JP2007056182A - Polyamic acid composition, polyimide endless belt and image-forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyamic acid composition having a stable viscosity, a manufacturing method thereof, a polyimide endless belt having uniform resistance and being excellent in mechanical properties and surface properties, a manufacturing method thereof, and an image-forming apparatus equipped with the polyimide endless belt that gives a transferred image of high qualities. <P>SOLUTION: The polyamic acid composition comprises a polyamic acid, a polyaniline, a dopant for making the polyaniline electroconductive, a solvent and a basic additive. The polyimide endless belt comprises a polyimide, the polyaniline, the dopant for making the polyaniline electroconductive and the basic additive. The image-forming apparatus is equipped with the polyimide endless belt. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is a polyamic acid composition used for the production of polyimide molded products having both mechanical properties and chemical properties such as high strength, high heat resistance and chemical resistance, and electrical properties such as conductivity, semiconductivity and chargeability. And a polyimide endless belt obtained by using the polyamic acid composition, and an image forming apparatus provided with the polyimide endless belt.

  In an electrophotographic apparatus, an electric charge is uniformly formed on a photosensitive member made of a conductive material, an electrostatic latent image is formed with a modulated image signal using a laser beam or the like, and then the electrostatic latent image is developed with charged toner. Thus, a toner image is obtained. Next, the toner image is transferred to a recording medium such as paper directly or via an intermediate transfer member to obtain an image.

  Here, a method of primary transfer of a toner image on a photosensitive member to an intermediate transfer member, and then secondary transfer of the toner image on the intermediate transfer member to a recording medium such as paper, image formation employing a so-called intermediate transfer method The intermediate transfer belt used in the apparatus is, for example, a conductive endless belt in which a conductive agent such as carbon black is dispersed in a thermoplastic resin such as polyvinylidene fluoride, polycarbonate, or a blend of an ethylene-tetrafluoroethylene copolymer and polycarbonate. Has been proposed.

  Furthermore, in recent years, a method for fixing a toner image on a recording medium by heating the intermediate transfer member, that is, an intermediate transfer and fixing method has been disclosed (for example, Patent Document 1). In the intermediate transfer / fixing method, after the toner image is secondarily transferred to the recording medium via the intermediate transfer member, the intermediate transfer member is directly or indirectly heated to contact the intermediate transfer member. This is a method for fixing a toner image on a recording medium, and has an advantage that the apparatus can be reduced in size and cost compared with a conventional apparatus in which the intermediate transfer mechanism and the fixing mechanism are separated.

Here, the belt material used in the intermediate transfer and fixing method is required to have a mechanical strength that can withstand the stress during driving and at the same time be able to withstand the heat of about 200 ° C. that is applied during fixing. From this demand, a polyimide resin having both high mechanical strength and heat resistance is suitable for the material used for the intermediate transfer and the fixing belt.
When the polyimide resin is molded into a belt shape, since the polyimide resin is generally insoluble, a polyamic acid solution that is a precursor thereof is used as a coating solution, and this is applied to the front or back surface of the cylindrical mold, It heats after drying and performs dehydration imidation reaction of an amic acid group. Under the present circumstances, when the defect arises in application of a polyamic acid solution, it has become a problem that the quality of a molded product will fall. In particular, sagging or flow occurs when the viscosity of the polyamic acid solution is insufficient, resulting in in-plane thickness unevenness of the molded product. On the contrary, when the viscosity of the polyamic acid solution is higher than the setting, it is difficult for the coating liquid to develop during coating, and a part of the coating surface may be thickened to become a void during heat treatment. .
From the above points, the control of the viscosity of the coating solution (polyamic acid solution) is an important issue when manufacturing molded products of polyimide resin, not limited to belt-shaped molded products formed on a cylindrical mold. Yes.

  On the other hand, as a method for imparting conductivity to a molded article of polyimide resin, a method using a conductive polymer such as polyaniline as a conductive material is known. Since conductive polymers such as polyaniline are easily dissolved or dispersed uniformly in the polyimide varnish, it is easy to adjust the molded product to a predetermined resistance value, and a uniform resistance value can be obtained. . Thus, the method of providing electroconductivity by adding polyaniline as a electrically conductive material in a polyimide resin is disclosed by the cited literatures 2-4, for example.

However, when using a conductive polymer (polyaniline) as in the above cited references 2 to 4, a large amount of an acidic compound serving as a dopant for making polyaniline conductive must be added to the polyamic acid solution. First, due to the presence of the acidic compound, the hydrolysis of the polyamic acid is promoted and the viscosity of the polyamic acid solution is decreased, or the imidation reaction is promoted to increase the viscosity of the coating liquid. In some cases, the polyimide polymer was precipitated. As a result, there has been a problem that the viscosity of the polyamic acid solution becomes unstable. Thus, when the viscosity of the polyamic acid solution is not stable, the quality of the molded product obtained by using it as a coating solution, for example, uneven local resistance, deterioration of mechanical properties, and surface roughness There was a risk of causing deterioration of surface properties such as non-uniformity.
JP-A-6-258960 JP-A-8-259709 Japanese Patent Laid-Open No. 9-176329 JP 2000-226765 A

Therefore, the present invention aims to solve the conventional problems and achieve the following object.
That is, it aims at providing the polyamic acid composition which contains polyamic acid and polyaniline, and has the stable viscosity.
Another object of the present invention is to provide a polyimide endless belt having uniform resistance and excellent mechanical properties and surface properties.
It is another object of the present invention to provide an image forming apparatus that includes the polyimide endless belt and can obtain a high-quality transfer image.

  As a result of intensive studies to solve the above problems, the present inventors have found that the following problems can be solved by the present invention. That is, the present invention

<1> A polyamic acid composition comprising a polyamic acid, polyaniline, a dopant for making the polyaniline conductive, a solvent, and a basic additive.

<2> The polyamic acid composition according to <1>, wherein the basic additive is one or more compounds selected from the group consisting of basic inorganic particles and tertiary amines.

<3> The polyamic acid composition according to <1> or <2>, wherein the dopant is an acidic compound.

<4> The polyamic acid composition according to <3>, wherein the acidic compound is dodecylbenzenesulfonic acid and / or phenolsulfonic acid.

<5> The polyamic acid composition according to any one of <1> to <3>, wherein the addition amount of the dopant is 0.1 to 5 equivalents with respect to the structural unit of the polyaniline.

<6> Any one of <1> to <5>, wherein the viscosity ratio V2 / V0 between the viscosity V0 immediately after the adjustment and the viscosity V2 after the passage of 2 days in a room temperature environment is in the range of 0.8 to 1.2 2. The polyamic acid composition according to item 1.

<7> A polyimide endless belt comprising polyimide, polyaniline, a dopant for making the polyaniline conductive, and a basic additive.

<8> The polyimide endless belt according to <7>, further comprising a conductive agent.

<9> The polyimide endless belt according to <7>, which is formed using the polyamic acid composition according to any one of <1> to <6>.

<10> An image forming apparatus comprising the polyimide endless belt according to any one of <7> to <9>.

According to the present invention, a polyamic acid composition having a stable viscosity can be provided.
Further, it is possible to provide a polyimide endless belt having uniform resistance and excellent mechanical properties and surface properties, and a method for producing the same.
Furthermore, by providing the polyimide endless belt of the present invention, an image forming apparatus capable of obtaining a high-quality transfer image can be provided.

  Hereinafter, the polyamic acid composition, the polyimide endless belt, and the image forming apparatus of the present invention will be described in detail.

<Polyamic acid composition>
The polyamic acid composition of the present invention is characterized by containing a polyamic acid, polyaniline, a dopant for making the polyaniline conductive, a solvent, and a basic additive.
Thus, the basic additive which comprises the polyamic acid composition of this invention can suppress the hydrolysis of the polyamic acid produced with the dopant which consists of an acidic compound by showing basicity. As a result, it becomes possible to suppress the viscosity change of the polyamic acid over time, and the viscosity can be stabilized.
Hereinafter, each component which comprises the polyamic acid composition of this invention is demonstrated.

[Basic additives]
As the basic additive in the present invention, any compound can be used as long as it is a compound showing basicity when dissolved in a solvent constituting the polyamic acid composition. Examples include particles and tertiary amines.
The basic inorganic particles used here mean inorganic particles having a pH value of 7.0 or more at 25 ° C. when 1 g of inorganic particles are dispersed in 100 ml of water. Specifically, particles having a number average particle diameter of 10 nm to 100 μm, such as zinc oxide, zinc carbonate, calcium oxide, calcium carbonate, aluminum hydroxide, alumina, mica, talc, and kaolin are used. These are used alone or in combination.
Here, the particle size of the basic inorganic particles is measured by a laser scattering type particle size distribution analyzer.

  The addition amount of the basic inorganic particles is preferably 0.01 to 20 parts by mass when the total amount of the resin composed of polyamic acid and polyaniline in the polyamic acid composition is 100 parts by mass. If it is less than 0.01 mass part, the viscosity stabilization of the polyamic acid composition which is the effect of this invention cannot be achieved. Moreover, when it exceeds 20 mass parts, the flexibility of a polyimide molding will be lost.

  In this way, by adding basic inorganic particles, in addition to the effects expressed due to the basicity of the basic inorganic particles as described above, the inorganic particles function as fillers, so that It is possible to improve the strength.

Examples of the tertiary amine include trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, pyridine, picoline, collidine, lutidine, quinoline, and isoquinoline. Of these, pyridine, picoline, quinoline, isoquinoline, and triethylamine are preferably used. These are used alone or in combination.
The molar amount of the tertiary amine is preferably 0.7 to 1.3 times the dopant. When the amount is less than 0.7 times, the function as an acid strongly acts on the resin, and the polyamic acid may be decomposed to cause a decrease in viscosity. On the other hand, when the amount is more than 1.3 times, excessive tertiary amine may accelerate imidization of polyamic acid and cause gelation.
When such a tertiary amine is added, it may be added as a salt together with the dopant, or may be added alone.

  Thus, by adding a tertiary amine, in addition to the effect expressed due to the basicity of the tertiary amine as described above, the tertiary amine functions as a catalyst for promoting the conversion of polyamic acid to polyimide. Thus, it is possible to mold polyimide at a low temperature.

  In addition, in a polyimide resin molded product obtained by coating and drying a polyamic acid composition containing a tertiary amine, the tertiary amine volatilizes during the drying process, so the amount of the tertiary amine remaining in the molded product is small. Become. For example, when a polyimide endless belt described later is molded as a polyimide resin molded product, the tertiary amine remaining in the polyimide endless belt is preferably in the range of 1 to 5% by mass, and in the range of 1 to 4% by mass. It is more preferable that it is in the range of 1 to 3% by mass. If the remaining amount is within this range, the influence on the image quality can be reduced when a polyimide endless belt is provided as an intermediate transfer belt of the image forming apparatus. When the residual amount of the tertiary amine is more than 5% by mass, the strength of the polyimide endless belt is weak, and when it is less than 1% by mass, the flexibility of the belt is lowered.

  As the basic additive of the present invention, it is preferable to use one or more selected from the group consisting of the above basic inorganic particles and tertiary amines, and a mixture of two or more may be used. Furthermore, basic inorganic particles and tertiary amines may be used in combination.

[Polyamic acid]
The polyamic acid in the present invention is obtained by polymerizing a tetracarboxylic dianhydride and a diamine compound in a substantially equimolar amount in an organic polar solvent.
Hereinafter, the tetracarboxylic dianhydride and the diamine compound will be described.

(Tetracarboxylic dianhydride)
There is no restriction | limiting in particular as tetracarboxylic dianhydride which can be used for manufacture of a polyamic acid, Either an aromatic type or an aliphatic type compound can be used.
Examples of the aromatic tetracarboxylic acid include pyromellitic dianhydride, 3,3 ′, 4,4′-benzoenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl sulfone. Tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl Ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilane tetracarboxylic dianhydride, 1, 2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) Diphenylsulfo Dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3' , 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthal Acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, and the like.

  Aliphatic tetracarboxylic dianhydrides include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane. Tetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbonane-2-acetic acid dianhydride Anhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, Aliphatic or alicyclic tetracarboxylic dianhydrides such as bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride; 4 5,9b-Hexahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl -5- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl Examples include aliphatic tetracarboxylic dianhydrides having an aromatic ring such as -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione. Can do.

The tetracarboxylic dianhydride used in the present invention is preferably an aromatic tetracarboxylic dianhydride, and more preferably pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid. The dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, is optimally used.
These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

(Diamine compound)
Next, the diamine compound that can be used for the production of the polyamic acid is not particularly limited as long as it is a diamine compound having two amino groups in the molecular structure.
Specifically, for example, p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide 4,4′-diaminodiphenylsulfone, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4′-diaminobiphenyl, 5-amino-1- (4′-aminophenyl) -1,3,3 -Trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 4,4'-diaminobenzanilide, 3,5-diamino-3'-trifluoromethylbenzanilide 3,5-diamino-4′-trifluoromethylbenzanilide, 3,4′-diaminodiphenyl ether, 2,7-dia Nofluorene, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4'- Diaminobiphenyl, 2,2′-dichloro-4,4′-diamino-5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 4,4′-diamino-2,2 '-Bis (trifluoromethyl) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1, 4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) -biphenyl, 1,3′-bis (4-aminophenoxy) benzene, 9,9-bis (4-amino) Nophenyl) fluorene, 4,4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-(m-phenyleneisopropylidene) bisaniline, 2,2′-bis [4- (4-amino-2-trifluoro) Aromatic diamines such as methylphenoxy) phenyl] hexafluoropropane, 4,4′-bis [4- (4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl; aromatic rings such as diaminotetraphenylthiophene An aromatic diamine having two bonded amino groups and a hetero atom other than the nitrogen atom of the amino group; 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, octa Methylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylene Diamine, 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoin danylene dimethylene diamine, tricyclo [6,2,1,02.7] -undecylenedimethyl Examples include diamines, aliphatic diamines such as 4,4′-methylenebis (cyclohexylamine), and alicyclic diamines.

Examples of the diamine compound used in the present invention include p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenylsulfone, Is preferred.
These diamine compounds can be used alone or in combination of two or more.

(Preferable combination of tetracarboxylic dianhydride and diamine compound)
As a polyamic acid in this invention, Preferably, what consists of aromatic tetracarboxylic dianhydride and aromatic diamine from a viewpoint of the intensity | strength of a molded object is preferable.

(Synthetic solvent)
Examples of the organic polar solvent used in the polyamic acid production reaction include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, N, Acetamide solvents such as N-dimethylacetamide and N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m-, or p-cresol Phenol solvents such as xylenol, halogenated phenol and catechol, ether solvents such as tetrahydrofuran, dioxane and dioxolane, alcohol solvents such as methanol, ethanol and butanol, cellosolve such as butyl cellosolve and hexamethyl. Phosphoramides, .gamma.-butyrolactone, etc. can be mentioned, but it is desirable to use them alone or as a mixture, further, xylene, aromatic hydrocarbons such as toluene can be used.

(Solid content concentration during polyamic acid polymerization)
Although the solid content concentration in the reaction solution at the time of polyamic acid polymerization is not particularly defined, it is preferably 5 to 50% by mass. Furthermore, 10-30 mass% is especially suitable. When the solid content concentration is less than 5% by mass, the degree of polymerization of the polyamic acid is low, and the strength of the molded product finally obtained is lowered. Moreover, when the solid content concentration at the time of polymerization is higher than 50% by mass, an insoluble part of the raw material monomer is generated and the reaction does not proceed.

(Polyamic acid polymerization temperature)
As reaction temperature at the time of polyamic acid polymerization, it is carried out in the range of 0 ° C to 80 ° C. This is because when the reaction temperature is 0 ° C. or lower, the viscosity of the solution increases and the reaction system cannot be sufficiently stirred. Further, when the reaction temperature is higher than 80 ° C., there is a problem in terms of reaction control because a part of imidization reaction occurs in parallel with the polymerization of polyamic acid.

[Polyaniline]
The polyaniline in the present invention is used as a conductive material, and the synthesis and structure of the polyaniline are described in detail in JP-A-3-28229.
The polyaniline in the present invention can be easily produced from aniline or an aniline derivative by oxidative polymerization. It is known that polyaniline has a structure of leucoemeraldine (or leucoemeraldine), emeraldine (or emeraldine) and pernigraniline depending on its oxidation state. Of these, polyaniline having an emeraldine structure is most useful because it has the highest electrical conductivity during doping and is stable in air.
In the synthesis of polyaniline, as described in detail in JP-A-3-28229, the temperature of aniline is maintained at 5 ° C. or lower, preferably 0 ° C. or lower in a solvent in the presence of a protonic acid. Meanwhile, an oxidant polymerization is performed by causing an oxidant to act to produce an oxidized polymer of aniline doped with a protonic acid (to be described later) (hereinafter referred to as doped polyaniline). This doped polyaniline can then be obtained by undoping with a basic material.

  The addition amount (use amount) of polyaniline in the polyamic acid composition is appropriately adjusted depending on the conductivity to be expressed. Generally, the polyaniline to be added is preferably 5 to 40 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the polyamic acid resin content in the polyamic acid composition. If the amount of polyaniline added is less than 5 parts by mass, the predetermined electrical conductivity cannot be expressed, and if it exceeds 40 parts by mass, the flexibility of the polyimide molded product using the polyamic acid composition is lost. This is because, for example, when a polyimide endless belt is molded, it does not have a function as a belt.

  The polyaniline in the present invention may be dissolved in a suitable solvent and used as a polyaniline solution. Moreover, a part of polyaniline may be dispersed. In that case, a dispersant may be used to disperse the polyaniline. The dispersant is preferably a nonionic polymer compound, such as polyvinyl pyrrolidone, polyvinyl alcohol, polyether hydroxypropyl cellulose, poly (N, N′-diethylacrylazide), poly (N-vinylformamide), poly (N -Vinylacetamide), poly (N-vinylphthalamide), poly (N-vinylsuccinamide), poly (N-vinylurea), poly (N-vinylpiperidone), poly (N-vinylcaprolactam), poly (N- Vinyl oxazoline) and the like.

The polyaniline solution can be obtained by dissolving polyaniline in an appropriate solvent (for example, a solvent described later) and crushing the polyaniline aggregate. Here, as a method of crushing the aggregate of polyaniline, physical mixing such as stirring with a mixer or stirrer, parallel roll, ultrasonic dispersion, jet mill, bead mill, ball mill, paint shaker, speed rotor mill, three rolls, etc. Examples of the method include chemical methods such as introduction of a dispersant, but are not limited thereto.
The volume average particle size of the polyaniline particles after the pulverization treatment is preferably in the range of 10 nm to 1 μm. When the thickness is larger than 1 μm, for example, when a polyimide endless belt is molded using the polyamic acid composition of the present invention, it appears as a defect on the surface and the in-plane uniformity of electrical resistance is impaired.

[Dopant]
In the present invention, an acidic compound such as protonic acid can be preferably used as a dopant for doping polyaniline to make it conductive. A preferable protonic acid as a dopant is a compound that does not volatilize or decompose by heat treatment at the time of polyimide molding. As such a protonic acid, for example, a sulfonic acid compound and an organic carboxylic acid compound are preferably used.

  Examples of the sulfonic acid compound include aminonaphthol sulfonic acid, metanilic acid, sulfanilic acid, allyl sulfonic acid, lauryl sulfuric acid, xylene sulfonic acid, chlorobenzene sulfonic acid, methane sulfonic acid, ethane sulfonic acid, 1-propane sulfonic acid, 1- Butanesulfonic acid, 1-hexanesulfonic acid, 1-heptanesulfonic acid, 1-octanesulfonic acid, 1-nonanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, benzenesulfonic acid, styrenesulfonic acid, p- Toluenesulfonic acid, naphthalenesulfonic acid, ethylbenzenesulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, pentylbenzenesulfonic acid, hexylbenzenesulfonic acid, heptylbenzenesulfonic acid, octylbenzenesulfonic acid Nonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, octadecylbenzenesulfonic acid, diethylbenzenesulfonic acid, dipropylbenzenesulfonic acid, dibutylbenzenesulfonic acid, methylnaphthalenesulfone Acid, ethyl naphthalene sulfonic acid, propyl naphthalene sulfonic acid, butyl naphthalene sulfonic acid, pentyl naphthalene sulfonic acid, hexyl naphthalene sulfonic acid, heptyl naphthalene sulfonic acid, octyl naphthalene sulfonic acid, nonyl naphthalene sulfonic acid, decyl naphthalene sulfonic acid, undecyl naphthalene Sulfonic acid, dodecylnaphthalenesulfonic acid, pentadecylnaphthalenesulfonic acid, octadecylnaphtha Sulfonic acid, dimethylnaphthalenesulfonic acid, diethylnaphthalenesulfonic acid, dipropylnaphthalenesulfonic acid, dibutylnaphthalenesulfonic acid, dipentylnaphthalenesulfonic acid, dihexylnaphthalenesulfonic acid, diheptylnaphthalenesulfonic acid, dioctylnaphthalenesulfonic acid, dinonylnaphthalenesulfonic acid , Trimethylnaphthalenesulfonic acid, triethylnaphthalenesulfonic acid, tripropylnaphthalenesulfonic acid, tributylnaphthalenesulfonic acid, camphorsulfonic acid, acrylamide-t-butylsulfonic acid, and the like. Among these, dodecylbenzenesulfonic acid and phenolsulfonic acid are preferably used.

  Specific examples of the organic carboxylic acid compound include benzoic acid, m-bromobenzoic acid, p-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, o-nitrobenzoic acid, 2,4-dinitrobenzoic acid. Acid, 3,5-dinitrobenzoic acid, picric acid, o-chlorobenzoic acid, p-nitrobenzoic acid, m-nitrobenzoic acid, trimethylbenzoic acid, p-cyanobenzoic acid, m-cyanobenzoic acid, thymol blue, And salicylic acid, 5-aminosalicylic acid, o-methoxybenzoic acid, 1,6-dinitro-4-chlorophenol, 2,6-dinitrophenol, 2,4-dinitrophenol, p-oxybenzoic acid, and the like. .

Further, in the present invention, the proton acid used as the dopant may be a polymer acid. Examples of such a polymer acid include polyvinyl sulfonic acid, polyvinyl sulfuric acid, polystyrene sulfonic acid, sulfonated styrene-butadiene copolymer, polyallyl sulfonic acid, polymethallyl sulfonic acid, and poly-2-acrylamido-2-methyl. Examples thereof include propane sulfonic acid and polyisoprene sulfonic acid.
Of these dopants, dodecylbenzenesulfonic acid, phenolsulfonic acid, and phenylphosphonic acid are particularly preferable.

  These dopants are added in an amount of 0.1 to 5 equivalents, more preferably 1 to 3 equivalents, relative to the structural unit of polyaniline.

[solvent]
The solvent in the present invention is not particularly limited as long as it dissolves polyamic acid. Specifically, for example, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, N, N-dimethylformamide, N, N- Formamide solvents such as diethylformamide, N, N-dimethylacetamide, acetamide solvents such as N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, phenol solvents such as o-, m-, or p-cresol, xylenol, halogenated phenol, catechol, ether solvents such as tetrahydrofuran, dioxane, dioxolane, alcohol solvents such as methanol, ethanol, butanol, butyl cellosol And cellosolve such as hexamethylphosphoramide, γ-butyrolactone, etc., and these are preferably used alone or as a mixture, but aromatic hydrocarbons such as xylene and toluene can also be used. is there.

This solvent may be used in preparing the polyamic acid solution. Moreover, this solvent may be used from the above-mentioned polyamic acid polymerization or may be replaced with a predetermined solvent after the polyamic acid polymerization. For solvent replacement, a method in which a predetermined amount of solvent is added to the polyamic acid polymerization solution for dilution, a method in which the polyimide polymer is reprecipitated and then re-dissolved in the predetermined solvent, and the solvent is gradually distilled off. Any of the methods for adjusting the composition by adding a predetermined solvent may be used.
The concentration of the polyamic acid in the polyamic acid solution is preferably adjusted in the range of 10 to 50 parts by mass.

  This solvent may also be used in preparing the polyaniline solution / dispersion. In that case, the content of polyaniline in the polyaniline solution / dispersion is preferably adjusted in the range of 0.1 to 30% by mass.

[Additive]
Moreover, carbon black etc. are mentioned as an arbitrary component (additive) which can be added to the polyamic acid composition of this invention.

(Carbon black)
Carbon black which is an optional component is used, for example, for the purpose of adjusting the resistance value of a molded product obtained using the polyamic acid composition of the present invention.
For example, when using the polyamic acid composition of the present invention to obtain a polyimide endless belt applied to an electrophotographic image forming apparatus, the amount of carbon black added is 100 parts by mass of the polyamic acid in the polyamic acid composition. On the other hand, it is preferably 0 to 20 parts by mass, and more preferably 5 to 10 parts by mass. When the added amount of carbon black exceeds 20 parts by mass, it becomes difficult to obtain a desired resistance value. Furthermore, by containing 5 to 10 parts by mass of carbon black, the effect can be maximized, and the in-plane unevenness of the surface resistivity and the electric field dependency can be remarkably improved.

[Preparation of polyamic acid composition]
In the present invention, the polyamic acid composition is prepared according to the following procedures (a) and (b).
(A) A polyaniline solution obtained by dissolving polyaniline and a polyamic acid solution obtained by dissolving polyamic acid are prepared. After the dopant is added to the prepared polyaniline solution to make the polyaniline conductive, the polyamic acid solution is gradually added to this mixed solution, followed by stirring and mixing. Then, a polyamic acid composition is obtained by adding a basic additive.
(B) A polyaniline solution in which polyaniline is dissolved and a polyamic acid solution in which polyamic acid is dissolved are prepared. The polyaniline solution is gradually added to the mixture obtained by adding the dopant to the prepared polyamic acid solution, and the mixture is stirred and mixed. Then, a polyamic acid composition is obtained by adding a basic additive.
In addition, preparation of a polyamic acid composition may include the process of adding arbitrary components, such as the above-mentioned carbon black, and stirring and disperse | distributing as needed.

  In addition, after adding a basic additive, as a method of dispersing the basic additive or disrupting the aggregate, physical methods such as stirring with a mixer or a stirrer, parallel rolls, ultrasonic dispersion, etc. Furthermore, chemical methods such as introduction of a dispersant are exemplified, but the present invention is not limited thereto.

The polyamic acid composition thus obtained had a viscosity ratio V2 / V0 of 0 immediately after the adjustment and a viscosity V2 after 2 days in a room temperature environment (25 ° C. in the present invention). It is preferably from 0.8 to 1.2, and more preferably from 0.9 to 1.15. When V2 / V0 is less than 0.8, sagging or the like may occur during coating due to a decrease in viscosity, resulting in a defective part of the molded product. On the other hand, when it exceeds 1.2, a polyaniline gel is generated, It may cause non-uniform resistance and image quality defects. In addition, the measurement of the viscosity immediately after adjustment of a polyamic acid composition is performed immediately after stirring is complete | finished after mixing said five essential components.
The viscosity ratio V2 / V0 can be controlled within the above range by adjusting the type and amount of the basic compound contained in the polyamic acid composition.
Here, the viscosity of the polyamic acid composition is a viscosity at a liquid temperature of 25 ° C., and is a value measured using a constant velocity viscometer PK100 manufactured by HAKKE Corporation.

  The polyamic acid composition according to the present invention has been described above, but the present invention is not limited only to these embodiments, and various improvements can be made based on the knowledge of those skilled in the art without departing from the spirit of the present invention. The present invention can be implemented in a mode in which changes, modifications are made.

<Polyimide endless belt>
The polyimide endless belt of the present invention comprises polyimide, polyaniline, a dopant for making the polyaniline conductive, and a basic additive.
As described above, the polyimide endless belt of the present invention only needs to contain the above four essential components, but in order to efficiently obtain the effect of adding the basic additive, the above polyamic acid composition of the present invention is used. It is preferable that it is obtained using.
The polyimide endless belt of the present invention is preferably used in an electrophotographic apparatus such as an electrophotographic copying machine, a laser beam printer, a facsimile, and a composite apparatus thereof. More specifically, the polyimide endless belt is preferably applied to a transfer belt, a conveyance belt, and an intermediate transfer belt in an intermediate transfer type electrophotographic apparatus.

If the difference between the maximum thickness and the minimum thickness of the polyimide endless belt of the present invention is too large, it causes wrinkles. When the belt is used in an electrophotographic apparatus, it is necessary to reduce the wrinkle of the belt as much as possible because it induces a decrease in image quality when transferring or fixing. From this point, it is desirable that the difference between the maximum thickness and the minimum thickness of the polyimide endless belt is 20% or less of the average thickness of the polyimide endless belt. The “belt thickness” refers to a thickness that can be measured with a thickness meter that measures the distance between flat plates in contact with the belt at an area of 5 mm ² or more, and has a width of 50 μm or less that exists specifically on the belt surface. The height of the protrusion is ignored.
Moreover, when the thickness of a polyimide endless belt is too thick, it is unpreferable from viewpoints, such as thermal conductivity and resistance value, and when too thin, its toughness is too small, and is not preferable. Therefore, considering the use of the belt, the thickness of the belt is preferably 10 μm or more and 1000 μm or less, and preferably 30 μm or more and 150 μm or less.

In addition, the conductivity, particularly volume resistivity, of the polyimide endless belt of the present invention may be adjusted as appropriate in accordance with the application. For example, when the polyimide endless belt of the present invention is applied to an intermediate transfer belt, the volume resistivity is preferably 10 ⁶ Ω · cm or more and 10 ¹² Ω · cm or less. More preferably, it is 10 ⁹ Ω · cm or more and 10 ¹² Ω · cm or less. If the volume resistivity is less than 1 × 10 ⁶ [Omega] cm, since the electrostatic force holding the electric charge of the unfixed toner image transferred from the image carrier to the intermediate transfer belt is less likely to work, toner particles Due to the electrostatic repulsive force and the force of the fringe electric field in the vicinity of the image edge, the toner may be scattered around the image (blur), and an image having a large noise may be formed. On the other hand, when the volume resistivity is higher than 1 × 10 ¹² Ωcm, since the charge retention is large, the surface of the intermediate transfer belt is charged by the transfer electric field in the primary transfer, so that a static elimination mechanism is necessary. There is. Therefore, by setting the volume resistivity within the above range, it is possible to solve toner scattering and problems that require a charge removal mechanism.

  Furthermore, the polyimide resin endless belt of the present invention preferably has a surface roughness Ra defined by JIS B 0601 (2001) of the belt surface of 0.1 μm or more and 0.5 μm or less. If the surface roughness Ra of the belt surface exceeds 0.5 μm, electric field concentration is likely to occur, which causes a decrease in resistance. Further, from the viewpoint of further improving resistance maintainability, Ra is more preferably 0.1 μm or less, and particularly preferably 0.05 μm or less. Although not particularly limited, if the surface roughness of the surface that contacts the belt mold (that is, the surface roughness of the mold) is too small, the adhesion between the belt and the mold becomes too strong, From the viewpoint of difficulty in demolding, the lower limit is generally 0.01 μm or more.

  In the present invention, the surface roughness Ra was measured according to JIS B 0601 (2001) using a surface roughness shape measuring instrument (Surfcom 1400A series manufactured by Tokyo Seimitsu Co., Ltd.). Specifically, under the conditions of a measurement length of 2.5 mm, a cut-off wavelength of 0.8 mm, and a measurement speed of 0.60 mm / s, 24 points are measured per belt (3 in the width direction × 8 in the circumferential direction) The average value was defined as the surface roughness Ra of the belt.

Such a polyimide endless belt of the present invention heats the polyamic acid composition coated on the cylindrical substrate and the step of coating the above-described polyamic acid composition of the present invention on the cylindrical substrate. It is preferable to manufacture by going through a heat treatment step.
The polyimide endless belt thus obtained is mainly composed of a polyimide molded body.

An example of the manufacturing method of the polyimide endless belt of this invention is demonstrated concretely.
First, the above-described polyamic acid composition of the present invention is applied to the inner surface or outer surface of a mold that is a cylindrical substrate. In addition, instead of the mold, cylindrical molds made of various known materials such as resin, glass, and ceramic can be used. It is also possible to appropriately select to provide a glass coat or ceramic coat on the surface of the cylindrical mold or cylindrical mold, and to use a silicone-based or fluorine-based release agent.
Also, by moving the film thickness control mold with the clearance adjusted to the cylindrical mold through the cylindrical mold in parallel, the excess solution is eliminated and the thickness of the solution on the cylindrical mold is made uniform. You may apply the method to do. If the uniform thickness control of the solution is performed at the stage of applying the solution onto the cylindrical mold, it is not necessary to use a film thickness control mold.

Next, the cylindrical mold to which the polyamic acid composition is applied is placed in a heating environment, and drying is performed to volatilize 30% by mass or more, preferably 50% by mass or more of the contained solvent. At this time, the drying temperature is preferably in the range of 50 to 200 ° C.
Furthermore, this cylindrical mold is heated at a temperature of 150 ° C. to 450 ° C. above the boiling point of the tertiary amine to sufficiently advance the imide conversion reaction. The temperature of the imide conversion reaction varies depending on the types of the raw material tetracarboxylic dianhydride and diamine, or the tertiary amine added, but if imidization is insufficient, the mechanical properties and electrical properties are reduced. Since it becomes inferior, it must be set to a temperature at which imide conversion is completed.
Thereafter, the polyimide resin is removed from the cylindrical mold, and an endless belt-like polyimide belt (polyimide endless belt) can be obtained.

Since the polyimide endless belt of the present invention thus obtained is obtained using the polyamic acid composition of the present invention having a stable viscosity as described above, the resistance is uniform, and the machine It has the effect that it is excellent in mechanical properties and surface properties.
The polyimide endless belt in the present invention has been described above, but the present invention is not limited only to these embodiments, and various modifications based on the knowledge of those skilled in the art without departing from the spirit thereof. The present invention can be implemented in a mode in which changes and modifications are made.

<Image forming apparatus>
The image forming apparatus of the present invention may have any configuration as long as it includes the above-described polyimide endless belt of the present invention. Specifically, for example, a monocolor electrophotographic apparatus having only a single color (usually black) in the apparatus, a color electrophotographic apparatus that repeats primary transfer of a toner image carried on a photoreceptor to an intermediate transfer belt sequentially, Any of the tandem color electrophotographic apparatuses in which a plurality of latent image carriers having developing units for respective colors are arranged in series on an intermediate transfer belt may be used. Further, it may be an intermediate transfer system using an intermediate transfer belt, and / or an image forming apparatus having a mechanism for directly or indirectly heating the belt.
In these image forming apparatuses, the polyimide endless belt of the present invention described above can be used not only for intermediate transfer and fixing, but also as an intermediate transfer belt, a conveyance belt, and a fixing belt. The intermediate transfer and fixing belt is a belt that performs an intermediate transfer process and a fixing process on the same belt.
As described above, the polyimide endless belt of the present invention has uniform resistance and excellent mechanical properties and surface properties. By applying this to an image forming apparatus, a high-quality transfer image can be stabilized. Can be obtained.

  Hereinafter, a configuration example of the image forming apparatus of the present invention including the polyimide endless belt of the present invention will be described in detail with reference to the drawings. Here, FIG. 1 shows a schematic configuration diagram of a color electrophotographic copying machine 100 as an example of the image forming apparatus of the present invention using the above-described polyimide endless belt of the present invention as an intermediate transfer belt.

  In FIG. 1, reference numerals 101BK, 101Y, 101M, and 101C denote photosensitive drums (image carriers), and the surface thereof is converted into image information by a known electrophotographic process (not shown) as it rotates in the direction of arrow A. A corresponding electrostatic latent image is formed.

  Further, around the photosensitive drums 101BK, 101Y, 101M, and 101C, developing units 105 to 108 corresponding to black (BK), yellow (Y), magenta (M), and cyan (C) colors, respectively. The electrostatic latent images formed on the photosensitive drums 101BK, 101Y, 101M, and 101C are developed by the developing units 105 to 108 to form toner images. Therefore, for example, the electrostatic latent image written on the photosensitive drum 101Y corresponds to yellow image information, and this electrostatic latent image is developed by the developer 106 containing yellow (Y) toner, A yellow toner image is formed on the photosensitive drum 101Y.

  Reference numeral 102 denotes a belt-shaped intermediate transfer belt disposed so as to be in contact with the surfaces of the photosensitive drums 101BK, 101Y, 101M, and 101C. The belt-shaped intermediate transfer belt is stretched around a plurality of rolls 117 to 120 and rotated in the arrow B direction. Move.

  Since the polyimide endless belt of the present invention described above is used for the intermediate transfer member 102, defects due to non-uniform film thickness, non-uniform conductivity, etc. of the conventional endless belt can be reduced. As a result, the quality of the transferred image obtained by this image forming apparatus is excellent.

  Unfixed toner images formed on the photosensitive drums 101BK, 101Y, 101M, and 101C are sequentially exposed at respective primary transfer positions where the photosensitive drums 101BK, 101Y, 101M, and 101C are in contact with the intermediate transfer member 102. Each color is superimposed and transferred onto the surface of the intermediate transfer body 102 from the body drums 101BK, 101Y, 101M, and 101C.

  At the primary transfer position, corona dischargers 109 to 112 that prevent the transfer prenip from being charged by transfer baffles 121 to 124 are disposed on the back side of the intermediate transfer member 102. The corona dischargers 109 to 112 are disposed. By applying a voltage having the opposite polarity to the toner charging polarity, the unfixed toner images on the photosensitive drums 101BK, 101Y, 101M, and 101C are electrostatically attracted to the intermediate transfer member 102. The primary transfer means is not limited to a corona discharger as long as it uses an electrostatic force, and may be a conductive roll or a conductive brush to which a voltage is applied. The reason for using such an electrostatic force is that if the adhesive force of toner due to heat or pressure is used for primary transfer, the photoreceptor is easily damaged.

  The unfixed toner image primarily transferred to the intermediate transfer member 102 in this way is conveyed to a secondary transfer position facing the conveyance path of the recording medium 103 as the intermediate transfer member 102 rotates. At the secondary transfer position, a heating transfer roll 120 incorporating a heating source such as a ceramic heater or a halogen lamp is in contact with the back side of the intermediate transfer member 102. In addition, a pressure roll 125 is disposed facing the heating transfer roll 120 at the secondary transfer position. The pressure roll 125 preferably has a surface coated with a fluororesin, and may include a heating source in the same manner as the heating transfer roll 120.

  The recording medium 103 carried out from the tray 113 at a predetermined timing by the feed roller 126 is inserted between the pressure roll 125 and the intermediate transfer member 102. At this time, a voltage may be applied between the heat transfer roll 120 and the pressure roll 125. The unfixed toner image carried on the intermediate transfer member 102 is heat-melted and transferred to the recording medium 103 at the secondary transfer position. Since the toner image is melted and transferred by heating and pressure means, even if an intermediate transfer member 102 without charge attenuation is used, a discharge occurs between the intermediate transfer member 102 and the recording medium 103 and the toner scatters. It does not cause the problem of image quality defects.

  Then, the recording medium 103 on which the unfixed toner image is transferred is peeled off from the intermediate transfer body 102 by the peeling claw 114, and sent to a fixing device (not shown) by the conveying belt 115 to fix the unfixed toner image. The At this time, the secondary transfer device (the heat transfer roll 120 and the pressure roll 125) may serve as fixing, but in order to obtain sufficient color fixing properties, it is preferable to make the fixing process independent as described above. .

  The pressure roll 125, the peeling claw 114, and the cleaning device 116 are disposed so as to be in contact with and away from the intermediate transfer member 102, and these members are separated from the intermediate transfer member 102 until the secondary transfer is performed.

  A plurality of examples corresponding to the present invention and comparative examples for these examples will be described below. These examples are all illustrative, and the scope of the present invention is not limited by this description.

[Example 1]
<Preparation of polyamic acid solution (a)>
Into a flask equipped with a stirrer, a thermometer and a dropping funnel, nitrogen gas dried with phosphorus pentoxide was passed through 29.42 g (0.1 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride. ) And 117.68 g of N-methyl-2-pyrrolidone (NMP) were injected. After sufficiently stirring and dissolving, a solution prepared by dissolving 20.02 g (0.1 mol) of 4,4′-diaminodiphenyl ether in 80.08 g of N-methyl-2-pyrrolidone was gradually put in a flask maintained at 10 ° C. It was dripped. After dropwise addition of the diamine solution, stirring and polymerization were performed at 10 to 15 ° C. The reaction solution was poured into a large amount of methanol, and reprecipitation purification was performed. The precipitated white polymer was separated by filtration and dried, and then redissolved in N-methyl-2-pyrrolidone to obtain a 20% by mass polyamic acid solution (a).

<Synthesis of polyaniline>
In a 10 L-separable flask, 6000 g of ion-exchanged water, 400 ml of 35% hydrochloric acid, and 400 g (4.295 mol) of aniline were charged and stirred to dissolve aniline. While cooling with ice water in a beaker container, 434 g (4.295 mol) of 98% concentrated sulfuric acid was added to and mixed with 1493 g of ion-exchanged water to prepare an aqueous sulfuric acid solution. This sulfuric acid aqueous solution was gradually added to the aniline solution while cooling with ice.
Next, an aqueous oxidizing agent solution in which 980 g (4.295 mol) of ammonium peroxodisulfate was dissolved in 2300 g of ion exchange was gradually added dropwise to the aniline solution while cooling with ice. After the dropping, the colorless and transparent solution changed from greenish blue to blackish green as the polymerization proceeded, and then a blackish green powder precipitated. And stirring was further continued for 1 hour after dripping ammonium peroxodisulfate aqueous solution.
The obtained powder was filtered off, washed with water, washed with acetone, and vacuum dried at room temperature to obtain 430 g of conductive polyaniline doped with sulfuric acid as a black-green powder.
Subsequently, 350 g of doped conductive polyaniline powder was added to 4 liters of 2N aqueous ammonia, and the mixture was stirred for 5 hours at a rotation speed of 5000 rpm with a homomixer. The mixture changed from black-green to blue-violet. The powder was filtered off, washed with ion-exchanged water / acetone, and vacuum-dried at room temperature for 10 hours to obtain 280 g of black-brown dedope polyaniline powder. The molecular weight of the dedoped polyaniline structural unit was 182.2.

<Preparation of polyaniline solution (b)>
A polyaniline solution (b) was obtained by dissolving 18.22 g (0.10 mol) of the polyaniline powder (undoped state) obtained by the above method in 180 g of N-methyl-2-pyrrolidone (NMP).

<Preparation of polyamic acid composition (c-1)>
To the polyaniline solution (b) prepared by the above method, 32.65 g (0.10 mol) of dodecylbenzenesulfonic acid was added as a dopant. This was gradually added to 500 g of the 20% by mass polyamic acid solution (a) obtained by the above method while stirring. Furthermore, 5.91 g of zinc oxide (Zinc oxide LPZINC-2 manufactured by Sakai Chemical Co., Ltd .; number average particle size 2 μm), which is a basic additive, was added, and dispersed with a homogenizer at 3000 rpm for 5 minutes. Then, the aggregate was removed with a 50-micrometer hole metal mesh, and the polyamic acid composition (c-1) was obtained.

The composition of the polyamic acid composition (c-1) thus obtained is as follows.
-Composition of polyamic acid composition (c-1)-
・ Polyamic acid; 100g
・ Polyaniline; 18.22g
(0.1 mol; 18.22 parts by mass with respect to 100 parts by mass of polyamic acid)
・ Zinc oxide; 5.91 g
(Basic inorganic particles, polyamic acid + 5 parts for 100 parts by weight of polyaniline)
・ Dopant; 32.65 g
(0.1 mol; 1 equivalent to polyaniline structural unit)
・ Solvent: 580 g

With respect to the obtained polyamic acid composition (c-1), the sample immediately after the adjustment and the sample after 2 days (room temperature storage) were evaluated for the dispersibility and viscosity by visual observation. The evaluation method is shown below.
(Evaluation of dispersibility)
The polyamic acid composition (c-1) was filled in a 20 ml capacity transparent glass tube, and the aggregated and precipitated components appearing on the liquid surface were observed on white paper.
(Viscosity measurement conditions)
The liquid temperature of the polyamic acid composition (c-1) was adjusted to 25 ° C. and measured using a constant velocity viscometer PK100 manufactured by HAKKE.
(result)
Immediately after the adjustment, both after the lapse of 2 days, no aggregation or precipitation of particles was observed, and the particles were uniformly dispersed. Further, the viscosity was 30 Pas immediately after the adjustment, and 31 Pas after the lapse of 2 days. There was almost no change and the stability was maintained.

<Preparation of polyamic acid compositions (c-2) to (c-8)>
In the preparation of the polyamic acid composition (c-1), the type and amount of basic inorganic particles that are basic additives, the type and amount of dopant, and the use of other additives (carbon black) About presence or absence and its usage-amount, as described in Table 1 below, except that it was appropriately changed, the same treatment as in the preparation of the polyamic acid composition (c-1) was carried out, and the polyamic acid composition (c-2) To (c-8) were obtained.
Moreover, dispersibility and viscosity were visually evaluated by the above-described methods for the obtained polyamic acid compositions (c-2) to (c-8). The evaluation results are also shown in Table 1.

<Preparation of polyamic acid composition (c-9)>
To the polyaniline solution (b) prepared by the above method, 32.65 g (0.10 mol) of dodecylbenzenesulfonic acid was added as a dopant. This was gradually added to 500 g of the 20% by mass polyamic acid solution (a) obtained by the above method while stirring. Further, 7.91 g (0.10 mol) of pyridine, which is a basic additive, was added, and dispersion was performed with a homogenizer at 3000 rpm for 5 minutes. Then, the aggregate was removed with a 50-micrometer hole metal mesh, and the polyamic acid composition (c-9) was obtained.

The composition of the polyamic acid composition (c-9) thus obtained is as follows.
-Composition of polyamic acid composition (c-9)-
・ Polyamic acid; 100g
・ Polyaniline; 18.22g
(0.1 mol; 18.22 parts by mass with respect to 100 parts by mass of polyamic acid)
・ Pyridine; 7.91 g
(Basic inorganic particles, 0.10 mol; molar ratio to the dopant is 1 time)
・ Dopant; 32.65 g
(0.1 mol; 1 equivalent to polyaniline structural unit)
・ Solvent: 580 g

With respect to the obtained polyamic acid composition (c-9), the sample immediately after the adjustment and the sample after 2 days (room temperature storage) were evaluated for the dispersibility and the viscosity by visual observation. The evaluation method is the same as in the case of the polyamic acid composition (c-1).
As a result, immediately after the adjustment, both after the lapse of 2 days, no aggregation or precipitation of particles was observed, and the particles were uniformly dispersed. Further, the viscosity was 30 Pas immediately after the adjustment, and 31 Pas after the lapse of 2 days. There was almost no change and the stability was maintained.

<Preparation of polyamic acid compositions (c-10) to (c-15)>
In the preparation of the polyamic acid composition (c-9), the type and amount of tertiary amine as a basic additive, the type and amount of dopant, and the use of other additives (carbon black) And the amount used thereof, as described in Table 2 below, except that it was appropriately changed, in the same manner as in the preparation of the polyamic acid composition (c-9), and the polyamic acid composition (c-10) to (C-15) was obtained.
Moreover, dispersibility and a viscosity were visually evaluated by the above method for the polyamic acid compositions (c-10) to (c-15). The evaluation results are also shown in Table 2.

<Preparation of polyamic acid compositions (c-16) and (c-17)>
In the preparation of the polyamic acid composition (c-9), the types and amounts of basic additives, the types and amounts of dopants, and the presence and usage of other additives (carbon black) As described in Table 3 below, the polyamic acid compositions (c-16) and (c-17) were treated in the same manner as in the preparation of the polyamic acid composition (c-9) except that they were appropriately changed. Respectively.
In addition, in polyamic acid composition (c-16) and (c-17), content of zinc oxide is 5 parts with respect to 100 mass parts of polyamic acid + polyaniline, and content of pyridine is 0.1. Mol: The molar ratio to the dopant is 1 time.
Moreover, dispersibility and a viscosity were visually evaluated by the above method for the polyamic acid compositions (c-16) and (c-17). The evaluation results are also shown in Table 3.

<Preparation of polyamic acid compositions (cr-1) to (cr-3)>
In the preparation of the polyamic acid composition (c-1), the presence / absence of use of basic additives, the type and blending amount of dopants, and the presence / absence of use of other additives (carbon black) and the use amounts thereof are described below. As shown in Table 3, except that it was changed appropriately, the same treatment as in the preparation of the polyamic acid composition (c-1) was performed, and the comparative polyamic acid compositions (cr-1) to (cr-3) were treated. I got each.
Moreover, dispersibility and a viscosity were visually evaluated with respect to the comparative polyamic acid compositions (cr-1) to (cr-3) by the above method. The evaluation results are also shown in Table 3.

[Examples 1-17, Comparative Examples 1-3]
<Manufacture of polyimide endless belt>
The obtained polyamic acid compositions (c-1) to (c-17) and (cr-1) to (cr-3) were uniformly applied to the surface of a cylindrical SUS mold having an inner diameter of 90 mm and a length of 450 mm, respectively. It was applied to. The cylindrical mold is preliminarily coated with a fluorine-based release agent to improve the peelability after belt molding. Thereafter, a drying process was performed for 30 minutes at a temperature of 120 ° C. while rotating the cylindrical mold. After the drying treatment, the cylindrical mold was placed in an oven and baked at 300 ° C. for about 30 minutes to advance the imide conversion reaction. Subsequently, the cylindrical mold was allowed to cool at room temperature, the resin was removed from the mold, and the target polyimide endless belt was obtained.
The obtained polyimide endless belt had a circumferential length of 283 mm and a width of 400 mm.

[Evaluation]
In the production of the polyimide endless belt, the coating performance was evaluated visually.
Moreover, in addition to the surface properties (appearance, Ra) and thickness of the obtained polyimide endless belt, electrical characteristics (surface resistance value, volume resistance value), mechanical characteristics (Young's modulus, tensile strength, elongation), to electrophotographic apparatus The quality of the transferred image when mounted was evaluated as follows. The evaluation results are shown in Tables 4 to 6 below.

"Evaluation of surface properties"
(appearance)
The appearance (transfer surface) of the obtained polyimide endless belt was visually observed and evaluated as follows. Here, the surface defect represents the presence or absence of aggregates appearing on the belt surface and the presence or absence of a pattern that disturbs the uniformity of the belt surface.
○: No surface defects are observed, and the film is excellent in uniformity.
○ to Δ: Some surface defects are observed, but there is no problem in practical use.
(Triangle | delta): Generation | occurrence | production of a surface defect is seen and there exists some trouble in practical use.
X: Surface defects frequently occur and cannot be used practically.

(Measurement of surface roughness Ra)
The surface roughness Ra of the transfer surface of the obtained polyimide endless belt was measured according to JIS B 0601 (2001) using a surface roughness shape measuring instrument (Surfcom 1400A series manufactured by Tokyo Seimitsu Co., Ltd.). Specifically, under the conditions of a measurement length of 2.5 mm, a cut-off wavelength of 0.8 mm, and a measurement speed of 0.60 mm / s, 24 points are measured per belt (3 in the width direction × 8 in the circumferential direction) The average value was defined as the surface roughness Ra of the belt.

(Thickness)
Ten pieces of 20 × 200 mm test pieces were randomly cut out from the obtained polyimide endless belt and measured using a constant pressure thickness measuring instrument (PG-02 manufactured by TECLOCK).

"Evaluation of electrical characteristics"
(Measurement of surface resistance)
The surface resistivity of the obtained polyimide endless belt was measured using an R8340A digital ultra-high resistance / microammeter (manufactured by Advantest Co., Ltd.) and a double ring electrode structure UR probe MCP- whose connection was modified for R8340A. HTP12 and register UFL MCP-ST03 (both manufactured by Dia Instruments Co., Ltd.) were used.
In addition, each polyimide endless belt manufactured by the Example and the comparative example was used for the test piece in the case of a measurement as it was.

  On the register UFL MCP-ST03 (using a fluororesin surface), the test piece was placed with the measurement surface facing up, and the double electrode of the UR probe MCP-HTP12 was applied so as to contact the measurement surface. A 19.6N ± 1N weight was attached to the upper part of the UR probe MCP-HTP12 so that a uniform load was applied to the test piece.

The measurement conditions of the R8340A digital ultra-high resistance / microammeter were a charge time of 30 sec, a discharge time of 1 sec, and an applied voltage of 100V.
At this time, assuming that the surface resistivity of the test piece is ρs, the reading value of the R8340A digital ultrahigh resistance / microammeter is R, and the surface resistivity correction coefficient of the UR probe MCP-HTP12 is RCF (S), According to the “Rate meter series” catalog, since RCF (S) = 10.00, the following equation (1) is obtained.
That is, Formula (1): ρs [Ω / □] = R × RCF (S) = R × 10.

(Measurement of volume resistivity)
For measuring the volume resistivity of the intermediate transfer belt, an R8340A digital ultra-high resistance / microammeter (manufactured by Advantest Co., Ltd.), a UR probe MCP-HTP12 having a double ring electrode structure in which the connection portion is modified for R8340A, and Resist UFL MCP-ST03 (both manufactured by Dia Instruments Co., Ltd.) was used.
In addition, the polyimide endless belt manufactured in the Example and the comparative example was used for the test piece in the case of a measurement as it was.

  A test piece was placed on the register UFL MCP-ST03 (the metal surface was used as the lower electrode), and the double electrode part of the UR probe MCP-HTP12 was applied as the upper electrode. A 19.6N ± 1N weight was attached to the upper part of the UR probe MCP-HTP12 so that a uniform load was applied to the test piece.

The measurement conditions of the R8340A digital ultra-high resistance / microammeter were a charge time of 30 sec, a discharge time of 1 sec, and an applied voltage of 100V.
At this time, the volume resistivity of the test piece is ρv, the thickness t (μm) of the intermediate transfer member, the R8340A digital ultrahigh resistance / microammeter reading is R, and the volume resistivity correction coefficient of the UR probe MCP-HTP12 is When RCF (V) is used, according to the Mitsubishi Chemical "Resistivity Meter Series" catalog, RCF (V) = 2.011, so the following equation (2) is obtained.
That is, Formula (2): ρv [Ω · cm] = R × RCF (V) × (10000 / t) = R × 2.111 × (10000 / t).

"Evaluation of mechanical properties"
(Measurement of Young's modulus, tensile strength, and elongation)
A test piece of 5 × 80 mm was produced from the obtained polyimide endless belt. This was measured for Young's modulus, tensile strength, tensile and elongation using a tensile tester (1605N manufactured by Aiko Engineering Co., Ltd.).

"Evaluation of the quality of transferred images"
The obtained polyimide endless belt was incorporated in an electrophotographic apparatus (DocuCenterColor400CP) manufactured by Fuji Xerox Co., Ltd. as an intermediate transfer belt, and the image quality of the initial transferred image was evaluated. As evaluation items for the image quality of the transferred image, the presence / absence of printing deviation, the presence / absence of printing density unevenness, the presence / absence of ghost, etc. were evaluated.
The presence or absence of printing misalignment, the presence or absence of uneven printing density, and the presence or absence of ghosts were confirmed visually.
Further, after passing 50,000 sheets, the same method as described above was used to evaluate the presence / absence of printing deviation, the presence / absence of printing density unevenness, and the presence / absence of ghost.

As is apparent from Tables 4 to 6, it can be seen that the coating performance in producing a polyimide endless belt using the polyamic acid composition of the present invention is excellent.
Moreover, it can be seen that the polyimide endless belt of the present invention obtained using the polyamic acid composition of the present invention has a good belt appearance and surface roughness and a uniform belt thickness. In addition, since it is excellent in mechanical strength and electrical characteristics, it exhibits suitable characteristics as an intermediate transfer and fixing belt, an intermediate transfer belt, a conveyance belt, and a fixing belt.
On the other hand, a polyimide endless belt obtained using a polyamic acid composition outside the scope of the present invention is not stable in viscosity of the polyamic acid composition and cannot be uniformly coated, resulting in As a result, the thickness of the belt became non-uniform and non-uniformity occurred in the plane of resistance characteristics. In addition, the quality of the transferred image when mounted on an electrophotographic apparatus was extremely poor.
It can also be seen that when such a polyimide endless belt of the present invention is mounted on an image forming apparatus, the quality of the transferred image is excellent.

1 is a schematic explanatory diagram illustrating a configuration of an image forming apparatus of the present invention.

Explanation of symbols

100 ... color electrophotographic copying machine (image forming apparatus)
101BK-Y ... photosensitive drum 102 ... intermediate transfer belt 103 ... recording medium 105-108 ... developer 109-112 ... corona discharge device 113 ... tray 114 ... peeling claw 115 ... Conveying belt 116 ... Cleaning device 117 ... Roll 120 ... Heating transfer rolls 121-124 ... Transfer baffle 125 ... Pressure roll 126 ... Feed roller

Claims (3)

  A polyamic acid composition comprising a polyamic acid, polyaniline, a dopant for making the polyaniline conductive, a solvent, and a basic additive.   A polyimide endless belt comprising polyimide, polyaniline, a dopant for making the polyaniline conductive, and a basic additive.   An image forming apparatus comprising the polyimide endless belt according to claim 2.

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