JP2009096867A - Resin composition, resin molded product and its manufacturing method, belt-stretching apparatus, process cartridge, and image-forming device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition to be molded into a resin molded product that permits easy adjustment of an initial resistivity value and suppression of increase of the resistivity value with time. <P>SOLUTION: The resin composition comprises an organic acid having a total carbon number of at least 10 in the portion other than an acid group, an inorganic protonic acid, an electroconductive polymer, and a resin. The resin molded product for an image-forming device is molded using the resin composition. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a resin composition, a resin molded product, a manufacturing method thereof, a belt stretching device, a process cartridge, and an image forming apparatus.

In order to use a conductive composition used for an electrophotographic apparatus member such as a transfer belt suitably, it is essential to control electric resistance.
Conventionally, resistance has been controlled by adding a conductive agent such as an ionic conductive agent or carbon black to the conductive composition.

In addition, polyaniline that exhibits conductivity by adding an acid is known as a conductive agent that is not easily affected by moisture that causes resistance fluctuations, and also has a small resistance fluctuation when the voltage is changed ( For example, see Patent Document 1 or Patent Document 2).
Japanese Patent No. 3409232 JP 2005-194528 A

  However, when a conductive polymer such as polyaniline is used, depending on the type of acid added, an appropriate resistance value cannot be obtained in the initial stage, or even if the initial resistance value is appropriate, the resistance value increases over time. It became clear to do.

This invention is made | formed in view of the above, and makes it a subject to achieve the following objectives.
That is, an object of the present invention is to provide a resin composition in which, when a resin molded product is molded, the resistance value in the initial stage can be easily adjusted, and an increase in the resistance value during repeated use can be suppressed. To do.
Moreover, an object of this invention is to provide the resin molding using the said resin composition, and its manufacturing method. Another object of the present invention is to provide a process cartridge for an image forming apparatus, a belt stretching apparatus, and an image forming apparatus using the resin composition.

The above problem is solved by the following means. That is, the present invention
The invention according to claim 1
It is a resin composition containing an organic acid having a total carbon number of 10 or more at a site excluding an acid group, an inorganic protonic acid, a conductive polymer, and a resin.

The invention according to claim 2
The mixing ratio of the organic acid having a total carbon number of 10 or more excluding the acid group and the inorganic protonic acid (molar ratio [the organic acid having the total carbon number of the site excluding the acid group of 10 or more / the inorganic 2. The resin composition according to claim 1, wherein the protonic acid]) is 3/7 or more and 7/3 or less.

The invention according to claim 3
A resin molded product for an image forming apparatus, which is molded using the resin composition according to claim 1.

The invention according to claim 4
The resin molded product for an image forming apparatus according to claim 3, which has a roll shape.

The invention according to claim 5
The resin molded product for an image forming apparatus according to claim 3, wherein the resin molded product is a belt shape.

The invention according to claim 6
6. The resin molded product for an image forming apparatus according to claim 3, which is used for a charging roll, an intermediate transfer belt, a recording medium conveyance belt, a fixing belt, or a transfer roll. .

The invention according to claim 7 provides:
A method for producing a resin molded product for an image forming apparatus according to any one of claims 3 to 6, wherein the resin composition according to claim 1 or 2 is 200 ° C to 300 ° C. It is a manufacturing method of the resin molding for image forming apparatuses characterized by including the process heat-processed at the following temperatures.

The invention according to claim 8 provides:
6. A belt stretcher for an image forming apparatus, comprising: the belt-shaped resin molded product according to claim 5; and a plurality of stretching members that stretch the belt-shaped resin molded product from the inner surface side. Device.

The invention according to claim 9 is:
A process cartridge for an image forming apparatus comprising the resin molded product according to any one of claims 3 to 6.

The invention according to claim 10 is:
An image forming apparatus comprising the process cartridge according to claim 9.

The invention according to claim 11 is:
An image forming apparatus comprising the belt stretching device according to claim 8.

ADVANTAGE OF THE INVENTION According to this invention, when a resin molding is shape | molded, the adjustment of the resistance value in an initial stage is easy, and the resin composition which can suppress the raise of a resistance value with time can be provided.
Moreover, according to this invention, the resin molding using the said resin composition and its manufacturing method can be provided. Furthermore, according to the present invention, it is possible to provide a process cartridge for an image forming apparatus, a belt stretching apparatus, and an image forming apparatus using the resin composition.

<Resin composition>
The resin composition according to the present embodiment is configured to include an organic acid having a total carbon number of 10 or more in a portion excluding acid groups, an inorganic protonic acid, a conductive polymer, and a resin.
When the resin composition has the above-described configuration, it is easy to adjust the resistance value in the initial stage when the resin composition is molded using the resin composition, and the effect of suppressing an increase in the resistance value during repeated use. Play.

The following reason is presumed as one of the causes for obtaining the above effect.
That is, since the inorganic protonic acid excellent in resistance adjustment penetrates into the inside of the conductive polymer, it has an advantage that the initial resistance value can be easily adjusted when a resin molded product is molded. In the case of bonding near the surface of the metal, there is a drawback that it is easily affected by disturbances, it is difficult to maintain the doping effect, and resistance is likely to increase during heating and repeated use. On the other hand, the organic acid having a total carbon number of 10 or more excluding the acid group can prevent the influence of disturbance when molding a resin molded product due to its bulkiness, and can easily maintain a resistance value. On the other hand, it has a drawback that it does not easily penetrate into the inside of the conductive polymer and hardly contributes to the initial resistance value. Therefore, by using these acids in combination, it is possible not only to obtain the advantages of each at the same time, but also to make up for each of the disadvantages of each, resulting in ease of initial resistance adjustment and repeated use. It is presumed that it is possible to achieve coexistence with the suppression of the increase in resistance value.

Hereinafter, each component of the resin composition will be described.
The resin composition according to the present embodiment includes, as a dopant for the conductive polymer, at least one organic acid having a total carbon number of 10 or more excluding acid groups and at least one inorganic protonic acid. contains.

[Organic acid in which the total number of carbon atoms in the site excluding the acid group is 10 or more]
The resin composition according to the present embodiment contains at least one organic acid (hereinafter, also referred to as “dopant A”) having a total carbon number of 10 or more in the portion excluding the acid group.
That is, the dopant A has at least one acid group in one molecule. A plurality of acid groups may be contained in one molecule of the dopant A.
Examples of the acid group include a sulfo group, a carboxyl group, a phosphoric acid group, and a hydroxyl group. Among these, a sulfo group is preferable from the viewpoint of obtaining the above effect more effectively.

Further, the dopant A preferably has at least one hydrocarbon group having a total carbon number of 10 or more in one molecule.
Examples of the hydrocarbon group having a total carbon number of 10 or more include a linear or branched chain or cyclic alkyl group, a linear or branched chain or cyclic alkenyl group, a linear or branched chain or cyclic alkynyl group. , An aryl group, or a combination of these, a group having a total carbon number of 10 or more.
Among them, from the viewpoint of obtaining the above effect more effectively, an aryl group substituted with a linear or branched alkyl group, preferably a group having a total carbon number of 10 or more, and substituted with a linear alkyl group An aryl group having a total carbon number of 10 or more is more preferable.

  The hydrocarbon group having 10 or more carbon atoms may be substituted with a substituent other than the acid group and the hydrocarbon group.

Although the preferable specific example of the organic acid whose total carbon number of the site | part except an acid group is 10 or more is shown below, it is not limited to these.
For example, aminonaphtholsulfonic acid, allylsulfonic acid, laurylsulfuric acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, naphthalenesulfonic 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, dibutylbenzenesulfone Acid, methylnaphthalenesulfonic acid, ethylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, pentylnaphthalene Sulfonic acid, hexylnaphthalenesulfonic acid, heptylnaphthalenesulfonic acid, octylnaphthalenesulfonic acid, nonylnaphthalenesulfonic acid, decylnaphthalenesulfonic acid, undecylnaphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, pentadecylnaphthalenesulfonic acid, octadecylnaphthalenesulfonic acid, Dimethylnaphthalenesulfonic acid, diethylnaphthalenesulfonic acid, dipropylnaphthalenesulfonic acid, dibutylnaphthalenesulfonic acid, dipentylnaphthalenesulfonic acid, dihexylnaphthalenesulfonic acid, diheptylnaphthalenesulfonic acid, dioctylnaphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, trimethylnaphthalene Sulfonic acid, triethylnaphthalenesulfonic acid, tripropylnaphthalenesulfonic acid, Li butyl naphthalenesulfonic acid, camphorsulfonic acid, acrylamide -t- butyl sulfonic acid, and thymol blue, and the like.
Furthermore, examples of the polybasic acid include polyvinyl sulfonic acid, polyvinyl sulfuric acid, polystyrene sulfonic acid, sulfonated styrene-butadiene copolymer, polyallyl sulfonic acid, polymethallyl sulfonic acid, poly-2-acrylamido-2-methyl. Examples thereof include propane sulfonic acid and polyisoprene sulfonic acid.
Of these, dodecylbenzenesulfonic acid is particularly preferable.

[Inorganic protonic acid]
The resin composition according to the present embodiment contains at least one inorganic protonic acid (hereinafter also referred to as “dopant B”).
There are no particular limitations on the type of inorganic protonic acid, and examples include phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, hydrobromic acid, boric acid, carbonic acid, and perchloric acid.
Among these, phosphoric acid, hydrochloric acid, and sulfuric acid are preferable, and phosphoric acid is more preferable.

The dopant A or the dopant B preferably includes at least one acid having the following acid dissociation constant.
That is, it is preferable to use a protonic acid having an acid dissociation constant pKa of 5 or less, and a protonic acid having a pKa in the range of 1 to 4 is particularly preferably used. As the form of the protonic acid, any form of acid such as monobasic acid, dibasic acid, tribasic acid, and polybasic acid can be used. For example, in the case of phosphoric acid which is a tribasic acid, the pKa of three protons contained in phosphoric acid is: pKa1 = 2.1, pKa2 = 7.2, pKa3 = 12.3, and two protons In this embodiment, phosphoric acid is added in a controlled manner so that only one proton is used as an effective protonic acid for the structural unit of polyaniline. As the type of proton acid, for example, a sulfonic acid compound, a carboxylic acid compound, and a phosphonic acid compound are preferably used.

[Preferred form of dopant]
As a preferable combination of the dopant A and the dopant B described above, from the viewpoint of obtaining the above effect more effectively, the dopant A is an organic acid having an aryl group substituted with a linear alkyl group (more preferably , Dodecylbenzenesulfonic acid), and the dopant B is preferably phosphoric acid.

Next, from the viewpoint of obtaining the above effect more effectively, preferable addition amounts of the dopant A and the dopant B will be described.
That is, the molar ratio of the dopant A to the dopant B [the dopant A / the dopant B] in the resin composition is preferably 3/7 or more and 7/3 or less, and preferably 5/5 or more and 7/3 or less. Is more preferable.
The total amount of dopant A and dopant B in the resin composition is preferably 0.25 mol or more and 1.2 mol or less, and 0.25 mol or more, with respect to 1 mol of the repeating unit of the conductive polymer. 0.75 mol or less is more preferable.

[Conductive polymer]
The resin composition according to this embodiment contains at least one conductive polymer.
The particle size of the conductive polymer is preferably 0.1 μm or more and 1.0 μm or less.
Examples of the conductive polymer include polyaniline, polypyrrole, polythiophene, etc. Among them, polyaniline is preferable. The polyaniline in this embodiment is used as a conductive material as described above, and the synthesis and structure of the polyaniline are described in detail in JP-A-3-28229.
The polyaniline in this embodiment can be easily produced from aniline or an aniline derivative by oxidative polymerization. As shown below, the structural unit in the main chain of polyaniline is supposed to take four structures of A: leuco emeraldine, B: emeraldine, C: pernigraniline, D: emeraldine salt by oxidation-reduction.

Of these, polyaniline having an emeraldine structure is most useful because it has the highest electrical conductivity during doping and is stable in air. Since polyaniline is usually easily oxidized, it is preferable that there is less perniguraniline structure in order to improve and stabilize conductivity, and it can be efficiently doped by doping from a reduced state. In this embodiment, the resin composition which can form the intermediate transfer body of this embodiment is obtained by carrying out the reduction process using a reducing agent, melt | dissolving in a solvent, and performing a doping process.
Here, as the reducing agent, phenylhydrazine, hydrazine, hydrazine hydrate, hydrazine compounds such as hydrazine sulfate and hydrazine hydrochloride, and reducing metal hydride compounds such as lithium aluminum hydride and lithium borohydride are preferable. Used.

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 oxidizing agent is allowed to act to conduct oxidative polymerization to produce an oxidized polymer of aniline doped with protonic acid (hereinafter referred to as doped polyaniline). This doped polyaniline can then be obtained by undoping with a basic material.
Moreover, as a commercial item, "Panipol PA" by Panipol is mentioned.

  In addition, since polyaniline is usually easily oxidized, it is preferable that there is less perniguraniline structure in order to improve conductivity and stabilize it, and it can be efficiently doped by doping treatment from a reduced state. In this embodiment, a reducing agent such as phenylhydrazine, hydrazine, hydrazine hydrate, hydrazine compounds such as hydrazine sulfate and hydrazine hydrochloride, and reducible metal hydride compounds such as lithium aluminum hydride and lithium borohydride is used. A reduction treatment, dissolution in a solvent, and a doping treatment are performed to obtain polyaniline in a dedope state.

The addition amount (use amount) of the dedope polyaniline in a resin composition is suitably adjusted with the electrical conductivity made to express. Generally, the added polyaniline is preferably 3 parts by mass or more and 20 parts by mass or less, and more preferably 5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the resin in the resin composition.
Moreover, it is preferable that the number average molecular weights of polyaniline in a dedope state are 4000 or more and 400000 or less.

〔resin〕
The resin composition according to this embodiment contains at least one resin.
Examples of the resin include polyamic acid, polyimide, polyamideimide, and polycarbonate.

(Polyamideimide)
The polyamideimide can be produced by a known method such as an acid chloride method or an isocyanate method.
For example, polyamideimide can be easily produced by stirring the acid component and the diamine in an organic polar solvent while heating at 60 ° C. or higher and 200 ° C. or lower, preferably 100 ° C. or higher and 180 ° C. or lower. .

  Examples of the acid component include trimellitic acid and its acid anhydride or acid chloride, pyromellitic acid, biphenyltetracarboxylic acid, biphenylsulfonetetracarboxylic acid, benzophenonetetracarboxylic acid, biphenylethertetracarboxylic acid, ethylene glycol bistrimellitate, Tetracarboxylic acids such as propylene glycol bis trimellitate and their anhydrides, oxalic acid, adipic acid, malonic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, dicarboxypolybutadiene, dicarboxypoly (acrylonitrile-butadiene), di Aliphatic dicarboxylic acids such as carboxypoly (styrene-butadiene), 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 4,4'-dicyclohexylmethane dicar Examples include alicyclic dicarboxylic acids such as acid and dimer acid, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, and naphthalenedicarboxylic acid. Among these, reactivity, heat resistance And cyclohexanedicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid are preferable from the viewpoints of solubility and solubility.

  Examples of the diamine (diisocyanate) include aliphatic diamines such as ethylenediamine, propylenediamine, and hexamethylenediamine, and diisocyanates thereof, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, isophoronediamine, and 4,4′-diaminodicyclohexylmethane. Alicyclic diamines such as these and their diisocyanates, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, benzidine, o- Examples include aromatic diamines such as toridine, 2,4-tolylenediamine, 2,6-tolylenediamine, and xylylenediamine, and diisocyanates thereof. Properties, etc. solubility of 4,4'-diaminodiphenylmethane (diisocyanate), isophorone diamine (diisocyanate), 4,4'-diaminodicyclohexylmethane (diisocyanate) and the like are preferable.

  Examples of the organic polar solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphortriamide and the like. These organic polar solvents can be mixed with phenols such as cresol, phenol, and xylenol, and hydrocarbons such as hexane, benzene, and toluene as necessary. These solvents can be used alone or in two kinds. It can be used as a mixture of the above.

(Polyamic acid)
The polyamic acid is obtained by polycondensation of tetracarboxylic dianhydride and a diamine compound. For example, the polyamic acid is obtained by polymerizing a substantially equimolar amount of the amphoteric component in an organic polar solvent. It is. In addition, the polyamic acid may be partially imidized.
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 butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic 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, An aliphatic or alicyclic tetracarboxylic dianhydride 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 embodiment is preferably an aromatic tetracarboxylic dianhydride, and more preferably pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic. Acid 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-a 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-diaminoheptamethyle Diamine, 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylene methylene 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 embodiment include p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, and 4,4′-diaminodiphenylsulfone. Are 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 embodiment, what consists of aromatic tetracarboxylic dianhydride and aromatic diamine is preferable. Furthermore, what consists of biphenyltetracarboxylic dianhydride and oxydianiline 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-
The solid content concentration in the reaction solution during the polyamic acid polymerization is not particularly specified, but is preferably 5% by mass or more and 50% by mass or less, and particularly preferably 10% by mass or more and 30% by mass or less. When the solid content concentration is less than 5% by mass, the polymerization degree of the polyamic acid is low, and the strength of the finally obtained molded product may be 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 may be generated and the reaction may not proceed.

~ Polyamic acid polymerization temperature ~
The reaction temperature during the polyamic acid polymerization is preferably 0 ° C or higher and 80 ° C or lower. If the reaction temperature is 0 ° C. or lower, the viscosity of the solution may increase, and the reaction system may not be sufficiently stirred. Further, when the reaction temperature is higher than 80 ° C., a part of imidization reaction may occur in parallel with the polymerization of polyamic acid, which may cause a problem in terms of reaction control.

〔solvent〕
The resin composition according to this embodiment may contain at least one solvent.
The solvent is not particularly limited. For example, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, N, N-dimethylacetamide, N , N-diethylacetamide and other acetamide solvents, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone and other pyrrolidone solvents, phenol, o-, m-, or p-cresol, xylenol, halogenated phenol , Phenol solvents such as catechol, ether solvents such as tetrahydrofuran, dioxane and dioxolane, alcohol solvents such as methanol, ethanol and butanol, cellosolve such as butyl cellosolve or hexamethylphosphoramide, γ-butyro Etc. can be exemplified lactone, but it is desirable to use them alone or as a mixture, further, xylene, aromatic hydrocarbons such as toluene can be used.

This solvent may be used in preparing the resin composition. 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 composition is preferably adjusted in the range of 10 to 50 parts by mass.

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

〔Additive〕
Moreover, carbon black etc. are mentioned as an arbitrary component (additive) which can be added to a resin composition.

(Carbon black)
Carbon black, which is an optional component, is used, for example, for the purpose of adjusting the resistance value of a resin molded product obtained using the resin composition.
For example, when using a polyamic acid composition 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. 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 parts by mass or more and 10 parts by mass or less of carbon black, the effect can be exhibited to the maximum, and the in-plane unevenness and electric field dependency of the surface resistivity can be remarkably improved.

  Although the resin composition has been described above, the present invention is not limited only to these embodiments, and various improvements, changes, and modifications are made based on the knowledge of those skilled in the art without departing from the spirit of the resin composition. Can be implemented.

<Resin molding for image forming apparatus and method for producing the same>
The resin molded product for an image forming apparatus according to the present embodiment is molded using the above-described resin composition. At this time, a form formed into a roll shape or a belt shape is preferable.

The roll-shaped resin molded product for an image forming apparatus can be applied to a charging roll or a transfer roll.
Further, the resin molded product for the belt-shaped image forming apparatus can be applied to an intermediate transfer belt, a recording medium conveyance belt, a fixing belt, or the like. The belt can be stretched on a plurality of rotatable stretching members to form a belt stretching device.

Hereinafter, the example of the manufacturing method of an endless belt is demonstrated as an example of the manufacturing method of a resin molding.
The manufacturing method of the endless belt can be roughly divided into the following four forms (1) to (4).
(1) The above-mentioned resin composition is applied in a liquid form, a cylindrical mold is used, the resin composition is applied to the inside or outside of the mold, heat-treated and dried or cured, and then from the mold. It is a form which is taken out and is a seamless endless belt.
(2) The above-described resin composition is heat-treated, extruded through a ring die or the like, cut into an appropriate length, and formed into a seamless endless belt.
(3) The above resin composition is heat-treated, extruded into a film shape from a T-die or the like, cut into an appropriate size, and opposite ends are joined together to form an endless belt.
(4) The above resin composition is made into a coating liquid, the resin composition is formed into a film by extrusion coating such as a T-die, heat-treated and dried or cured to form a sheet, and then the sheet is required It is a form which cuts out to a large size and joins both opposite ends to each other to form an endless belt.

Hereinafter, specific examples in the case of using the polyamideimide resin composition will be described with respect to the form (1).
This form is a form having a heating step of heating the polyamideimide resin composition at a maximum temperature of 200 ° C. or higher and 300 ° C. or lower.

Specifically, first, the polyamideimide resin composition is applied to the inner surface or the outer surface of a cylindrical mold that is a cylindrical substrate (application step).
Instead of the mold, cylindrical molds 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, a ceramic coat or the like on the surface of the mold or mold, and to use a silicone-based or fluorine-based release agent.
In addition, by moving the film thickness control mold with the clearance adjusted to the cylindrical mold parallel through the cylindrical mold, the excess solution is eliminated and the thickness of the solution on the cylindrical mold is uniform. You may apply the method. Here, as long as the uniform thickness control of the coating liquid is performed at the stage of applying the coating liquid onto the cylindrical mold, it is not particularly necessary to use a film thickness control mold.

Next, in order to volatilize 30% by mass or more, preferably 50% by mass or more, of the solvent in the polyamide-imide resin composition by placing the cylindrical mold coated with the polyamide-imide resin composition in an environment where it is heated while rotating. Is dried (primary drying treatment).
At this time, the drying temperature is preferably in the range of 50 ° C. or higher and 150 ° C. or lower.

Further, the cylindrical mold is heated at a maximum temperature of at least 200 ° C. to 300 ° C. for 10 minutes to 60 minutes to volatilize the solvent (secondary drying treatment).
In addition, this secondary drying process is corresponded to the process of heat-processing of the manufacturing method of a resin molding. Hereinafter, this secondary drying process is appropriately referred to as a heating process.

  In the heating step, when the maximum temperature is lower than 200 ° C., the primary drying process and the secondary drying process of the obtained semiconductive member may be insufficient, and the mechanical characteristics may be deteriorated. In the heating step, when the maximum temperature exceeds 300 ° C., degradation of polyaniline may cause degradation of mechanical properties of the obtained semiconductive member, and conductivity efficiency may be reduced. .

  It is preferable that the maximum temperature in the heating step is set to 200 ° C. or more and 300 ° C. or less as appropriate depending on the film thickness of the obtained member and the heat transfer state of the mold.

  In addition, if the solvent remains in the coating film made of the polyamideimide composition applied on the cylindrical mold, the coating film may swell, so that it remains completely until the maximum temperature is reached. It is preferable to remove the solvent. For this reason, in this heating process, it is preferable to raise the temperature stepwise up to the maximum temperature or slowly.

In addition, the maximum temperature holding time in this heating step varies depending on the film thickness of the obtained member, the heat transfer state of the mold, and the maximum temperature, but it may be 10 minutes or more, and specifically satisfies the following relationship. That's fine.
That is, in the heating step, the maximum temperature X (° C.) when heating the polyamideimide resin composition and the maximum temperature holding time Y (hr) are related to the relationship between the reaction rate and temperature of the Arrhenius rule. Based on
(Formula) Y · 2 ^{(X−200) / 10} It is sufficient that the relationship of ≦ 128 is satisfied.

If the value indicated by “Y · 2 ^{(X−200) / 10} ” is greater than 128, there may be a problem that the polyaniline is poorly conductive and the polyaniline is thermally deteriorated.

  After the heating step, the polyamideimide resin can be removed from the cylindrical mold to obtain a semiconductive member.

Next, in the methods (3) and (4) described above, a configuration in which opposite ends are joined together will be described.
As the configuration, (a) a puzzle cut seam (see, for example, JP-A-11-325189, JP-A-8-99737, JP-A-2000-145895) in which one end and the other end are engaged with each other, b) an overlap seam (see, for example, JP-A-2000-66907) in which one end and the other end are overlapped with each other, (c) a butt seam in which one end and the other end are brought into contact with each other (eg, actual open flat 4) -70668, JP-A-11-282260, JP-A-2001-215817), and the like.
Among the above, from the viewpoint of reducing the level difference of the seamed part, the viewpoint of the strength of the seamed part, the viewpoint of improving the positional accuracy and reducing the banding when the formed endless belt is used repeatedly, (a) puzzle cut Seams are preferred.

Here, (a) A preferred form of the puzzle cut seam will be described with reference to FIGS.
FIG. 1 is a view showing a state in which puzzle cut seams are provided at one end 1 and the other end 2 of a belt-shaped resin molded product. By the puzzle cut seam, the one end 1 and the other end 2 are engaged with each other and joined to form an endless belt.
At this time, as shown in FIG. 2, the auxiliary sheet agent 4 can be reinforced along the meshing portion (joining portion) 3. As the auxiliary sheet agent 4, a thermoplastic or thermosetting sheet adhesive may be used, but from the viewpoint of productivity, etc., an auxiliary sheet agent made of the same material as the resin molded product is used for ultrasonic welding. Thus, it is preferable to weld the one end 1, the other end 2, and the auxiliary sheet agent 4 together.
Further, as shown in FIG. 3, it is preferable that the meshing portion (joining portion) 3 is inclined with respect to the circumferential direction L of the belt-shaped resin molded product. The inclination angle θ (acute angle) of the meshing portion (joining portion) 3 with respect to the width direction of the belt-shaped resin molded product at this time is preferably 2 ° or more and 5 ° or less.

In the above methods (3) and (4), as means for fixing the joining portion, (A) the joining portion is heated with a thermoplastic or thermosetting sheet-like adhesive by using hot pressure. Means for fixing (for example, see JP-A-11-325189, JP-A-8-99737, JP-A-2000-145895), (B) ultrasonic waves for welding and fixing a splicing portion using ultrasonic waves There are welding means (for example, see JP-A-2001-187423, JP-A-4-70668, JP-A-11-282260, JP-A-2001-215817).
Among the above, from the viewpoint of reducing the level difference of the seamed part, the viewpoint of the strength of the seamed part, the viewpoint of improving the positional accuracy when the formed endless belt is repeatedly used and reducing the banding, etc., (B) Ultrasound Welding means are preferred.
(B) As the ultrasonic welding machine used for the ultrasonic welding means, various ultrasonic welding machines provided by Branson (Nippon Emerson Corporation) and Prosonic Corporation can be used. The frequency of the vibrator (converter) of the ultrasonic welder is preferably high, and is preferably 40 kHz or more. A larger output is better, preferably 800 W or more, and more preferably 1000 W or more.

The manufacturing method of the endless belt has been described above, but the manufacturing method is not limited to the endless belt, but can be similarly applied to other resin moldings such as a charging roll, an intermediate transfer belt, a recording medium conveyance belt, and a fixing belt.
That is, the resin molded product according to the present embodiment can be manufactured including a step of heat-treating the resin composition at 200 ° C. or more and 300 ° C. or less. When the dopant A is not contained in the resin composition and only the dopant B is contained, the doping effect is lost by the heat treatment in the temperature range, and the resistance value of the formed resin molding may be increased. By using both dopant A and dopant B in combination, it is possible to suppress an increase in resistance value.

The temperature of the heat treatment needs to be 200 ° C. or higher and 300 ° C. or lower, and more preferably 200 ° C. or higher and 250 ° C. or lower.
Further, the heat treatment may be performed at any time after the resin composition is prepared, but preferably after the primary drying treatment at 150 ° C. or less, 200 ° C. or more and 300 ° C. or less (preferably 200 or more and 250 ° C. The following heat treatment is preferably performed.

  Since the resin molded product described above is formed using the above-described resin composition, it exhibits an appropriate resistance value in the initial stage and suppresses an increase in resistance value during repeated use. For this reason, when applied to an image forming apparatus, it contributes to an improvement in image quality during initial use and repeated use.

<Process cartridge for image forming apparatus, image forming apparatus>
The image forming apparatus according to the present embodiment may have any configuration as long as it includes the resin molded product. Specifically, for example, a monocolor electrophotographic apparatus that forms a single-color (usually black) image in the apparatus, or a color electrophotographic apparatus that sequentially repeats primary transfer of a toner image carried on a photoreceptor onto an intermediate transfer belt Alternatively, it may be any of tandem type color electrophotographic apparatuses in which a plurality of photoconductors each having a developing device for each color are arranged in series on an intermediate transfer belt.
Since the process cartridge for an image forming apparatus and the image forming apparatus provided with the resin molded product include the resin molded product, the image forming apparatus can exhibit excellent image performance at the initial and repeated use.

  FIG. 4 is a schematic diagram showing a preferred embodiment of the image forming apparatus. An image forming apparatus 100 shown in FIG. 4 includes, in an image forming apparatus main body (not shown), a process cartridge 20 including an electrophotographic photosensitive member 10, an exposure device (latent image forming device) 30, a transfer device 40, and an intermediate device. A transfer body 50. In the image forming apparatus 100, the exposure device 30 is disposed at a position where the electrophotographic photosensitive member 10 can be exposed from the opening of the process cartridge 20, and the transfer device 40 is interposed between the electrophotographic photosensitive member via the intermediate transfer member 50. The intermediate transfer member 50 is disposed so as to be in contact with the electrophotographic photosensitive member 10 while being in contact therewith.

  The process cartridge 20 is integrated in the case with the electrophotographic photosensitive member 10 together with the charging device 21, the developing device 25, the cleaning device 27, and the fibrous member (flat brush shape) 29, and is attached to the image forming apparatus main body by a mounting rail. It can be attached. The case is provided with an opening for exposure.

The above-described resin molded product can be applied to the charging device 21 in FIG.
The developing device 25 develops the electrostatic latent image on the electrophotographic photoreceptor 10 to form a toner image.

  The cleaning device 27 includes a fibrous member (roll shape) 27a and a cleaning blade (blade member) 27b. In the cleaning device 27 shown in FIG. 4, the fibrous member 27 a and the cleaning blade 27 b are provided, but the cleaning device 27 may include either one. The fibrous member 27a may have a toothbrush shape in addition to the roll shape. Further, the fibrous member 27a may be fixed to the cleaning device main body, may be supported so as to be rotatable, and may be supported so as to be capable of reciprocating in the photosensitive member axial direction.

The cleaning device 27 is required to remove deposits (for example, discharge products) on the surface of the photoreceptor with a cleaning blade and a cleaning brush, and the fibrous member 27a includes metal soap, higher alcohol, wax, silicone oil, and the like. It is preferable to supply the lubricating component (lubricating component) 14 to the surface of the electrophotographic photosensitive member.

  The process cartridge 20 described above is detachable from the image forming apparatus main body, and constitutes the image forming apparatus together with the image forming apparatus main body.

  The exposure device 30 may be any device that exposes the charged electrophotographic photoreceptor 10 to form an electrostatic latent image. Further, it is preferable to use a multi-beam surface emitting laser as the light source of the exposure apparatus 30.

  As the transfer device 40, the toner image on the electrophotographic photosensitive member 10 is a transfer medium (in FIG. 4, an intermediate transfer body 50 is shown as the transfer medium. However, instead of the intermediate transfer body 50, a recording medium conveying belt (FIG. Or a sheet for direct transfer without using the intermediate transfer member 50). A commonly used roll shape is used.

As the intermediate transfer member 50, the above-described resin molded product can be applied to form a belt shape (for example, the above-mentioned endless belt). As the form of the intermediate transfer member 50, a drum-shaped member can be used in addition to the belt-shaped member.
When a recording medium conveyance belt is used instead of the intermediate transfer member 50, the above-described resin molded product can be applied to the recording medium conveyance belt.

  The transfer medium referred to in this embodiment is not particularly limited as long as it is a medium that transfers a toner image formed on the electrophotographic photoreceptor 10. For example, when transferring directly from the electrophotographic photoreceptor 10 to paper or the like, paper or the like is a transfer medium, and when the intermediate transfer body 50 is used, the intermediate transfer body is a transfer medium.

  FIG. 5 is a schematic diagram illustrating another embodiment of the image forming apparatus. In the image forming apparatus 110 shown in FIG. 5, the electrophotographic photosensitive member 10 is fixed to the image forming apparatus main body, and the charging device 22, the developing device 25, and the cleaning device 27 are respectively formed into cartridges. It is provided independently as a cleaning cartridge. Note that the charging device 22 in FIG. 5 includes a charging device that charges by a corona discharge method, but may be a contact-type charging device.

  In the image forming apparatus 110, the electrophotographic photosensitive member 10 and other devices are separated, and the charging device 22, the developing device 25, and the cleaning device 27 are not fixed to the image forming apparatus main body, for example, drawn out, Detachable by push-in operation.

  In the electrophotographic photosensitive member of this embodiment, it may be unnecessary to form a cartridge. Therefore, the charging device 22, the developing device 25, or the cleaning device 27 is not fixed to the main body, and can be detached and attached by an operation by pulling out and pushing in, thereby reducing the member cost per print. Can do. Further, two or more of these devices can be detachable as an integrated cartridge.

  The image forming apparatus 110 has the same configuration as that of the image forming apparatus 100 except that the charging device 22, the developing device 25, and the cleaning device 27 are each formed as a cartridge.

  FIG. 6 is a schematic diagram illustrating another embodiment of the image forming apparatus. The image forming apparatus 120 is a tandem full-color image forming apparatus equipped with four process cartridges 20. In the image forming apparatus 120, four process cartridges 20 are arranged in parallel on the intermediate transfer member 50, and one electrophotographic photosensitive member can be used for one color. The image forming apparatus 120 has the same configuration as that of the image forming apparatus 100 except that it is a tandem system.

  EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited at all by these Examples. In the following examples, “part” means part by mass.

[Example 1]
<Preparation of polyaniline solution>
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, add and mix 434 g of concentrated sulfuric acid (4.295 mol, 97% concentrated sulfuric acid), a protonic acid having an acid dissociation constant pka value of 4.0 or less, with 1493 g of ion-exchanged water while cooling with ice water. A sulfuric acid aqueous solution was prepared. This sulfuric acid aqueous solution was gradually added to the aniline solution while cooling with ice.

Next, an oxidizing agent aqueous solution in which 980 g (4.295 mol) of ammonium peroxodisulfate was dissolved in 2300 g of ion-exchanged water was gradually added dropwise to the aniline solution while cooling with ice at −4 ° C. or lower. After dropping, the colorless and transparent solution changed from greenish blue to blackish green as the oxidative polymerization progressed, 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 L of 2N ammonia water, and the mixture was stirred with an auto homomixer at a rotation speed of 5000 rpm for 5 hours, whereby a polyaniline dispersion in a dedope state (concentration: 7% by mass) ) The dispersion was filtered with a Buchner funnel, washed with distilled water, and further washed with acetone until neutral. Thereafter, the powder was dried for 10 hours to obtain 280 g of a black-brown dedope powder. 50 g of this powder was dissolved in 950 g of N-methyl-2pyrrolidone to obtain a 5% by mass dedope polyaniline solution.

<Preparation of coating liquid (polyamideimide resin composition)>
A solution obtained by adding 0.7 mol of dodecylbenzenesulfonic acid and 0.3 mol of phosphoric acid to 300 g of the dedope polyaniline solution prepared by the above method was used as an N-methyl-2-pyrrolidone solution of polyamideimide resin (Toyobo Co., Ltd.). In addition to 900 g of Viromax HR16NN (concentration 15% by mass), the mixture was stirred for 30 minutes using a container with stirring blades. This obtained the coating liquid (polyamideimide resin composition) which consists of polyaniline in a dedope state, dodecylbenzenesulfonic acid which is the dopant A, phosphoric acid which is the dopant B, and polyamideimide.

<Manufacture of polyamide-imide endless belt>
The coating solution (polyamideimide resin composition) obtained above was uniformly applied to the surface of an aluminum cylindrical mold having a diameter of 170 mm and a length of 500 mm to a thickness of 640 μm. The cylindrical mold is preliminarily coated with a silicone-based release agent to improve the peelability of the semiconductive member after molding.
Thereafter, a drying process (primary drying process) was performed for 30 minutes at a temperature of 120 ° C. while rotating the cylindrical mold. After the primary drying treatment, the cylindrical mold was placed in an oven, and the temperature was increased stepwise at 200 ° C. for 30 minutes and 260 ° C. for 30 minutes to perform secondary drying treatment (heating step).
Subsequently, the cylindrical mold was allowed to cool at room temperature, the semiconductive member was removed from the mold, and a polyamideimide endless belt having a thickness of 80 μm was obtained.

<Evaluation>

(Measurement of surface resistivity)
About the polyamideimide endless belt obtained above, the initial surface resistivity (before being incorporated into the following device) and the surface resistance after passing 100,000 sheets as an intermediate transfer belt in Fuji Xerox's electrophotographic device (DocuCentreColor400CP) The rate was measured respectively.
The surface resistivity is a numerical value obtained by dividing the potential gradient in the direction parallel to the current flowing along the surface of the belt by the current per unit width of the surface. This numerical value is equal to the surface resistance between two electrodes each having an opposite side of a square of 1 cm on each side as an electrode. The unit of surface resistivity is formally (Ω), but is generally written as (Ω / □) to distinguish it from simple resistance. Therefore, in this application, (Ω / □) and (Ω / cm ² ) are equivalent units.
The surface resistivity of the obtained polyamide-imide endless belt was measured using an R8340A digital ultra-high resistance / microammeter (manufactured by Advantest Co., Ltd.), and a UR probe MCP with a double ring electrode structure modified for R8340A. -HTP12 and register table UFL MCP-ST03 (both manufactured by Dia Instruments Co., Ltd.) were used, and the test was performed in accordance with JIS K6911 (1995).
In addition, the belt piece manufactured in the Example and the comparative example was used for the test piece in the case of a measurement.

  On the register table UFL MCP-ST03 (using a fluororesin surface), the test surface 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 weight of 2.00 kg ± 0.10 kg (19.6 N ± 1.0 N) was attached to the top of the UR probe MCP-HTP 12 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 × 10.00.

  Under the conditions of this example, if the initial surface resistivity (log Ω / □) is 9.0 or more and 13.0 or less, it is practically acceptable. Also, under the conditions of this example, if the surface resistivity after processing 100,000 sheets (logΩ / □) −the initial surface resistivity (logΩ / □) is 1.0 or less, it is within a practically acceptable range. is there.

(Image quality evaluation)
The obtained polyamideimide endless belt was incorporated into an electrophotographic apparatus (DocuCentreColor400CP) manufactured by Fuji Xerox Co., Ltd. as an intermediate transfer belt, and image quality evaluation was performed after passing 100,000 sheets.
As the image quality evaluation items, the presence or absence of blur and the presence or absence of black spots were visually confirmed. The evaluation criteria are as follows.

-Presence or absence of blur-
A: The presence of blur is not confirmed at all.
B: Although the presence of blur was confirmed, there was no practical problem.
C: There are many blurs and there are practical problems.
Note that blur refers to toner scattering at the edge of an image.

-Existence of black spots-
A: The presence of black spots is not confirmed at all.
B: Although the presence of black spots was confirmed (1 to 5), there was no practical problem.
C: There are many black spots (6 or more), and there is a problem in practical use.
The black spots were evaluated by printing a white image on the entire surface after passing 100,000 sheets and checking the black spots in the image.

[Examples 2 to 12, Comparative Examples 1 to 3]
In Example 1, an endless belt was produced in the same manner as in Example 1 except that each component of the resin composition was changed as shown in Table 1, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 1.

~ Explanation of terms in Table 1 ~
· Dopant A · · · Organic acid having a total carbon number of 10 or more excluding acid groups · Dopant B · · · Inorganic proton acid · PAI · Polyamideimide · PI · Polyimide

As shown in Table 1, in Examples 1 to 12, when a resin molded product was molded, the initial resistance value was appropriate, and an increase in resistance value over time could be suppressed. In Examples 3 and 4, no blur or black spot was observed even after 200,000 sheets were processed.
On the other hand, in Comparative Example 1 containing no dopant A, and Comparative Example 3 using an organic acid having a total carbon number of less than 10 excluding the acid group instead of the dopant A, an increase in resistance over time was observed. In Comparative Example 2 that did not contain dopant B, the resistance value in the initial stage was high, and both exceeded the practically acceptable range.

It is a schematic diagram which shows the preferable form of the belt-shaped resin molding which concerns on this embodiment. It is a schematic diagram which shows the preferable form of the belt-shaped resin molding which concerns on this embodiment. It is a schematic diagram which shows the preferable form of the belt-shaped resin molding which concerns on this embodiment. 1 is a schematic diagram illustrating an image forming apparatus according to an exemplary embodiment. It is a schematic diagram showing an image forming apparatus according to another embodiment. It is a schematic diagram showing an image forming apparatus according to another embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Electrophotographic photosensitive member 20 Process cartridge 21, 22 Charging device 25 Developing device 27 Cleaning device 30 Exposure device 40 Transfer device 50 Intermediate transfer body 100, 110, 120 Image forming device

Claims (11)

  A resin composition comprising an organic acid having a total carbon number of 10 or more except for an acid group, an inorganic protonic acid, a conductive polymer, and a resin.   The mixing ratio of the organic acid having a total carbon number of 10 or more excluding the acid group and the inorganic protonic acid (molar ratio [the organic acid having the total carbon number of the site excluding the acid group of 10 or more / the inorganic 2. The resin composition according to claim 1, wherein the protonic acid]) is 3/7 or more and 7/3 or less.   A resin molded product for an image forming apparatus, which is molded using the resin composition according to claim 1.   The resin molded product for an image forming apparatus according to claim 3, wherein the resin molded product is a roll shape.   The resin molded product for an image forming apparatus according to claim 3, wherein the resin molded product is a belt shape.   6. The resin molded product for an image forming apparatus according to claim 3, which is used for a charging roll, an intermediate transfer belt, a recording medium conveyance belt, a fixing belt, or a transfer roll.   A method for producing a resin molded product for an image forming apparatus according to any one of claims 3 to 6, wherein the resin composition according to claim 1 or 2 is 200 ° C to 300 ° C. The manufacturing method of the resin molding for image forming apparatuses characterized by including the process heat-processed at the following temperatures.   6. A belt stretcher for an image forming apparatus, comprising: the belt-shaped resin molded product according to claim 5; and a plurality of stretching members that stretch the belt-shaped resin molded product from the inner surface side. apparatus.   A process cartridge for an image forming apparatus, comprising the resin molded product according to any one of claims 3 to 6.   An image forming apparatus comprising the process cartridge according to claim 9.   An image forming apparatus comprising the belt stretching device according to claim 8.

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