JPH1081737A - Resin composition, its production, coated membrane by using the same and electronic photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition excellent in transparency, solubility in a solvent and especially abrasion resistance, and to provide a method for producing the composition, a membrane coated by the composition or an electronic photosensitive material. SOLUTION: This resin composition comprises (A) 5-70wt.% aromatic polyester part composed of a condensation polymerization part consisting essentially of an aromatic dicarboxylic acid residue and an aromatic diol residue, (B) 10-75wt.% polyester part composed of a condensation polymerization part consisting essentitaly of the aromatic dicarboxylic acid residue or an aliphatic carboxylic acid residue, and an aliphatic diol residue and (C) 20-85wt.% polycarbonate part composed of a condensation polymerization part consisting essentially of the aromatic dicarboxylic acid residue and carbonate residue and each part thereof is chemically bonded to each other. The resin composition has 2,000-200,000 number average molecular weight (Mn).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition, a method for producing the same, and a coating film or an electrophotographic photosensitive member using the same.
The present invention relates to a resin composition comprising an aromatic polyester-polyester-polycarbonate copolymer having excellent transparency and excellent solvent solubility, a method for producing the same, and a coating film or an electrophotographic photoreceptor using the same.

[0002]

2. Description of the Related Art In recent years, resins for coating films having transparency and abrasion resistance have been used in various applications such as electric, electronic and mechanical fields. 2. Description of the Related Art Coating the surface of a material including a metal with a resin is widely performed. As the method, there are a method in which a resin is melted by heat to coat a material, and a method in which a resin is dissolved in a solvent to form a solution, and then applied to the material and dried. The method of melting the resin by heat and coating the material is limited to the thermoplastic resin, and it is difficult to control the film thickness of the resin and the deterioration of the resin, including decomposition by heat, and to add additives. . On the other hand, a method in which a resin is dissolved in a solvent to form a solution, and then applied to a material and dried, is a widely used method because it is easy to control the film thickness and to add an additive. Transparency and abrasion-resistant coating film resins used in the fields of electricity, electronics, and machinery have high utility and various studies have been conducted.

[0003] In particular, the resin for a coating film is widely used as a binder resin for an organic photoreceptor. It is known that an organic photoreceptor has good processability as an electrophotographic photoreceptor, is advantageous in terms of manufacturing cost, and has a large degree of freedom in functional design. This organic photoreceptor usually has a photosensitive layer formed on a conductive substrate, and the photosensitive layer includes a charge generation material that generates charges by light irradiation, a charge transfer material that transfers generated charges, and a binder resin. A single-layer photosensitive layer containing a charge-generating layer, a charge-generating layer having a charge-generating material and a binder resin, and a charge-transferring layer having a charge-transporting material and a binder resin are known. Have been.

On the other hand, in the electrophotographic process, since the corona charging, development with toner, transfer and cleaning steps are repeatedly performed, the photosensitive layer is resistant to abrasion and abrasion against light, electric and mechanical action. It is required that the photosensitive properties, the charging properties, and the like do not deteriorate even when repeatedly used in various environments.
Copiers and printers using this organic photoreceptor are increasing year by year. It has sensitivity over a wide range of wavelengths from 400 to 800 nm, has higher sensitivity than inorganic photoreceptors, and has a low manufacturing cost. However, when the mechanical durability of the a-Si and a-Se-based photoconductors of the inorganic photoconductors is compared with each other, the photoconductors are liable to be worn, and the sensitivity is reduced. It is no exaggeration to say that the abrasion resistance and the abrasion resistance are almost determined by the choice of the binder resin, but at present, the friction resistance is limited in practical use.

As a method for improving the abrasion resistance of the electrophotographic photosensitive member, various olefin-based and engineering plastic-based binder resins have been studied, and some of them have been tried by blending different resins. As other methods, a binder resin having abrasion-resistant silicon resin or fluororesin dispersed therein, heat, using a photocurable resin,
Various studies have been made, such as an electrophotographic photosensitive member having a protective layer as the outermost layer, a charge transfer layer divided into two layers, and a resin having wear resistance being used as the outermost layer. However,
Conventionally known electrophotographic photoreceptors have not been sufficiently satisfactory, such as inferior electrical properties, even if the abrasion resistance is improved.

Further, various olefin-based and engineering plastic-based binder resins have been studied, and it is known that bisphenol A-type polycarbonate exhibits excellent properties in terms of abrasion resistance, charging characteristics, sensitivity, residual potential and the like. I have.
However, bisphenol A-type polycarbonate has a drawback that the solution tends to gel because the polymer has high crystallinity and becomes unusable in about 1 to 4 days. In addition, when a film is formed by coating, crystalline polycarbonate is precipitated on the film surface during the formation of a coating film, and a convex portion is easily generated, toner adheres, and an image defect due to poor cleaning is easily generated. Therefore, bisphenol Z-type polycarbonates with suppressed crystallinity were studied, and the solution became less likely to gel. However, at present, the speed of copiers and printers is increasing, and the abrasion resistance of polycarbonate is not satisfactory.

For example, Japanese Patent Application Laid-Open No. 5-34 discloses a method in which different resins are blended and used as a binder resin.
951 discloses a blend of bisphenol Z-type polycarbonate and etherimide or urethane or polyarylate, JP-A-6-273948 discloses a blend of polycarbonate and polyester, and JP-A-6-289629 discloses a polycarbonate and polyester. A blend of polyester and polyarylate, JP-A-1-282558 discloses a blend of polycarbonate and polyester, and JP-A-57-40.
No. 51 discloses a blend of polycarbonate and a polystyrene-acrylate ester.
No. 293548 discloses the use of a blend of polystyrene-acrylonitrile and polyphenylene oxide as a binder resin.
However, these blend-based binder resins have limited coating solvents, and have different compatibility between the resin and the solvent, so that phase separation occurs when left for a long time, and the stability of the coating solution can be said to be sufficient. Did not.

Japanese Patent Application Laid-Open No. 63-65449 discloses that
It is disclosed to use a dispersion of a silicone resin or a fluorine resin having abrasion resistance in a binder resin.
However, these resins have poor compatibility with the charge transfer agent and the binder resin, cause opacity of the charge transfer layer, cause uneven light transmittance in the opaque portion, and cause background contamination due to uneven sensitivity. Have a point.

Japanese Patent Application Laid-Open No. Sho 58-17448 discloses that a thermosetting resin such as urethane or epoxy is used as a binder resin. Japanese Patent Application Laid-Open No. 5-40358 discloses that epoxy is photocured and used as a binder resin. It is disclosed for use. And Japanese Patent Laid-Open No. Hei 4-2066
No. 51 discloses that an acrylic polymerizable monomer is photocured from a photoinitiator and used as a binder resin. However, there are problems such as the reaction deterioration of the charge generating agent and the charge transfer agent at the time of curing, and by-products such as unreacted functional groups and polymerization initiators remaining as impurities, leading to deterioration of electric characteristics. JP-A-1-172951, JP-A-2-158746, and JP-A-5-216249 disclose that a protective layer is provided on the outermost layer of an electrophotographic photosensitive member to improve abrasion resistance. Also, Japanese Patent Laid-Open No. 5-7
No. 2751 discloses a method in which a charge transfer layer is divided into two layers and a resin having wear resistance is used for the outermost layer.
However, the protective layer or the charge transfer layer provided with the outermost layer divided into two layers is considered to be caused by unstable charging due to disorder of the interface between layers, accumulation of residual potential due to continuous repetition, and scratches. There is a problem that white streaks and black streaks are easily generated.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an aromatic polyester-polyester-polycarbonate resin composition having excellent transparency, excellent solvent solubility, and particularly excellent wear resistance, and a method for producing the same. In addition, using the aromatic polyester-polyester-polycarbonate-based resin composition as a coating film or a binder resin of a photosensitive layer, to solve the above problems,
An object of the present invention is to provide a practically excellent electrophotographic photosensitive member that maintains excellent transparency, solvent solubility and abrasion resistance for a long time.

[0011]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that aromatic polyester-polyester-polycarbonate resin compositions have improved transparency, solvent solubility and resistance to solvent. It is excellent in abrasion, and it is suitable as a paint or a binder resin of an electrophotographic photoreceptor, and it has been found that a paint or an electrophotographic photoreceptor using the same is excellent in abrasion resistance. It was completed.

That is, the present invention relates to an aromatic polyester part (A) comprising a polycondensation part containing an aromatic dicarboxylic acid residue and an aromatic diol residue as main components, in an amount of 5 to 70% by weight.
10 to 75% by weight of a polyester part (B) composed of an aromatic dicarboxylic acid residue or a polycondensation part having an aliphatic dicarboxylic acid residue and an aliphatic diol residue as main components, and an aromatic dicarboxylic acid residue. 20 to 85% by weight of a polycarbonate part (C) composed of a condensation polymerization part having a group and a carbonic acid residue as main components, and these parts are chemically bonded and have a number average molecular weight (Mn). 2,000-200,
000, the elongation percentage at the time of tensile break according to ASTM D638 is 50% or more, and the coating film having a thickness of 15 μm is 400 to 800 nm.
The light transmittance in the region is 70% or more, and the solubility in chloroform or methylene chloride at 25 ° C. is 10 g.
/ 100 ml or more.

[0013] The present invention also provides an aromatic polyester resin composed of 5 to 70% by weight of an aromatic polyester resin composed of a condensation polymerization part containing an aromatic dicarboxylic acid residue and an aromatic diol residue as main components; Alternatively, 10 to 75% by weight of a polyester resin composed of a condensation polymerization part mainly containing an aliphatic dicarboxylic acid residue and an aliphatic diol residue, and a condensation resin mainly containing an aromatic dicarboxylic acid residue and a carbonate residue. 20 to 85% by weight of a polycarbonate resin composed of a polymerized part is melt-kneaded in the presence or absence of an ester polymerization catalyst until the phase becomes one phase, the method for producing the above resin composition, It is.

Further, the present invention is a coating film formed from the above resin composition, wherein the light transmittance is 15 μm thick and 70% or more in a 400 to 800 nm region.

Further, the present invention is an electrophotographic photosensitive member having a photosensitive layer on a conductive substrate, wherein the photosensitive layer contains the above resin composition as a binder resin.

Hereinafter, the resin composition of the present invention will be described. The resin composition of the present invention basically comprises an aromatic polyester part (A), a polyester part (B), and a polycarbonate part (C), and these parts are chemically bonded, and It has specific physical properties described in detail below.

First, the aromatic polyester portion (A) is composed of a condensation polymerization portion (ester bond) containing an aromatic dicarboxylic acid residue and an aromatic diol residue as main components.

Examples of the aromatic dicarboxylic acid compound as a raw material of the aromatic dicarboxylic acid residue include terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid,
2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenic acid, and the like (including derivatives such as acid anhydrides and acid halides; the same applies hereinafter). You may mix and use more than one type. Among them, 25/7 of terephthalic acid and isophthalic acid
A mixture of 5 to 75/25 is preferred.

As an example of an aromatic diol compound serving as a raw material of the aromatic diol residue, 2,2'-bis (4-
Hydroxyphenyl) propane (hereinafter abbreviated as “bisphenol A”), 4,4 ′-(1-methyl-ethylidene) bis (2-methylphenol) (hereinafter abbreviated as “bisphenol C”), 4,4′- Cyclohexylidene bisphenol (hereinafter abbreviated as “bisphenol Z”), 4,4′-ethylidene bisphenol, 4, 4 ′
-Methylidenebis (2,6-dimethylphenol),
4,4 '-(1,3-dimethylbutylidene) bisphenol, 4,4'-(1-methylethylidene) bis (2,
6-dimethylphenol), 4,4 ′-(1-phenylethylidene) bisphenol, 5,5 ′-(1-methylethylidene) (1,1′-biphenyl) -2-ol,
(1,1′-biphenyl) -4,4′-diol,
4'-methylenebisphenol, 4,4'-methylenebis (2-methylphenol), 4,4 '-(1-methyl-propylidene) bisphenol, 4,4'-(2-methyl-propylidene) bisphenol, 4,4 -(Phenylmethylene) bisphenol, 4,4'-cyclohexylidenebis (3-methylphenol), 4,4'-
(9H-fluoren-9-ylidene) bisphenol,
5,5 ′-(1,1′-cyclohexylidene) bis (1,1′-biphenyl) -2-ol, 4,4′-oxybisphenol, bis (4-hydroxy-phenyl) methanone, 4,4 '-(Diphenyl-methylene) bisphenol, 4,4'-propylidenebisphenol, 4,4'-(1-ethylethylidene) bisphenol, 4,4 '-(3-methylbutylidene) bisphenol, 4,4'- Cyclopentylidenebisphenol,
4,4'-cyclopentylidenebis (2-methylphenol), 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxy) Phenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-chloro-4-hydroxyphenyl)
Propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (4-hydroxyphenyl) propane, 4,4 -Biphenol, 3,3 ', 5,5'-
Tetramethyl-4,4'-dihydroxybiphenyl,
Aromatic diols such as 4,4'-dihydroxybenzophenone may be used, and these may be used alone or 2
More than one type may be used in combination. In particular, bisphenol A,
Bisphenol C and bisphenol Z are preferably used.

The polyester part (B) is composed of a condensation polymerization part (ester bond) containing an aromatic dicarboxylic acid residue or an aliphatic dicarboxylic acid residue and an aliphatic diol residue as main components.

Examples of the aliphatic dicarboxylic acid compound serving as a raw material for the aliphatic dicarboxylic acid residue include adipic acid,
Bimelic acid, sebacic acid, malonic acid, succinic acid, malic acid, aliphatic dicarboxylic acids such as citric acid and the like,
These may be used alone or in combination of two or more.

Examples of the aromatic dicarboxylic acid compound as a raw material of the aromatic dicarboxylic acid residue include terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid,
Examples thereof include 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and diphenic acid. These may be used alone or in combination of two or more.
Among them, terephthalic acid is preferably used. The aromatic dicarboxylic acid and the aliphatic dicarboxylic acid may be either one or both.

Next, examples of the aliphatic diol compound serving as a raw material of the aliphatic diol residue include ethylene glycol, propylene glycol, 1,4-butanediol,
Examples thereof include aliphatic diols such as pentamethylene glycol and hydrogenated bisphenol A, and these may be used alone or in combination of two or more. In particular, ethylene glycol and 1,4-butanediol are preferably used.

The polycarbonate part (C) is composed of a condensation polymerization part (carbonate bond) having an aromatic diol residue and a carbonate residue as main components.

Examples of the aromatic diol compound serving as a raw material of the aromatic diol residue include bisphenol A, bisphenol C, bisphenol Z, 4,4′-ethylidenebisphenol, 4,4′-methylidenebis (2,
6-dimethylphenol), 4,4 '-(1,3-dimethylbutylidene) bisphenol, 4,4'-(1-methylethylidene) bis (2,6-dimethylphenol), 4,4 '-(1 -Phenylethylidene) bisphenol, 5,5 '-(1-methylethylidene) (1,
1′-biphenyl) -2-ol, (1,1′-bi-phenyl) -4,4′-diol, 4,4′-methylenebisphenol, 4,4′-methylenebis (2-methylphenol), , 4 '-(1-methyl-propylidene)
Bisphenol, 4,4 '-(2-methyl-propylidene) bisphenol, 4,4'-(phenylmethylene)
Bisphenol, 4,4'-cyclohexylidenebis (3-methylphenol), 4,4 '-(9H-fluoren-9-ylidene) bisphenol, 5,5'-
(1,1′-cyclohexylidene) bis (1,1′-biphenyl) -2-ol, 4,4′-oxybisphenol, bis (4-hydroxy-phenyl) methanone,
4,4 ′-(diphenyl-methylene) bisphenol,
4,4'-propylidenebisphenol, 4,4'-
(1-ethylethylidene) bisphenol, 4,4'-
(3-methylbutylidene) bisphenol, 4,4'-
Cyclopentylidenebisphenol, 4,4′-cyclopentylidenebis (2-methylphenol), 2,2-
Bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-
4-hydroxyphenyl) propane, 2,2-bis (3
-Chloro-4-hydroxyphenyl) propane, 2,2
-Bis (3-bromo-4-hydroxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2
-Bis (4-hydroxyphenyl) propane, 4,4 '
-Biphenol, 3,3 ', 5,5'-tetramethyl-
Aromatic diols such as 4,4'-dihydroxybiphenyl and 4,4'-dihydroxybenzophenone;
These may be used alone or in combination of two or more. Particularly, bisphenol A, bisphenol C and bisphenol Z are preferably used.

The resin composition of the present invention comprises 5 to 70% by weight of an aromatic polyester part (A) and one polyester part (B).
0 to 75% by weight and the polycarbonate part (C) 20 to 8
5% by weight, these parts are chemically bonded, and the number average molecular weight (Mn) is 2,000 to 2
It must be 00,000.

When the content of the aromatic polyester resin part (A) is less than 5% by weight, the crystallinity of the resin composition becomes high and the transparency of the coating film is impaired. When it exceeds 70% by weight, the abrasion resistance is improved. The effect decreases. The polyester resin part (B) is 1
If the amount is less than 0% by weight, the effect of improving wear resistance decreases,
If it exceeds 75% by weight, the solubility of the solvent will be deteriorated and it will be difficult to dissolve it in a chlorine-based solvent. Polycarbonate resin part (C)
If the content is less than 20% by weight, coloring derived from the ester bond of the resin composition may be increased, and the application is limited. If the content is more than 85% by weight, the effect of improving abrasion resistance is reduced.

The number average molecular weight of the resin composition greatly affects the mechanical strength and abrasion resistance of the molded product. When the number average molecular weight is less than 2,000, the mechanical strength and abrasion resistance are significantly reduced, and exceed 200,000. In this case, the solution viscosity increases significantly, and the coating operation becomes difficult. The number average molecular weight is preferably at least 5,000, more preferably at least 10,000.

Further, the resin composition of the present invention needs to have an elongation at break of 50% or more, preferably 7%.
0% or more, more preferably 100% or more. In the present invention, the method of measuring the elongation at the time of tensile fracture is based on ASTM D638. In order to improve the elongation at the time of tensile break, it is necessary to copolymerize a resin part having a high elongation. Usually, the elongation percentage of a general aromatic polyester part is 60% or less, and the elongation percentage of a polycarbonate part is 130% or less. Therefore, in order to further increase the elongation of the resin composition of the present invention, it is desirable to introduce a polyester part having an elongation of 200% or more. However, although some polyesters do not show a high elongation rate by themselves, there are also products having a high elongation rate by being introduced into the copolymer, so that it is important to control the elongation rate of the copolymer.

The resin composition of the present invention needs to have a light transmittance of 70% or more. In the present invention, the light transmittance refers to a film having a thickness of 15 μm and a wavelength of 400 μm.
It refers to the transmittance when measured in the region of -800 nm. If the light transmittance is less than 70%, application to optical applications becomes difficult. In order to improve the light transmittance, it is necessary that the above components are chemically bonded to each other until the resin composition is observed as one phase by observation with a phase contrast microscope. When the phase becomes two or three due to low chemical bonding, the coating film becomes white and cloudy due to the difference in the refractive index of the resin part, and the light transmittance decreases.

Further, the resin composition of the present invention needs to have a solubility of 10 g / 100 ml or more. In the present invention, the solubility refers to the amount of the resin composition dissolved in chloroform or methylene chloride at 25 ° C. In resin coating applications, the higher the solubility of the resin in the solvent, the easier it is to control the film thickness. Usually, a chlorine-based solvent such as methylene chloride or chloroform is used as a coating solvent for the polyarylate and the polycarbonate. Therefore, it is preferable that the resin composition of the present invention is also dissolved therein. In order to improve the solvent solubility, it is not stricter to improve the light transmittance, but the polyester part having poor solvent solubility is introduced into the composition so as to be a copolymer, and the insoluble part is not present. Is essential.

Various resin additives can be mixed into the resin composition of the present invention, if necessary. These resin additives include heat stabilizers, antioxidants, light stabilizers, release agents, lubricants, pigments, flame retardants, plasticizers, antistatic agents, antibacterial antifungal agents, charge generators, charge transfer agents. And the like.
In addition, fiber reinforcement such as glass fiber, metal fiber, potassium whisker, carbon fiber, filler such as talc, calcium carbonate, mica, glass flake, milled fiber, metal flake, and metal powder are mixed. You may.

Next, a method for producing the resin composition of the present invention will be described. The resin composition of the present invention comprises an aromatic polyester resin (polyarylate), a polyester resin,
It can be produced by melt-kneading with a polycarbonate resin in the above-mentioned mixing ratio. That is, by melt-kneading these resins, an ester exchange reaction is induced between the ester bond of the aromatic polyester resin and the polyester resin and the carbonate bond of the polycarbonate resin, and the aromatic polyester-polyester-
A polycarbonate-based copolymer is formed. The resin composition of the present invention is obtained by copolymerizing this until it becomes one phase by observation with a phase contrast microscope.

As the melt-kneading method for producing the resin composition of the present invention, for example, a reaction vessel equipped with a stirring blade, a general extruder, an injection molding machine, a Brabender, a kneader, a Banbury mixer and the like can be used. The melt-kneading temperature is not lower than the glass transition temperature of these resins, and is preferably 50 ° C. or higher than the glass transition temperature in order to sufficiently plasticize these resins.

Further, in the present production method, a known ester polymerization catalyst may be added in order to promote the transesterification reaction between the aromatic polyester resin, the polyester resin and the polycarbonate resin. Specific examples of the ester polymerization catalyst include Na, Mg, Zn, Cd, Ti, Pb, Sb, and S.
metal acetates such as n, alkoxides, hydroxides and the like. Specifically, zinc acetate, magnesium acetate, antimony acetate, germanium acetate, lead monoxide, lead dioxide, tetramethyl titanate, tetraethyl titanate, tetrabutyl titanate, etc., may be used alone or in combination of two or more. You may use together. The method for adding the catalyst is not particularly limited. The transesterification catalyst was added in an amount of 3% by weight based on the total amount of the raw resin.
Or less, preferably 0.5% by weight or less. If it exceeds 3% by weight, the color tone of the resin composition may be deteriorated.

When the above catalyst is used, a known catalyst deactivator can be added to prevent a side reaction after the reaction. These deactivators may be any compounds that can suppress the function of decomposing an ester bond or a carbonate bond, and specifically a phosphorus compound. Examples of the phosphorus compound include orthophosphoric acid, phosphonic acid, and phosphite, and among them, phosphite is most preferably used. Examples of the phosphite include alkyl phosphite, aryl phosphite, alkyl / aryl phosphite, diphosphite, polyphosphite, thiophosphite, and the like. Specific examples thereof include diisooctyl phosphite, distearyl. Phosphite, triisodecyl phosphite, triisooctyl phosphite, trilauryl phosphite, tristeolyl phosphite, diphenyl phosphite,
Triphenyl phosphite, phenyl diisodecyl phosphite and the like. The method of adding the catalyst deactivator is not particularly limited, but preferably the above catalyst,
After sufficiently reacting the aromatic polyester resin, polyester resin and polycarbonate resin in the first step, the second step
It is preferable to add a deactivator as a step to deactivate the catalyst. In addition, as long as the progress of the transesterification reaction is not impaired, known resin additives such as a heat stabilizer, an antioxidant, and a release agent can be added at the time of melt-kneading.

Thus, according to the production method of the present invention, these resins react to form a resin composition comprising an aromatic polyester-polyester-polycarbonate copolymer. As a means for confirming the copolymerization, for example, it is preferable to prepare cast films from the resin mixture before melt-kneading and the product after kneading, respectively, and observe these with a phase contrast microscope. A phase contrast microscope image of one phase is obtained in a copolymerized system, and two or three phases are obtained in a non-copolymerized system.
A phase-contrast microscope image separated into phases is obtained.

Next, the coating film of the present invention will be described. The resin composition of the present invention uses an aromatic polyester-polyester-polycarbonate copolymer for various uses such as known electric, electronic, and mechanical fields, as long as it is used as a coating film on the surface of a material including metal. Is also good.
As the coating method, there are a method in which the resin is melted by heat to coat the material, and a method in which the resin is dissolved in a solvent to form a solution, and then applied to the material and dried, and either method may be used. The coating can be performed using various known coating apparatuses, and specifically, an applicator, a spray coater, a bar coater, a chip coater, a roll coater, a dip coater, a doctor blade, or the like can be used. This coating has a thickness of 15 μm and 4
The light transmittance in the range of 00 to 800 nm is 70% or more.

Next, the electrophotographic photosensitive member of the present invention will be described. The resin composition of the present invention can be applied to various known types of electrophotographic photoreceptors as long as it is used as a binder resin in a single-layer or laminated photoreceptor. It is preferably used as a binder resin of a charge transfer layer in a laminated electrophotographic photoreceptor having a charge generation layer and at least one charge transfer layer. In the electrophotographic photoreceptor of the present invention, at least the resin composition of the present invention may be contained in the photosensitive layer, and may be used in combination with another binder resin. In this case, the other binder resin can be used in an appropriate amount within a range that does not impair the abrasion resistance and transparency, which are the objects of the present invention.

Specific examples of such a binder resin include styrene-based polymers, styrene-butadiene copolymers, styrene-acrylonitrile copolymers, styrene-maleic acid copolymers, acrylic copolymers, and the like. Styrene-acrylic copolymer, ethylene-vinyl acetate copolymer, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyester, polyamide, polyurethane, polycarbonate, polyarylate, epoxy resin, polysulfone, diallyl phthalate resin, silicon Resins, ketone resins, polyvinyl butyral resins, polyether resins, phenolic resins, and photocurable resins such as epoxy acrylate and urethane acrylate are exemplified. In addition, a photoconductive polymer such as poly-N-vinylcarbazole which can also be used as a charge transfer agent can be used as a binder resin, and an additive such as an antioxidant may be added as necessary.

As the conductive substrate material used for the electrophotographic photoreceptor of the present invention, various materials such as known materials can be used, and specifically, for example, aluminum, brass, copper, nickel, steel, etc. A metal plate, a metal drum or a metal sheet, a plastic sheet, and a conductive material such as aluminum, nickel, chromium, palladium, graphite, or the like, which has been subjected to a conductive treatment by vapor deposition, sputtering, coating, or the like, metal A drum whose surface is treated with a metal oxide by electrode oxidation or the like, or a substrate such as glass, plastic plate, cloth, paper or the like which has been subjected to a conductive treatment can be used.

The charge generating layer of the multi-layer type electrophotographic photosensitive member has at least a charge generating material, and the charge generating layer is formed on a substrate serving as an underlayer by vacuum deposition, sputtering, or the like. Or by forming a layer in which a charge generating substance is bound using a binder resin on a substrate serving as an underlayer. As a method for forming the charge generation layer using a binder resin, various methods such as a known method can be used, and usually, for example, a coating liquid in which a charge generation material is dispersed or dissolved in a suitable solvent together with a binder resin. Is applied onto a substrate serving as a predetermined base and dried.

As the charge-generating substance, various substances such as known substances can be used. Specifically, for example, selenium alone such as amorphous selenium and trigonal selenium, selenium alloys such as selenium-tellurium, As ₂ Selenium compounds or selenium-containing compositions such as Se ₃ , zinc oxide, inorganic materials composed of Group II and IV elements such as CdS-Se, oxide semiconductors such as titanium oxide, silicon-based materials such as amorphous silicon, etc. And various organic materials such as metal or metal-free phthalocyanine, cyanine, anthracene, bisazo compound, pyrene, perylene, pyrylium salt, thiapyrylium salt, polyvinylcarbazole, and squarium pigment. These may be used alone or in combination of two or more.

The binder resin in the charge generation layer is not particularly limited, and various resins such as known ones can be used. Specifically, for example, styrene-based polymers, styrene-butadiene copolymers, styrene-acrylonitrile Copolymer, styrene-maleic acid copolymer, acrylic copolymer, styrene-acrylic copolymer, ethylene-vinyl acetate copolymer, polyvinyl chloride, vinyl chloride-
Vinyl acetate copolymer, polyester, polyamide, polyurethane, polycarbonate, polyarylate, epoxy resin, polysulfone, diallyl phthalate resin, silicone resin, ketone resin, polyvinyl butyral resin, polyether resin, phenol resin, epoxy acrylate, urethane acrylate, etc. And the like can be used. It is preferable to use the resin composition of the present invention as a binder resin in the charge generation layer.

The mixing ratio (weight ratio) of the charge generating substance to the binder resin is preferably in the range of 20: 1 to 1:20.
The thickness of the charge generation layer is generally 0.01 to 5 μm.
m, preferably in the range of 0.05 to 2.0 μm.

Next, the charge transfer layer can be obtained by forming a layer in which a charge transfer substance is bound to a binder resin on a base substrate. As a method for forming the charge transfer layer using the binder resin, various methods such as a known method can be used.In general, for example, a coating liquid in which a charge transfer material is dispersed or dissolved in a suitable solvent together with the binder resin is used. A method in which the composition is applied onto a substrate serving as a predetermined base and dried, and the like are preferably used.

The resin composition of the present invention is used for the charge transfer layer. In this case, the resin composition may be used alone or in combination of two or more. Further, other binder resins can be used in combination with the resin composition of the present invention as long as the object of the present invention is not impaired.

As the charge transfer material which can be used in the present invention, for example, there are an electron transfer material and a hole transfer material which are conventionally used. Specific examples of the electron-transporting substance include, for example, chloranil, bromanyl, 2, 3
-Dichloro-5,6-dicyano-p-benzoquinone, tetracyanoethylene, tetracyanoquinodimethane, 2,
4,7-trinitro-9-fluorenone, 2,4,5
7-tetranitro-9-fluorenone, 2,4,7-trinitro-9-dicyanomethylene fluorenone, 2,
4,5,7-tetranitroxanthone, 2,4,9-trinitrothioxanthone, or 3,5-dimethyl-
Examples thereof include electron withdrawing substances such as diphenoquinone derivatives such as 3 ′, 5′-di-t-butyl-4,4′-diphenoquinone, and those obtained by increasing the molecular weight of these electron withdrawing substances. These may be used alone or in combination of two or more.

The hole-transporting substance includes pyrene, N-ethylcarbazole, N-isopropylcarbazole,
-Methyl-N-phenylhydrazino-3-methylidene-
9-ethylcarbazole, N, N-diphenylhydrazino-3-methylidene-9-ethylcarbazole, N, N
-Diphenylhydrazino-3-methylidene-10-ethylphenothiazine, N, N-diphenylhydrazino-3
-Methylidene-10-ethylphenoxazine, p-diethylaminobenzaldehyde-N, N-diphenylhydrazone, p-diethylaminobenzaldehyde-N-α
-Naphthyl-N-phenylhydrazone, p-pyrrolidinobenzaldehyde-N, N-diphenylhydrazone,
1,3,3-trimethylindolenine-ω-aldehyde-N, N-diphenylhydrazone, p-diethylbenzaldehyde-3-methylbenzthiazolinone-2-hydrazone, 1-phenyl-1,2,3,4- Hydrazones such as tetrahydroquinoline-6-carboxaldehyde-1 ′, 1′-diphenylhydrazone, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 1-phenyl-3- ( p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [quinolyl (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [repidyl (2 )]-3- (p-
Diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [6-methoxy-pyridyl (2)]-3- (p-diethylaminostyryl) -5-
(P-diethylaminophenyl) pyrazolin, 1- [pyridyl (5)]-3- (p-diethylaminophenyl)
Pyrazoline, 1- [pyridyl (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazolin, 1- [pyridyl (2)]-3- (p
-Diethylaminostyryl) -4-methyl-5- (p-
Diethylaminophenyl) pyrazolin, 1- [pyridyl (2)]-3- (α-methyl-p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazolin, 1-phenyl-3- (p-diethylaminostyryl)- 4-methyl-5- (p-diethylaminophenyl) pyrazoline, 1-phenyl-3- (α-benzyl-
Pyrazolines such as diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline and spiropyrazoline, 2- (p-diethylaminostyryl) -δ-diethylaminobenzoxazole, 2- (p-diethylaminophenyl) -4- (p-diethylamino Phenyl)
Oxazole compounds such as -5- (2-chlorophyll) oxazole, 2- (p-diethylaminostyryl)-
Thiazole compounds such as 6-diethylaminobenzothiazole, triarylmethane compounds such as bis (4-diethylamino-2-methylphenyl) phenylmethane,
1,1-bis (4-N, N-diethylamino-2-methylphenyl) heptane, 1,1,2,2-tetrakis (4-N, N-diethylamino-2-methylphenyl)
Polyarylamines such as ethane, N, N′-diphenyl-N, N′-bis- (methylphenyl) benzidine;
N, N'-diphenyl-N, N'-bis- (ethylphenyl) benzidine, N, N'-diphenyl-N, N'-
Bis- (propylphenyl) benzidine, N, N′-diphenyl-N, N′-bis- (butylphenyl) benzidine, N, N′-diphenyl-N, N′-bis- (isopropylphenyl) benzidine, Benzidine compounds such as N'-diphenyl-N, N'-bis- (t-butylphenyl) benzidine and N, N'-diphenyl-N, N'-bis- (chlorophenyl) benzidine; butadiene compounds; Phenylamine, poly-N
-Vinyl carbazole, polyvinyl pyrene, polyvinyl anthracene, polyvinyl acridine, poly-9-vinyl phenyl anthracene, organic polysilane, pyrene-formaldehyde resin, ethyl carbazole-formaldehyde resin, and the like. These may be used alone or in combination of two or more.

The mixing ratio (weight ratio) of the charge transfer material and the binder resin is preferably in the range of 10: 1 to 1: 5. The thickness of the charge transfer layer is generally set in the range of 5 to 50 μm, preferably 10 to 30 μm.

Specific examples of the solvent used for forming the charge generation layer and the charge transfer layer include aromatic solvents such as benzene, toluene, xylene and chlorobenzene, ketones such as acetone, methyl ethyl ketone and cyclohexanone, and methanol. Alcohols such as ethanol, isopropanol, ethyl acetate, esters such as ethyl cellosolve, carbon tetrachloride, chloroform, dichloromethane, tetrachloroethane, halogenated hydrocarbons such as 1,2-dichloroethane, tetrahydrofuran, ethers such as dioxane, dimethylformamide, Dimethyl sulfoxide,
Diethylformamide and the like can be mentioned. These solvents may be used alone or in combination of two or more.

The coating of each layer can be performed using various coating apparatuses such as known ones. Specifically, for example, an applicator, a spray coater, a bar coater, a chip coater, a roll coater, a dip coater, a doctor blade, etc. Can be performed.

The photosensitive layer of the single-layer type electrophotographic photosensitive member contains the resin composition of the present invention as a binder resin, and at least the charge generating substance and the charge transfer substance. As the method, various methods such as a known method can be used. In general, for example, a method in which a coating liquid in which a charge generating substance and a charge transfer substance are dispersed or dissolved in a suitable solvent together with a binder resin, is applied onto a substrate serving as a predetermined base, and dried, can be suitably used. . In addition, other binder resins can be used in combination with the resin composition of the present invention as long as the object of the present invention is not impaired.

The electrophotographic photoreceptor of the present invention can be obtained by using the resin composition of the present invention as a binder resin.
An electrophotographic photoreceptor having excellent wear resistance and excellent optical properties, and can be suitably used in various electrophotographic fields.

[0055]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the present invention, and all of these are illustrative. In the following examples, parts and% indicate parts by weight and% by weight, respectively. The molecular weight is measured by gel permeation chromatography (GPC: manufactured by Tosoh Corporation) and is expressed in terms of styrene equivalent molecular weight. The aromatic polyester resin, polyester resin and polycarbonate resin used are as follows.

Sample 1 [Bisphenol A type aromatic polyester resin] Bisphenol was prepared by an interfacial polymerization method using a methylene chloride solution of a mixed acid chloride having a molar ratio of terephthalic acid dichloride to isophthalic acid dichloride of 1: 1 and an aqueous alkali solution of bisphenol A. An A-type aromatic polyester resin was obtained. (Mn = 19,000, Mw = 35,000)

Sample 2 [Bisphenol C Type Aromatic Polyester Resin] Bisphenol was prepared by an interfacial polymerization method using a methylene chloride solution of a mixed acid chloride having a molar ratio of terephthalic acid dichloride to isophthalic acid dichloride of 1: 1 and an aqueous solution of bisphenol C. A C-type aromatic polyester resin was obtained. (Mn = 24,000, Mw = 57,000)

Sample 3 [Bisphenol Z-Type Aromatic Polyester Resin] Bisphenol was prepared by interfacial polymerization from a methylene chloride solution of a mixed acid chloride having a molar ratio of terephthalic acid dichloride to isophthalic acid dichloride of 1: 1 and an aqueous alkali solution of bisphenol Z. A Z-type aromatic polyester resin was obtained. (Mn = 25,000, Mw = 57,000)

Sample 4 [Polyethylene terephthalate resin] manufactured by Toyobo Co., Ltd., trade name RE-530 Sample 5 [polybutylene terephthalate resin] manufactured by Asahi Kasei Corporation, trade name Hardik A5410 Sample 6 [amorphous polyethylene terephthalate] Modified resin] 40 manufactured by Toyobo Co., Ltd., trade name Byron 200 sample 7 [polyethylene naphthalate resin] manufactured by Teijin Limited, trade name: TN8060 sample 8 [bisphenol A type polycarbonate resin] manufactured by Mitsubishi Chemical Corporation Brand name NOVAREX 7025A Sample 9 [Bisphenol Z-type polycarbonate resin] (Mn = 24,000, Mw = 41,000)

Examples 1 to 9 An aromatic polyester resin, a polyester resin and a polycarbonate resin were melt-kneaded in a small Banbury mixer (manufactured by Toyo Seiki Co., Ltd.) connected to a Labo Plastomill without a catalyst (condition: 280 ° C.). , Normal pressure, 20 rpm). The production of the aromatic polyester-polyester-polycarbonate copolymer is performed by sampling a kneaded sample to form a cast film (solvent: chloroform) having a thickness of 5 μm and using a phase contrast microscope (Aristoplan manufactured by Leica Corporation). It was confirmed by analyzing the phase state (change to a one-phase state when the copolymer was formed). Table 1 shows the copolymer components and ratios of Examples 1 to 9.

Next, the kneaded sample was collected until the reaction completion time (about 30 minutes), and 1 part was added to 100 ml of chloroform.
0 g was dissolved to prepare a coating solution. This coating solution was applied to an aluminum substrate (10 cm × 10 cm) using a bar coater, and dried in an oven at 120 ° C. for 20 minutes to make the thickness of the coating film 15 μm.

The abrasion resistance of the above coating film was measured. The abrasion resistance test was performed with a Taber abrasion tester (condition: wear wheel C).
S-17, load 500g, 1,000 rotations, 60rpm
m). In addition, the elongation at the time of tensile break of the produced copolymer is:
A dumbbell-type test piece was molded and measured using an autograph (manufactured by Shimadzu Corporation). Further, the light transmittance of the copolymer was determined as follows. The above coating solution was applied to a glass substrate using a bar coater, and dried in an oven at 120 ° C. for 20 minutes to make the thickness of the coating film 15 μm. The obtained coating film was measured using a spectrum photometer (U-4000 manufactured by Hitachi, Ltd.) in a measurement wavelength range of 400 to 8.
The light transmittance was measured at 00 nm. Table 2 shows the evaluation results of the abrasion resistance of the coating film, the elongation at break of the copolymer, and the light transmittance of the coating film.

[0063]

[Table 1]

[0064]

[Table 2]

Comparative Examples 1-3, 11-15 Melting and kneading were performed using a small Banbury mixer (manufactured by Toyo Seiki Co., Ltd.) in which an aromatic polyester resin, a polyester resin and a polycarbonate resin were connected to a Labo Plastomill.
(Condition: 280 ° C., normal pressure, 20 rpm) The reaction time was about the same as that in the preparation of the examples (about 30 minutes). In Comparative Examples 11 and 12, a recovery step was performed to obtain a target molecular weight product. The preparation of the coating solution, the abrasion resistance test, the elongation measurement at the time of tensile rupture, and the light transmittance measurement were performed under the same conditions as in the examples.
Table 3 shows the copolymer components and ratios of Comparative Examples 1 to 3 and 11 to 15, and Table 5 shows the evaluation results.

Comparative Examples 4 to 10 An aromatic polyester resin, a polyester resin and a polycarbonate resin were individually evaluated. The preparation of the coating liquid, the abrasion resistance test, the elongation measurement at the time of tensile rupture, and the light transmittance measurement were performed under the same conditions as in the examples. Table 3 shows the components of Comparative Examples 4 to 10, and Table 5 shows the evaluation results.

Comparative Examples 16 and 17 Coating liquids were prepared by blending the aromatic polyester resin, polyester resin and polycarbonate resin shown in Samples 1 to 8 and evaluated. Preparation of the coating solution, abrasion resistance test, and light transmittance measurement were performed under the same conditions as in the examples. Table 4 shows the compositions and blend ratios of Comparative Examples 16 and 17, and Table 5 shows the evaluation results. In addition, among the comparative examples, 2, 3,
7, 13, 15 and 16 were insoluble in chloroform and could not form a coating film, so that the abrasion loss and light transmittance could not be measured. Comparative Examples 16 and 17 were simply blends, and thus could not be subjected to a tensile test using a molded product (a copolymerization reaction due to heat occurred during molding).

[0068]

[Table 3]

[0069]

[Table 4]

[0070]

[Table 5]

From the comparison between Examples 1 to 9 and Comparative Examples 1 to 17, the aromatic polyester-polyester-polycarbonate copolymer, which is the resin composition of the present invention, is excellent in transparency and particularly resistant to abrasion. It is recognized that the property is excellent.

[0072]

The resin composition of the present invention comprises an aromatic polyester-polyester-polycarbonate copolymer excellent in transparency, solvent solubility and abrasion resistance. And the manufacturing cost is low. Further, by using the resin composition of the present invention, a coating film having excellent abrasion resistance can be formed, and an electrophotographic photoreceptor having excellent optical characteristics and abrasion resistance can be formed.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 10, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C09D 169/00 PLP C09D 169/00 PLP G03G 5/047 G03G 5/047 5/05 101 5/05 101

Claims (5)

[Claims] 1. An aromatic polyester part (A) composed of a polycondensation part having an aromatic dicarboxylic acid residue and an aromatic diol residue as main components, 5 to 70% by weight, and an aromatic dicarboxylic acid residue or 10 to 75% by weight of a polyester part (B) composed of a condensation polymerization part having an aliphatic dicarboxylic acid residue and an aliphatic diol residue as main components, and an aromatic dicarboxylic acid residue and a carbonic acid residue as main components. 20 to 85% by weight of a polycarbonate part (C) composed of a polycondensation part, and these parts have a chemical bond and a number average molecular weight (Mn) of 2,000 to 200,000, ASTM D
Elongation at tensile break according to 638 is 50% or more, thickness 1
A resin composition having a light transmittance of 70% or more in a 400 to 800 nm region of a 5 µm coating film, and a solubility in chloroform or methylene chloride at 25 ° C of 10 g / 100 ml or more. 2. An aromatic polyester resin comprising 5 to 70% by weight of an aromatic polyester resin composed of a condensation polymerization part mainly composed of an aromatic dicarboxylic acid residue and an aromatic diol residue, and an aromatic dicarboxylic acid residue or an aliphatic dicarboxylic acid. Polyester resin 1 composed of polycondensation unit mainly composed of an acid residue and an aliphatic diol residue
0 to 75% by weight, and 20 to 85% by weight of a polycarbonate resin composed of a condensation polymerization unit containing an aromatic dicarboxylic acid residue and a carbonic acid residue as main components, in the presence or absence of an ester polymerization catalyst, The method for producing a resin composition according to claim 1, wherein the melt kneading is performed until the phases become one phase. 3. A coating film formed from the resin composition according to claim 1, which has a light transmittance of 400 μm at a thickness of 15 μm.
A coating film that is 70% or more in the 800 nm region. 4. An electrophotographic photosensitive member having a photosensitive layer on a conductive substrate, wherein the photosensitive layer contains the resin composition according to claim 1 as a binder resin. 5. The electrophotographic photosensitive member according to claim 4, wherein the charge transport layer of the electrophotographic photosensitive member having a laminated structure of a charge generating layer and a charge transfer layer is electron donating or electron accepting.