering to the photoreceptor 1 with a cleaning member and collecting the residual toner. However, when there is little or almost no toner remaining on the surface of the photoreceptor, the cleaning device 6 may be omitted.

When the toner transferred onto the recording paper P passes between the upper fixing member 71 and the lower fixing member 72 heated to a predetermined temperature, the toner is heated to a molten state and cooled after passing through the recording paper. Toner is fixed on P.
In the electrophotographic apparatus configured as described above, an image is recorded as follows. That is, first, the surface (photosensitive surface) of the photoreceptor 1 is charged to a predetermined potential (for example, −600 V) by the charging device 2. At this time, charging may be performed by a DC voltage, or charging may be performed by superimposing an AC voltage on the DC voltage.

Subsequently, the photosensitive surface of the charged photoreceptor 1 is exposed by the exposure device 3 according to the image to be recorded, and an electrostatic latent image is formed on the photosensitive surface. The developing device 4 develops the electrostatic latent image formed on the photosensitive surface of the photoreceptor 1.
The developing device 4 thins the toner T supplied by the supply roller 43 with a regulating member (developing blade) 45 and has a predetermined polarity (here, the same polarity as the charging potential of the photosensitive member 1) and the negative polarity. ), And conveyed while being carried on the developing roller 44 to be brought into contact with the surface of the photoreceptor 1.

When the charged toner T carried on the developing roller 44 comes into contact with the surface of the photoreceptor 1, a toner image corresponding to the electrostatic latent image is formed on the photosensitive surface of the photoreceptor 1. This toner image is transferred onto the recording paper P by the transfer device 5. Thereafter, the toner remaining on the photosensitive surface of the photoreceptor 1 without being transferred is removed by the cleaning device 6.
After the transfer of the toner image onto the recording paper P, the final image is obtained by passing the fixing device 7 and thermally fixing the toner image onto the recording paper P.

  In addition to the above-described configuration, the image forming apparatus may be configured to perform, for example, a static elimination process. The neutralization step is a step of neutralizing the electrophotographic photosensitive member by exposing the electrophotographic photosensitive member, and a fluorescent lamp, an LED, or the like is used as the neutralizing device. In addition, the light used in the static elimination process is often light having an exposure energy that is at least three times that of the exposure light.

The image forming apparatus may be further modified. For example, the image forming apparatus may be configured to perform a pre-exposure process, an auxiliary charging process, or the like, or may be configured to perform offset printing. A full-color tandem system configuration using toner may be used.
The electrophotographic photosensitive member 1 is combined with one or more of the charging device 2, the exposure device 3, the developing device 4, the transfer device 5, the cleaning device 6, and the fixing device 7 to form an integrated cartridge ( The electrophotographic photosensitive member cartridge may be configured to be detachable from a main body of an electrophotographic apparatus such as a copying machine or a laser beam printer.

Specific embodiments of the present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples unless it exceeds the gist.
[Production of ester oligomer]
Production Example 1 (Synthesis of ester oligomer (1))
Resorcinol (3.00 g), 1,1-bis (4-hydroxy-3, methylphenyl) ethane (13.20 g) (hereinafter referred to as BP-a) and diphenyl ether-4,4 were placed in a nitrogen-substituted 300 mL four-necked reaction vessel. '-Dicarboxylic acid chloride (16.08 g) was weighed and dissolved in dichloromethane (90 mL). Subsequently, a mixed solution of triethylamine (11.58 g) and dichloromethane (45 mL) was dropped into the reaction vessel cooled to 0 to 5 ° C. over 30 minutes. After stirring for 1 hour, demineralized water (100 mL) was added and stirred for 10 minutes. After stirring, the organic layer was separated, and this organic layer was washed twice with 0.1N hydrochloric acid (100 mL), and further washed twice with demineralized water (100 mL). Then, it concentrated and dried and obtained the ester oligomer (1) which has a phenol group in the molecule terminal.

Production Example 2 (Synthesis of ester oligomer (2))
Methylhydroquinone (3.00 g), BP-a (11.71 g) and diphenyl ether-4,4′-dicarboxylic acid chloride (14.26 g) are weighed in a nitrogen-substituted 300 mL four-necked reaction vessel and dissolved in dichloromethane (90 mL). Dissolved. Subsequently, a mixed solution of triethylamine (10.28 g) and dichloromethane (30 mL) was dropped into the reaction vessel cooled to 0 to 5 ° C. over 30 minutes. After stirring for 1 hour, demineralized water (100 mL) was added and stirred for 10 minutes. After stirring, the organic layer was separated, and this organic layer was washed twice with 0.1N hydrochloric acid (100 mL), and further washed twice with demineralized water (100 mL). Then, it concentrated and dried and obtained the ester oligomer (2) which has a phenol group at the molecule terminal.

Production Example 3 (Synthesis of ester oligomer (3))
BP-a (5.86 g) and diphenyl ether-4,4′-dicarboxylic acid chloride (14.29 g) were weighed in a 300 mL four-necked reaction vessel purged with nitrogen and dissolved in dichloromethane (60 mL). Subsequently, a mixed solution of triethylamine (5.14 g) and dichloromethane (40 mL) was dropped into the reaction vessel cooled to 0 to 5 ° C. over 30 minutes. After stirring for 30 minutes, BP-a (9.10 g) and hydroquinone (1.20 g) were added to the reaction vessel. Thereafter, a mixed solution of triethylamine (5.14 g) and dichloromethane (20 mL) was dropped into the reaction vessel over 30 minutes. After stirring for 1 hour, demineralized water (100 mL) was added and stirred for 10 minutes. After stirring, the organic layer was separated, and this organic layer was washed twice with 0.1N hydrochloric acid (100 mL), and further washed twice with demineralized water (100 mL). Then, it concentrated and dried and obtained the ester oligomer (3) which has a phenol group at the molecule terminal.

Production Example 4 (Synthesis of ester oligomer (4))
1,6-dihydroxynaphthalene (4.00 g), BP-a (12.10 g) and diphenyl ether-4,4′-dicarboxylic acid chloride (14.74 g) were weighed in a 300 mL four-necked reaction vessel purged with nitrogen, and dichloromethane. (80 mL). Subsequently, a mixed solution of triethylamine (10.62 g) and dichloromethane (45 mL) was dropped into a reaction vessel cooled to 0 to 5 ° C. over 30 minutes. After stirring for 1 hour, demineralized water (100 mL) was added and stirred for 10 minutes. After stirring, the organic layer was separated, and this organic layer was washed twice with 0.1N hydrochloric acid (100 mL), and further washed twice with demineralized water (100 mL). Then, it concentrated and dried and obtained the ester oligomer (4) which has a phenol group at the molecule terminal.

Production Example 5 (Synthesis of ester oligomer (5))
1,5-dihydroxynaphthalene (1.50 g), BP-a (12.86 g) and diphenyl ether-4,4′-dicarboxylic acid chloride (12.28 g) are weighed in a 300 mL four-necked reaction vessel purged with nitrogen, and dichloromethane. (80 mL). Subsequently, a mixed solution of triethylamine (8.84 g) and dichloromethane (40 mL) was dropped into the reaction vessel cooled to 0 to 5 ° C. over 30 minutes. After stirring for 1 hour, demineralized water (100 mL) was added and stirred for 10 minutes. After stirring, the organic layer was separated, and this organic layer was washed twice with 0.1N hydrochloric acid (100 mL), and further washed twice with demineralized water (100 mL). Then, it concentrated and dried and obtained the ester oligomer (5) which has a phenol group at the molecule terminal.

Production Example 6 (Synthesis of ester oligomer (6))
BP-a (7.00 g) and diphenyl ether-4,4′-dicarboxylic acid chloride (17.05 g) were weighed in a nitrogen-substituted 500 mL four-necked reaction vessel, and dichloromethane (1
60 mL). Subsequently, a mixed solution of triethylamine (6.14 g) and dichloromethane (20 mL) was dropped into a reaction vessel cooled to 0 to 5 ° C. over 20 minutes. After stirring for 5 minutes, BP-a (11.90 g) and 4-hydroxyphenyl 4-hydroxybenzoate (2.00 g) were added to the reaction vessel. Thereafter, a mixed solution of triethylamine (6.14 g) and dichloromethane (20 mL) was dropped into the reaction vessel over 20 minutes. After stirring for 1 hour, 0.1N hydrochloric acid (170 mL) was added and stirred for 30 minutes. After stirring, the organic layer was separated, and this organic layer was washed twice with 0.1N hydrochloric acid (170 mL), and further washed twice with demineralized water (170 mL). Then, it concentrated and dried and obtained the ester oligomer (6) which has a phenol group at the molecule terminal.

Production Example 7 (Synthesis of ester oligomer (7))
BP-a (18.54 g) and trans-1,4-cyclohexanedicarboxylic acid chloride (Ihara Nikkei Chemical Industries) (8.00 g) are weighed and dissolved in dichloromethane (160 mL) in a 500 mL four-necked reaction vessel purged with nitrogen. I let you. Subsequently, a mixed solution of triethylamine (8.52 g) and dichloromethane (30 mL) was dropped into the reaction vessel cooled to 0 to 5 ° C. over 30 minutes. After stirring for 1 hour, demineralized water (150 mL) was added and stirred for 10 minutes. After stirring, the organic layer was separated, and this organic layer was washed twice with 0.1N hydrochloric acid (150 mL), and further washed twice with demineralized water (150 mL). Then, it concentrated and dried and obtained the ester oligomer (7) which has a phenol group at the molecule terminal.

Production Example 8 (Synthesis of ester oligomer (8))
BP-a (17.31 g) and 1,4-phenylenediacetic acid dichloride (Ihara Nikkei Chemical Industries) (10.00 g) were weighed and dissolved in dichloromethane (150 mL) in a 500 mL four-necked reaction vessel purged with nitrogen. . Subsequently, a mixed solution of triethylamine (9.19 g) and dichloromethane (65 mL) was dropped into the reaction vessel cooled to 0 to 5 ° C. over 1 hour. After stirring for 1 hour, demineralized water (150 mL) was added and stirred for 10 minutes. After stirring, the organic layer was separated, and this organic layer was washed twice with 0.1N hydrochloric acid (150 mL), and further washed twice with demineralized water (150 mL). Then, it concentrated and dried and obtained the ester oligomer (8) which has a phenol group in the molecule terminal.

Production Example 9 (Synthesis of ester oligomer (9))
1,4-benzenedimethanol (3.00 g) and diphenyl ether-4,4′-dicarboxylic acid chloride (12.81 g) were weighed and dissolved in dichloromethane (130 mL) in a 500 mL four-necked reaction vessel purged with nitrogen. Subsequently, a mixed solution of triethylamine (4.61 g) and dichloromethane (20 mL) was dropped into the reaction vessel cooled to 0 to 5 ° C. over 30 minutes. After stirring for 2 hours, BP-a (10.52 g) was added to the reaction vessel. Thereafter, a mixed solution of triethylamine (4.61 g) and dichloromethane (20 mL) was dropped into the reaction vessel over 30 minutes. After stirring for 1 hour, demineralized water (150 mL) was added and stirred for 10 minutes. After stirring, the organic layer was separated, and this organic layer was washed twice with 0.1N hydrochloric acid (150 mL), and further washed twice with demineralized water (150 mL). Then, it concentrated and dried and obtained the ester oligomer (9) which has a phenol group at the molecule terminal.

Production Example 10 (Synthesis of ester oligomer (10))
Isosorbide (4.00 g) and terephthalic acid chloride (11.11 g) were weighed in a nitrogen-substituted 300 mL four-necked reaction vessel and dissolved in dichloromethane (90 mL). Subsequently, a mixed solution of triethylamine (5.82 g) and dichloromethane (26 mL) was dropped into the reaction vessel cooled to 0 to 5 ° C. over 30 minutes. After stirring for 3 hours, BP-a (13.26 g) was added to the reaction vessel. Thereafter, a mixed solution of triethylamine (5.82 g) and dichloromethane (20 mL) was dropped into the reaction vessel over 30 minutes. After stirring for 1 hour, demineralized water (100 mL) was added and stirred for 10 minutes. After stirring, the organic layer was separated, and this organic layer was washed twice with 0.1N hydrochloric acid (100 mL), and further washed twice with demineralized water (100 mL). Then, it concentrated and dried and obtained the ester oligomer (10) which has a phenol group in the molecule terminal.

Production Example 11 (Synthesis of ester oligomer (11))
4,4′-biphenyldimethanol (4.50 g) and diphenyl ether-4,4′-dicarboxylic acid chloride (12.04 g) were weighed in a 300 mL four-necked reaction vessel purged with nitrogen and dissolved in dichloromethane (120 mL). . Subsequently, a mixed solution of triethylamine (4.67 g) and dichloromethane (30 mL) was dropped into a reaction vessel cooled to 0 to 5 ° C. over 20 minutes. The temperature of the reaction vessel was raised to 20 ° C. and stirring was continued for 1 hour, and then BP-a (10.18 g) was added to the reaction vessel. After cooling the reaction vessel to 0 to 5 ° C., a mixed solution of triethylamine (4.67 g) and dichloromethane (30 mL) was dropped into the reaction vessel over 20 minutes. After stirring for 1 hour, 0.1N hydrochloric acid (150 mL) was added and stirred for 30 minutes. After stirring, the organic layer was separated, and this organic layer was washed twice with 0.1N hydrochloric acid (150 mL), and further washed twice with demineralized water (150 mL). Then, it concentrated and dried and obtained the ester oligomer (11) which has a phenol group at the molecule terminal.

Example 1 (Production of polyester resin (1))
Sodium hydroxide (1.57 g) and H ₂ O (188 ml) were weighed in a 500 mL beaker and dissolved with stirring. 2,3,5-trimethylphenol (0.21 g) and benzyltriethylammonium chloride (0.11 g) were added thereto and dissolved by stirring, and then the alkaline aqueous solution was transferred to a 1 L reaction vessel.

Separately, a mixed solution of the ester oligomer (1) synthesized in Production Example 1 (16.13 g) and diphenyl ether-4,4′-dicarboxylic acid chloride (4.87 g) and dichloromethane (107 mL) was transferred into the dropping funnel. .
While maintaining the external temperature of the reaction vessel at 20 ° C. and stirring the alkaline aqueous solution in the reaction vessel, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After stirring for another hour, dichloromethane (166 mL) was added and stirring was continued for 9 hours. Thereafter, stirring was stopped and the mixture was allowed to stand for 30 minutes, and then the organic layer was separated. This organic layer was washed 3 times with 0.1N hydrochloric acid (205 mL), and further washed twice with demineralized water (205 mL). Dichloromethane (100 ml) was added to the washed organic layer for dilution, and the precipitate obtained by pouring into methanol (1800 ml) was taken out by filtration and dried to obtain the desired polyester resin (1). The viscosity average molecular weight (Mv) of the obtained polyester resin was 44,200. The structural formula of the polyester resin (1) is shown below.

[Measurement of viscosity average molecular weight (Mv)]
The polyester resin was dissolved in dichloromethane to prepare a solution having a concentration C of 6.00 g / L. The flow time t of the sample solution was measured in a constant temperature water bath set at 20.0 ° C. using an Ubbelohde capillary viscometer with a flow time t ₀ of the solvent (dichloromethane) of 136.16 seconds. The viscosity average molecular weight (Mv) was calculated according to the following formula.
a = 0.438 × η _sp +1 η _sp = t / t ₀ −1
b = 100 × η _sp / C C = 6.00 (g / L)
η = b / a
Mv = 3207 × η ^1.205

Example 2 (Production of polyester resin (2))
Sodium hydroxide (1.55 g) and H ₂ O (188 ml) were weighed in a 500 mL beaker and dissolved with stirring. 2,3,5-trimethylphenol (0.21 g) and benzyltriethylammonium chloride (0.11 g) were added thereto and dissolved by stirring, and then the alkaline aqueous solution was transferred to a 1 L reaction vessel.

Separately, a mixed solution of the ester oligomer (2) synthesized in Production Example 2 (16.18 g) and diphenyl ether-4,4′-dicarboxylic acid chloride (4.81 g) and dichloromethane (107 mL) was transferred into the dropping funnel. .
While maintaining the external temperature of the reaction vessel at 20 ° C. and stirring the alkaline aqueous solution in the reaction vessel, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After stirring for another hour, dichloromethane (166 mL) was added and stirring was continued for 9 hours. Thereafter, stirring was stopped and the mixture was allowed to stand for 30 minutes, and then the organic layer was separated. This organic layer was washed 3 times with 0.1N hydrochloric acid (205 mL), and further washed twice with demineralized water (205 mL).

  Dichloromethane (100 ml) was added to the washed organic layer for dilution, and the precipitate obtained by pouring into methanol (1800 ml) was removed by filtration and dried to obtain the desired polyester resin (2). The viscosity average molecular weight (Mv) of the obtained polyester resin was 54,200. The structural formula of the polyester resin (2) is shown below.

Example 3 (Production of polyester resin (3))
Sodium hydroxide (1.87 g) and H ₂ O (235 ml) were weighed in a 500 mL beaker and dissolved with stirring. 2,3,5-trimethylphenol (0.32 g) and benzyltriethylammonium chloride (0.14 g) were added thereto and dissolved by stirring, and then the alkaline aqueous solution was transferred to a 1 L reaction vessel.

Separately, a mixed solution of the ester oligomer (3) synthesized in Production Example 3 (20.33 g) and diphenyl ether-4,4′-dicarboxylic acid chloride (5.78 g) and dichloromethane (134 mL) was transferred into the dropping funnel. .
While maintaining the external temperature of the reaction vessel at 20 ° C. and stirring the alkaline aqueous solution in the reaction vessel, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 1 hour, dichloromethane (200 mL) was added and stirring was continued for 9 hours. Thereafter, stirring was stopped and the mixture was allowed to stand for 30 minutes, and then the organic layer was separated. This organic layer was washed three times with 0.1N hydrochloric acid (250 mL), and further washed twice with demineralized water (250 mL).

  Dichloromethane (150 ml) was added to the washed organic layer for dilution, and the precipitate obtained by pouring into methanol (2000 ml) was removed by filtration and dried to obtain the desired polyester resin (3). The resulting polyester resin had a viscosity average molecular weight (Mv) of 43,500. The structural formula of the polyester resin (3) is shown below.

Example 4 (Production of polyester resin (4))
Sodium hydroxide (1.52 g) and H ₂ O (188 ml) were weighed in a 500 mL beaker and dissolved with stirring. 2,3,5-Trimethylphenol (0.24 g) and benzyltriethylammonium chloride (0.11 g) were added thereto and dissolved by stirring, and then the alkaline aqueous solution was transferred to a 1 L reaction vessel.

Separately, a mixed solution of the ester oligomer (4) synthesized in Production Example 4 (16.22 g) and diphenyl ether-4,4′-dicarboxylic acid chloride (4.70 g) and dichloromethane (107 mL) was transferred into the dropping funnel. .
While maintaining the external temperature of the reaction vessel at 20 ° C. and stirring the alkaline aqueous solution in the reaction vessel, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 1 hour, dichloromethane (176 mL) was added and stirring was continued for 9 hours. Thereafter, stirring was stopped and the mixture was allowed to stand for 30 minutes, and then the organic layer was separated. This organic layer was washed 3 times with 0.1N hydrochloric acid (210 mL), and further washed twice with demineralized water (210 mL).

  Dichloromethane (100 ml) was added to the washed organic layer for dilution, and the precipitate obtained by pouring into methanol (1800 ml) was collected by filtration and dried to obtain the desired polyester resin (4). The resulting polyester resin had a viscosity average molecular weight (Mv) of 39,000. The structural formula of the polyester resin (4) is shown below.

Example 5 (Production of polyester resin (5))
Sodium hydroxide (1.47 g) and H ₂ O (188 ml) were weighed in a 500 mL beaker and dissolved with stirring. 2,3,5-trimethylphenol (0.25 g) and benzyltriethylammonium chloride (0.11 g) were added thereto and dissolved by stirring, and then the alkaline aqueous solution was transferred to a 1 L reaction vessel.

Separately, a mixed solution of the ester oligomer (5) (16.32 g) synthesized in Production Example 5 and diphenyl ether-4,4′-dicarboxylic acid chloride (4.56 g) and dichloromethane (107 mL) was transferred into the dropping funnel. .
While maintaining the external temperature of the reaction vessel at 20 ° C. and stirring the alkaline aqueous solution in the reaction vessel, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 1 hour, dichloromethane (176 mL) was added and stirring was continued for 9 hours. Thereafter, stirring was stopped and the mixture was allowed to stand for 30 minutes, and then the organic layer was separated. This organic layer was washed 3 times with 0.1N hydrochloric acid (210 mL), and further washed twice with demineralized water (210 mL).

  Dichloromethane (100 ml) was added to the washed organic layer for dilution, and the precipitate obtained by pouring into methanol (1800 ml) was removed by filtration and dried to obtain the desired polyester resin (5). The resulting polyester resin had a viscosity average molecular weight (Mv) of 41,300. The structural formula of the polyester resin (5) is shown below.

Example 6 (Production of polyester resin (6))
Sodium hydroxide (1.78 g) and H ₂ O (188 ml) were weighed in a 500 mL beaker and dissolved with stirring. 2,3,5-trimethylphenol (0.26 g) and benzyltriethylammonium chloride (0.08 g) were added thereto and dissolved by stirring, and then the alkaline aqueous solution was transferred to a 1 L reaction vessel.

Separately, a mixed solution of the ester oligomer (6) (20.57 g) synthesized in Production Example 6 and diphenyl ether-4,4′-dicarboxylic acid chloride (5.53 g) and dichloromethane (135 mL) was transferred into the dropping funnel. .
While maintaining the external temperature of the reaction vessel at 20 ° C. and stirring the alkaline aqueous solution in the reaction vessel, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 1 hour, dichloromethane (179 mL) was added and stirring was continued for 9 hours. Thereafter, stirring was stopped and the mixture was allowed to stand for 30 minutes, and then the organic layer was separated. This organic layer was washed with 0.1N hydrochloric acid (235 mL) three times, and further washed twice with demineralized water (235 mL).

  Dichloromethane (180 ml) was added to the washed organic layer for dilution, and the precipitate obtained by pouring into methanol (2000 ml) was collected by filtration and dried to obtain the desired polyester resin (6). The resulting polyester resin had a viscosity average molecular weight (Mv) of 51,000. The structural formula of the polyester resin (6) is shown below.

Example 7 (Production of polyester resin (7))
Sodium hydroxide (2.31 g) and H ₂ O (188 ml) were weighed in a 500 mL beaker and dissolved with stirring. 2,3,5-trimethylphenol (0.25 g) and benzyltriethylammonium chloride (0.17 g) were added thereto and dissolved by stirring, and then the alkaline aqueous solution was transferred to a 1 L reaction vessel.

Separately, a mixed solution of the ester oligomer (7) synthesized in Production Example 7 (14.37 g) and diphenyl ether-4,4′-dicarboxylic acid chloride (7.16 g) and dichloromethane (107 mL) was transferred into the dropping funnel. .
While maintaining the external temperature of the reaction vessel at 20 ° C. and stirring the alkaline aqueous solution in the reaction vessel, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 1 hour, dichloromethane (160 mL) was added and stirring was continued for 9 hours. Thereafter, stirring was stopped and the mixture was allowed to stand for 30 minutes, and then the organic layer was separated. This organic layer was washed with 0.1 N hydrochloric acid (200 mL) three times, and further washed with demineralized water (200 mL) twice.

  Dichloromethane (100 ml) was added to the washed organic layer for dilution, and the precipitate obtained by pouring into methanol (1800 ml) was removed by filtration and dried to obtain the desired polyester resin (7). The resulting polyester resin had a viscosity average molecular weight (Mv) of 35,300. The structural formula of the polyester resin (7) is shown below.

Example 8 (Production of polyester resin (8))
Sodium hydroxide (2.26 g) and H ₂ O (188 ml) were weighed in a 500 mL beaker and dissolved with stirring. 2,3,5-trimethylphenol (0.25 g) and benzyltriethylammonium chloride (0.17 g) were added thereto and dissolved by stirring, and then the alkaline aqueous solution was transferred to a 1 L reaction vessel.

Separately, a mixed solution of the ester oligomer (8) synthesized in Production Example 8 (14.50 g) and diphenyl ether-4,4′-dicarboxylic acid chloride (6.99 g) and dichloromethane (107 mL) was transferred into the dropping funnel. .
While maintaining the external temperature of the reaction vessel at 20 ° C. and stirring the alkaline aqueous solution in the reaction vessel, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 1 hour, dichloromethane (160 mL) was added and stirring was continued for 9 hours. Thereafter, stirring was stopped and the mixture was allowed to stand for 30 minutes, and then the organic layer was separated. This organic layer was washed with 0.1 N hydrochloric acid (200 mL) three times, and further washed with demineralized water (200 mL) twice.

  Dichloromethane (100 ml) was added to the washed organic layer for dilution, and the precipitate obtained by pouring into methanol (1800 ml) was removed by filtration and dried to obtain the desired polyester resin (8). The resulting polyester resin had a viscosity average molecular weight (Mv) of 20,200. The structural formula of the polyester resin (8) is shown below.

Example 9 (Production of polyester resin (9))
Sodium hydroxide (2.72 g) and H ₂ O (188 ml) were weighed in a 500 mL beaker and dissolved with stirring. BP-a (4.64 g), 2,3,5-trimethylphenol (0.26 g), and benzyltriethylammonium chloride (0.20 g) were added thereto and dissolved by stirring. Moved to the tank.

Separately, a mixed solution of the ester oligomer (9) (8.76 g) synthesized in Production Example 9 and diphenyl ether-4,4′-dicarboxylic acid chloride (8.43 g) and dichloromethane (107 mL) was transferred into the dropping funnel. .
While maintaining the external temperature of the reaction vessel at 20 ° C. and stirring the alkaline aqueous solution in the reaction vessel, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 1 hour, dichloromethane (160 mL) was added and stirring was continued for 9 hours. Thereafter, stirring was stopped and the mixture was allowed to stand for 30 minutes, and then the organic layer was separated. This organic layer was washed with 0.1 N hydrochloric acid (200 mL) three times, and further washed with demineralized water (200 mL) twice.

  Dichloromethane (100 ml) was added to the washed organic layer for dilution, and the precipitate obtained by pouring into methanol (1800 ml) was collected by filtration and dried to obtain the desired polyester resin (9). The viscosity average molecular weight (Mv) of the obtained polyester resin was 33,200. The structural formula of the polyester resin (9) is shown below.

Example 10 (Production of polyester resin (10))
Sodium hydroxide (1.77 g) and H ₂ O (188 ml) were weighed in a 500 mL beaker and dissolved with stirring. 2,3,5-trimethylphenol (0.25g)
, And benzyltriethylammonium chloride (0.13 g) were added and dissolved by stirring, and the aqueous alkaline solution was transferred to a 1 L reaction vessel.

Separately, a mixed solution of the ester oligomer (10) synthesized in Production 10 (15.62 g) and diphenyl ether-4,4′-dicarboxylic acid chloride (5.50 g) and dichloromethane (107 mL) was transferred into a dropping funnel.
While maintaining the external temperature of the reaction vessel at 20 ° C. and stirring the alkaline aqueous solution in the reaction vessel, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 1 hour, dichloromethane (143 mL) was added and stirring was continued for 9 hours. Thereafter, stirring was stopped and the mixture was allowed to stand for 30 minutes, and then the organic layer was separated. This organic layer was washed with 0.1 N hydrochloric acid (190 mL) three times, and further washed with demineralized water (190 mL) twice.

  Dichloromethane (100 ml) was added to the washed organic layer for dilution, and the precipitate obtained by pouring into methanol (1800 ml) was collected by filtration and dried to obtain the desired polyester resin (10). The viscosity average molecular weight (Mv) of the obtained polyester resin was 22,500. The structural formula of the polyester resin (10) is shown below.

Example 11 (Production of polyester resin (11))
Sodium hydroxide (1.45 g) and H ₂ O (188 ml) were weighed in a 500 mL beaker and dissolved with stirring. 2,3,5-Trimethylphenol (0.20 g) and benzyltriethylammonium chloride (0.07 g) were added thereto and dissolved by stirring, and then the alkaline aqueous solution was transferred to a 1 L reaction vessel.

Separately, a mixed solution of the ester oligomer (11) synthesized in Production 11 (16.42 g) and diphenyl ether-4,4′-dicarboxylic acid chloride (4.62 g) and dichloromethane (94 mL) was transferred into the dropping funnel.
While maintaining the external temperature of the reaction vessel at 20 ° C. and stirring the alkaline aqueous solution in the reaction vessel, the dichloromethane solution was dropped from the dropping funnel over 1 hour. Stirring was continued for another hour, then dichloromethane (156 mL) was added and stirring was continued for 9 hours. Thereafter, stirring was stopped and the mixture was allowed to stand for 30 minutes, and then the organic layer was separated. This organic layer was washed with 0.1 N hydrochloric acid (190 mL) three times, and further washed with demineralized water (190 mL) twice.

  Dichloromethane (100 ml) was added to the washed organic layer for dilution, and the precipitate obtained by pouring into methanol (1800 ml) was collected by filtration and dried to obtain the desired polyester resin (11). The viscosity average molecular weight (Mv) of the obtained polyester resin was 40,200. The structural formula of the polyester resin (11) is shown below.

Example 12 (Production of polyester polycarbonate resin (12))
Sodium hydroxide (4.16 g) and H ₂ O (234 ml) were weighed in a 500 mL beaker and dissolved with stirring. 2,3,5-trimethylphenol (0.34 g), BP-a (10.15 g), and benzyltriethylammonium chloride (0.11 g) were added thereto and dissolved by stirring. Moved to the tank.

Separately, polycarbonate resin (Mv 26,000, terminal OH amount 63.8 μeq / g) produced by the melt polymerization method described in Production Example 1 of JP2012-185206A (4.81 g) A mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (12.86 g) and dichloromethane (117 mL) was transferred into the dropping funnel.
While maintaining the external temperature of the reaction vessel at 20 ° C. and stirring the alkaline aqueous solution in the reaction vessel, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 1 hour, dichloromethane (195 mL) was added and stirring was continued for 9 hours. Thereafter, stirring was stopped and the mixture was allowed to stand for 30 minutes, and then the organic layer was separated. This organic layer was washed with 0.1N hydrochloric acid (235 mL) three times, and further washed twice with demineralized water (235 mL).

  Dichloromethane (150 ml) was added to the washed organic layer for dilution, and the precipitate obtained by pouring into methanol (2300 ml) was collected by filtration and dried to obtain the desired polyester polycarbonate resin (12). The viscosity average molecular weight (Mv) of the obtained polyester resin was 40,100. The structural formula of the polyester resin (12) is shown below.

Comparative Example 1 (Production by interfacial polymerization of polyester resin (3))
Sodium hydroxide (4.23 g) and H ₂ O (188 ml) were weighed in a 500 mL beaker and dissolved with stirring. 2,3,5-trimethylphenol (0.26 g), BP-a (10.15 g), hydroquinone (0.47 g), and benzyltriethylammonium chloride (0.12 g) were added and dissolved with stirring. The aqueous alkaline solution was transferred to a 1 L reaction vessel.

Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (13.08 g) and dichloromethane (94 mL) was transferred into the dropping funnel.
While maintaining the external temperature of the reaction vessel at 20 ° C. and stirring the alkaline aqueous solution in the reaction vessel, the dichloromethane solution was dropped from the dropping funnel over 1 hour. Stirring was continued for another hour, then dichloromethane (156 mL) was added and stirring was continued for 9 hours. However, hydroquinone was oxidized during the polymerization and the water layer turned brown, and the divalent phenol was insufficient, so that a sufficiently elongated polymer could not be obtained.

Comparative Example 2 (Production by Interfacial Polymerization of Polyester Resin (6))
Sodium hydroxide (4.13 g) and H ₂ O (188 ml) were weighed and dissolved in a 500 mL beaker while stirring. 2,3,5-trimethylphenol (0.26 g), BP-a (9.16 g), 4-hydroxybenzoic acid 4-hydroxyphenyl ether (0.97 g), and benzyltriethylammonium chloride (0.12 g) ) Was added and dissolved by stirring, and the aqueous alkaline solution was transferred to a 1 L reaction vessel.

Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (12.75 g) and dichloromethane (94 mL) was transferred into the dropping funnel.
While maintaining the external temperature of the reaction vessel at 20 ° C. and stirring the alkaline aqueous solution in the reaction vessel, the dichloromethane solution was dropped from the dropping funnel over 1 hour. Stirring was continued for another hour, then dichloromethane (156 mL) was added and stirring was continued for 9 hours. However, 4-hydroxybenzoic acid 4-hydroxyphenyl ether is hydrolyzed during the polymerization, becomes hydroquinone, is oxidized, the water layer turns brown, and there is not enough divalent phenol, resulting in a sufficiently elongated polymer. There wasn't.

Comparative Example 3 (Production by Interfacial Polymerization of Polyester Resin (11))
Sodium hydroxide (4.14 g) and H ₂ O (188 ml) were weighed in a 500 mL beaker and dissolved with stirring. 2,3,5-trimethylphenol (0.26 g), BP-a (6.93 g), 4,4′-biphenyldimethanol (3.02 g), and benzyltriethylammonium chloride (0.12 g) After adding and dissolving with stirring, the aqueous alkaline solution was transferred to a 1 L reaction vessel.

Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (12.97 g) and dichloromethane (94 mL) was transferred into the dropping funnel.
While maintaining the external temperature of the reaction vessel at 20 ° C. and stirring the alkaline aqueous solution in the reaction vessel, the dichloromethane solution was dropped from the dropping funnel over 1 hour. Stirring was continued for another hour, then dichloromethane (156 mL) was added and stirring was continued for 9 hours. However, since the hydroxyl group of 4,4′-biphenyldimethanol has poor reactivity, a sufficiently elongated polymer could not be obtained.

<Preparation of photoreceptor sheet>
[Example 13]
10 parts by mass of oxytitanium phthalocyanine and 150 parts by mass of 4-methoxy-4-methyl-2-pentanone were mixed and pulverized and dispersed in a sand grind mill to produce a pigment dispersion. Oxytitanium phthalocyanine has Bragg angles (2θ ± 0.2) of 9.3 °, 10.6 °, 13.2 °, 15.1 °, 15.7 °, 16.5 ° in X-ray diffraction by CuKα ray. Strong diffraction peaks are shown at 1 °, 20.8 °, 23.3 °, 26.3 °, and 27.1 °.

  To this pigment dispersion, 50 parts by mass of a 5% by weight 1,2-dimethoxyethane solution of polyvinyl butyral (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name Denkabutyral # 6000C), phenoxy resin (manufactured by Union Carbide Co., Ltd., trade name) 50 parts by mass of a 5% by mass 1,2-dimethoxyethane solution of PKHH) and then adding an appropriate amount of 1,2-dimethoxyethane to prepare a coating solution for forming a charge generation layer having a solid content concentration of 4.0% did. This charge generation layer forming coating solution was applied on a polyethylene terephthalate sheet having aluminum deposited on the surface so that the film thickness after drying was 0.4 μm and dried to provide a charge generation layer.

  Next, as a charge transport material, a mixture (CTM-1) produced by the method described in Example 1 of JP-A-2002-080432, which comprises a group of geometric isomers having a structure shown below as a main component. ) 100 parts by mass of the polyester resin (1) produced in Example 1, 8 parts by mass of an antioxidant (Irganox 1076), 0.05 parts by mass of silicone oil as a leveling agent, tetrahydrofuran and toluene Was mixed with 640 parts by mass of a mixed solvent (80% by mass of tetrahydrofuran, 20% by mass of toluene) to prepare a coating solution for forming a charge transport layer.

This charge transport layer forming coating solution is applied onto the above-described charge generation layer using an applicator so that the film thickness after drying is 25 μm, and dried at 125 ° C. for 20 minutes to form a charge transport layer. A photoreceptor sheet was prepared.
[Example 14]
A photoreceptor sheet was produced in the same manner as in Example 1 except that the polyester resin (1) was changed to the polyester resin (2).

[Example 15]
A photoreceptor sheet was produced in the same manner as in Example 1 except that the polyester resin (1) was changed to the polyester resin (3).
[Example 16]
A photoreceptor sheet was produced in the same manner as in Example 1 except that the polyester resin (1) was changed to the polyester resin (4).

[Example 17]
A photoreceptor sheet was produced in the same manner as in Example 1 except that the polyester resin (1) was changed to the polyester resin (5).
[Example 18]
A photoreceptor sheet was produced in the same manner as in Example 1 except that the polyester resin (1) was changed to the polyester resin (6).

[Example 19]
A photoreceptor sheet was produced in the same manner as in Example 1 except that the polyester resin (1) was changed to the polyester resin (7).
[Example 20]
A photoreceptor sheet was produced in the same manner as in Example 1 except that the polyester resin (1) was changed to the polyester resin (8).

[Example 21]
A photoreceptor sheet was produced in the same manner as in Example 1 except that the polyester resin (1) was changed to the polyester resin (9).
[Example 22]
A photoreceptor sheet was produced in the same manner as in Example 1 except that the polyester resin (1) was changed to the polyester resin (10).

[Example 23]
A photoreceptor sheet was produced in the same manner as in Example 1 except that the polyester resin (1) was changed to the polyester resin (11).
[Example 24]
A photoreceptor sheet was produced in the same manner as in Example 1 except that the polyester resin (1) was changed to the polyester resin (12).

[Reference Example 1]
The polyester resin (1) was prepared by the method described in Example 6 of JP-A-2006-53549, and the polyester resin (14) having the structure shown below (14) (viscosity average molecular weight 36,200) was used except that the polyester resin (1) was changed. In the same manner as in No. 1, a photoreceptor sheet was produced.

[Electrical characteristics evaluation]
Using an electrophotographic characteristic evaluation apparatus (basic and applied electrophotographic technology, edited by the Electrophotographic Society, Corona, pages 404-405) prepared according to the Electrophotographic Society measurement standard, the photoconductor is made into an aluminum drum. Attached to a cylindrical shape, the aluminum drum and the aluminum base of the photoconductor are connected, and then the drum is rotated at a constant rotational speed, and an electrical property evaluation test is performed by a cycle of charging, exposure, potential measurement, and static elimination. went. At that time, the initial surface potential was set to −700 V, the exposure was performed at 780 nm, and the charge removal was performed at 660 nm. The surface potential (VL) at the time when the exposure light was irradiated by 2.4 μJ / cm 2 was measured. In the VL measurement, the time required from the exposure to the potential measurement was 139 ms. The irradiation energy (half exposure energy: μJ / cm ² ) when the surface potential was half of the initial surface potential (−350 V) was measured as sensitivity (E _1/2 ). The smaller the absolute value of the VL value, the better the electrical characteristics, and the smaller the E _1/2 value, the higher the sensitivity. The measurement environment was 25 ° C. and 50% relative humidity (N / N). The results are shown in Table-1.

[Abrasion test]
The photoreceptor film was cut into a circle having a diameter of 10 cm, and the wear was evaluated by a Taber abrasion tester (manufactured by Toyo Seiki Co., Ltd.). The test conditions were measured by comparing the mass before and after the test after 1000 rotations under a load of 500 g using a wear wheel CS-10F in an atmosphere of 25 ° C. and 50% RH. The results are shown in Table-2.

  From the above, it has been clarified that it is possible to produce a polyester resin into which a dihydric phenol having a problem of being easily oxidized or easily hydrolyzed by the present invention or a dihydric alcohol having poor reactivity is introduced. It has also been clarified that this method can produce a high molecular weight polyester resin required for a photoreceptor. It was also clarified that the polyester polycarbonate resin can be easily produced. Furthermore, it has been clarified that the photoreceptor provided from the polyester resin produced according to the present invention has good electrical properties and good properties such as wear resistance.

1 Photoconductor 2 Charging device (charging roller)
DESCRIPTION OF SYMBOLS 3 Exposure apparatus 4 Developing apparatus 5 Transfer apparatus 6 Cleaning apparatus 7 Fixing apparatus 41 Developing tank 42 Agitator 43 Supply roller 44 Developing roller 45 Control member 71 Upper fixing member (pressure roller)
72 Lower fixing member (fixing roller)
73 Heating device T Toner P Recording paper

Claims (9)

A method for producing a polyester resin, which comprises using at least one ester oligomer as a raw material. The method for producing a polyester resin according to claim 1, wherein the ester oligomer is obtained by a solution polymerization method or a melt polymerization method. The method for producing a polyester resin according to claim 1, wherein polymerization is performed by an interfacial polymerization method using at least one ester oligomer as a raw material. The method for producing a polyester according to any one of claims 1 to 3, wherein at least two kinds of dicarboxylic acid chlorides are used. The polyester production method according to any one of claims 1 to 4, wherein at least two kinds of dihydric phenols or dihydric alcohols are used. The polyester production method according to any one of claims 1 to 4, wherein the polyester resin is polymerized so that a viscosity average molecular weight is 15,000 to 100,000. A method for producing a polyester polycarbonate resin, which comprises polymerizing by an interfacial polymerization method using at least one carbonate oligomer or polycarbonate resin produced by a melt polymerization method as a raw material. The method for producing a polyester polycarbonate resin according to claim 7, wherein the polyester polycarbonate resin is polymerized so that the viscosity average molecular weight is 30,000 to 150,000. An electrophotographic photosensitive member having at least a photosensitive layer on a conductive support, wherein the photosensitive layer contains a polyester resin or a polyester polycarbonate resin produced by the production method according to claim 1. An electrophotographic photoreceptor characterized by the above.

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