JP2019059799A - Imide resin composition, tubular body for image formation device, transfer device, and image formation device - Google Patents

Abstract

To provide an imide resin composition that suppresses electric field dependence when it is made into a resin molding.SOLUTION: An imide resin composition contains a solvent mixture containing an aprotic polar solvent and a proton solvent, an imide resin dissolved in the solvent mixture or a precursor thereof, and a conductive polyaniline where a polyaniline is doped with a dopant, and a ratio of Ma/Mb is more than 0 and 1.95 or less when Ma is a molar content of the dopant and Mb is a molar content of a structural unit represented by a general formula (PA) in the polyaniline. The general formula (PA) is shown as below.SELECTED DRAWING: None

Description

  The present invention relates to an imide resin composition, a tubular body for an image forming apparatus, a transfer apparatus, and an image forming apparatus.

  In an image forming apparatus (such as a copying machine, a facsimile, or a printer) using an electrophotographic method, a toner image formed on the surface of an image carrier is transferred to the surface of a recording medium, and fixed on the recording medium to form an image. Be done. In the transfer device for transferring such a toner image to a recording medium, a tubular body is used as a belt member or the like. And the resin composition containing resin, such as imide type-resin, is used for formation of such a tubular body.

  For example, Patent Document 1 states that “the resin, the conductive polymer, the dopant, and the solvent are contained, and the dopant is 0.1 to 0.75 mol per 1 mol of the repeating unit of the conductive polymer. A resin composition to be contained is disclosed.

  Further, Patent Document 2 discloses an “intermediate transfer member having a function capable of receiving toner transfer, transporting it to another place, and holding the toner until transfer to a recording medium, and (A) polyimide An intermediate transfer member is disclosed which has at least a layer as a main constituent material, and (B) the polyimide layer contains polyaniline and a dopant capable of conducting the polyaniline.

  Moreover, Patent Document 3 “contains a polyamic acid, polyaniline, a dopant for making the polyaniline conductive, and a solvent, and changes in viscosity when held for one week at a temperature of 25 ° C. A polyamic acid composition "is disclosed which is in the range of ± 10 Pas.

  Patent Document 4 also describes that “the terminal amino group is a polyamic acid in which all the terminals are amino groups, and the terminal amino group to the total molar amount (X) of the terminal amino groups not sealed with carboxylic acid monoanhydride is (X) 10% by mass or more and 80% by mass relative to the total solid content of polyamic acid in which the ratio Z / X of the total molar amount (Z) of the terminal sealed with monoanhydride is 0 ≦ Z / X <0.4 Disclosed is a polyamic acid composition comprising carbon black having a pH of less than 7 and a solvent of less than 7%.

  Patent Document 5 also includes “a ratio λg of light transmittance λg for light of wavelength 520 nm and light transmittance λr for light of wavelength 670 nm, which includes polyaniline in a conductive state and a polyamideimide resin. A semiconductive member having a ratio of / λ r of 1 or more is disclosed.

Patent No. 5649765 gazette JP, 2001-109277, A Patent No. 5044907 JP, 2013-57051, A JP 2008-033203 A

  2. Description of the Related Art Conventionally, resin molded articles in which conductive polyaniline doped with a dopant as a conductive agent is added to an imide resin as a conductive agent have been used in resin molded articles that require conductivity such as a tubular body for an image forming apparatus. However, polyaniline tends to form aggregates when doped, and the occurrence of such aggregates may increase the electric field dependency of the resistance in the resin molded product.

  Therefore, an object of the present invention is an imide resin composition containing a solvent, an imide resin or a precursor thereof, and a conductive polyaniline doped and doped, wherein only the aprotic polar solvent is used as the solvent. Imide-based resin composition in which the ratio Ma / Mb of the imide-based resin composition to be contained, or the molar amount Ma of the dopant and the molar amount Mb of the structural unit represented by the following general formula (PA) in polyaniline is over 1.95 Provided is an imide resin composition in which the electric field dependency of the resistance when formed into a resin molded body is suppressed as compared to a resin.

  The above-mentioned subject is solved by the following means. That is,

The invention according to claim 1 is
A mixed solvent containing an aprotic polar solvent and a protic solvent;
An imide resin or its precursor dissolved in the mixed solvent;
When the polyaniline is doped with a dopant, and the molar amount of the dopant is Ma, and the molar amount of the structural unit represented by the following general formula (PA) in the polyaniline is Mb, the ratio Ma / Mb is more than 0. Conductive polyaniline which is 95 or less,
An imide resin composition containing

General formula (PA)

The invention according to claim 2 is
The imide resin composition according to claim 1, wherein the ratio Ma / Mb is 0.5 or more and 1.5 or less.

The invention according to claim 3 is
The imide resin composition according to claim 1 or 2, wherein a content of the conductive polyaniline is 10 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the imide resin or the precursor thereof.

The invention according to claim 4 is
The imide resin composition according to any one of claims 1 to 3, wherein the dopant is an organic acid.

The invention according to claim 5 is
The imide resin composition according to claim 4, wherein the organic acid has an alkyl group having 6 to 20 carbon atoms.

The invention according to claim 6 is
The imide resin composition according to any one of claims 1 to 5, wherein the protic solvent is water.

The invention according to claim 7 is
The imide resin according to any one of claims 1 to 6, wherein the aprotic polar solvent is at least one selected from 1,3-dimethyl-2-imidazolidinone and N-methyl pyrrolidone. Composition.

The invention according to claim 8 is
The mass ratio (protonic solvent / non-protonic polar solvent) of the non-protonic polar solvent to the protic solvent in the mixed solvent is 0.2 / 1 or more and 9/1 or less. The imide type-resin composition of any one of these.

The invention according to claim 9 is
The imide resin composition according to any one of claims 1 to 8, further comprising an organic amine compound.

The invention according to claim 10 is
The organic amine compound is 2-dimethylaminoethanol, 2-diethylaminoethanol, 2-dimethylaminopropanol, pyridine, triethylamine, picoline, N-methylmorpholine, N-ethylmorpholine, 1,2-dimethylimidazole, 2-ethyl- The imide resin composition according to claim 9, which is at least one selected from 4-methylimidazole, N-methylpiperidine, and N-ethylpiperidine.

The invention according to claim 11 is
11. The imide resin according to claim 9, wherein the content of the organic amine compound is 30 mol% or more and 200 mol% or less with respect to the amount of carboxy group in the imide resin or the precursor thereof. Composition.

The invention according to claim 12 is
A tubular body for an image forming apparatus, which is a tubular cured product obtained by curing the imide resin composition according to any one of claims 1 to 11.

The invention according to claim 13 is
The tubular body for an image forming apparatus according to claim 12, wherein a tensile elongation at break of the tubular body for an image forming apparatus is 70.0% or more.

The invention according to claim 14 is
13. The image forming apparatus tubular body according to claim 12, wherein the number of times of bending resistance by the MIT test under the condition of sample width: 15 mm, load: 1 kg, R: 0.38 of broken part of clamp jig is 15,000 or more. Item 13. A tubular body for an image forming apparatus according to item 13.

The invention according to claim 15 is
The ten-point average roughness Rz defined in JIS B 0601 (1994) of the surface of the tubular body for an image forming apparatus is 0.06 μm or more and 0.19 μm or less. The tubular body for an image forming apparatus according to claim 1.

The invention according to claim 16 is
A tubular body for an image forming apparatus according to any one of claims 12 to 15,
A transfer device for transferring a toner image formed on the surface of an image carrier to the surface of a recording medium.

The invention according to claim 17 is
An image carrier,
Toner image forming means for forming a toner image on the surface of the image carrier;
A transfer unit comprising the transfer device according to claim 16, for transferring the toner image to the surface of a recording medium.
An image forming apparatus comprising:

According to the invention of claim 1, 3, 4, 5, 6, 7, 8, 9, 10, or 11, a solvent, an imide resin or a precursor thereof, and a conductive polyaniline doped An imide resin composition containing the imide resin composition containing only an aprotic polar solvent as the solvent, or the structural unit represented by the general formula (PA) in the molar amount Ma of the dopant and polyaniline An imide resin composition is provided in which the electric field dependency of the resistance when formed into a resin molded article is suppressed as compared to an imide resin composition in which the ratio Ma / Mb to the molar amount Mb exceeds 1.95.
According to the invention of claim 2, the ratio Ma / Mb of the molar content Ma of the dopant to the molar quantity Mb of the structural unit represented by the general formula (PA) in polyaniline is less than 0.5 or more than 1.5. The imide type-resin composition which the electric field dependence of resistance at the time of setting it as a resin molding is suppressed compared with the imide type-resin composition which is these is provided.

According to the invention of claim 12, an image is formed as a tubular cured product obtained by curing an imide resin composition containing a solvent, an imide resin or a precursor thereof, and a conductive polyaniline doped. A tubular unit for a device, wherein an imide resin composition containing only an aprotic polar solvent is used as the solvent, or a structural unit represented by the general formula (PA) in the molar amount Ma of the dopant and polyaniline A tubular body for an image forming apparatus is provided in which the electric field dependency of the resistance is suppressed as compared with the case of using an imide resin composition in which the ratio Ma / Mb to the molar amount Mb of Mb exceeds 1.95.
According to the invention as set forth in claim 13, a tubular body for an image forming apparatus having excellent mechanical strength is provided as compared with the case where the tensile elongation at break is less than 70.0%.
According to the invention of claim 14, compared with the case where the number of times of bending resistance by the MIT test under the condition of sample width: 15 mm, load: 1 kg, and R of the bending portion of the clamp jig: 0.38 is less than 15,000. Provided is a tubular body for an image forming apparatus excellent in mechanical strength.
According to the invention of claim 15, the image forming apparatus in which the occurrence of the image quality defect in the image is suppressed as compared with the case where the ten-point average roughness Rz specified in JIS B0601 (1994) is over 0.19 μm. A tubular body is provided.

  According to the invention as set forth in claim 16 or 17, it is a tubular cured product obtained by curing an imide resin composition containing a solvent, an imide resin or a precursor thereof, and a conductive polyaniline doped. A tubular body for an image forming apparatus, wherein the tubular body for an image forming apparatus comprises an imide resin composition containing only an aprotic polar solvent as the solvent, or a general formula of the molar amount Ma and polyaniline contained in the dopant It is formed compared with the case where a tubular body for an image forming apparatus using an imide resin composition having a ratio Ma / Mb to the molar amount Mb of the structural unit represented by PA) exceeds 1.95 is applied. There is provided a transfer device or an image forming device in which the occurrence of ghosts and micro white spots in an image is suppressed.

FIG. 1 is a schematic configuration view showing an example of an image forming apparatus according to the present embodiment.

  Hereinafter, an embodiment which is an example of the present invention will be described.

[Imide-based resin composition]
The imide resin composition according to the present embodiment contains a solvent, an imide resin dissolved in the solvent or a precursor thereof, and a conductive polyaniline.
The solvent is a mixed solvent containing an aprotic polar solvent and a protic solvent.
In conductive polyaniline, polyaniline is doped with a dopant, and the molar amount of dopant contained is Ma, the molar amount of a structural unit represented by the following general formula (PA) in polyaniline (hereinafter simply referred to as "one unit in polyaniline") And Mb is a conductive polyaniline having a ratio Ma / Mb of more than 0 and not more than 1.95.

General formula (PA)

According to the imide resin composition according to the present embodiment, the electric field dependency of the resistance when formed into a resin molded body is suppressed by having the above configuration.
The reason is presumed as follows.

Conventionally, as a member for which conductivity is required such as a tubular body (for example, a tubular body for transfer) for an image forming apparatus, a resin molded body obtained by adding a conductive agent to a resin such as imide resin to impart conductivity is used. It is done. In addition, although electroconductive particles, such as carbon black, are used abundantly as this electroconductive agent, using the electroconductive polyaniline doped by the dopant is also tried in recent years.
However, when polyaniline is protonated by a doping treatment to be in a conductive state, it becomes hydrophilic and becomes difficult to dissolve in an organic solvent. Therefore, when the solvent is volatilized during molding of the resin molded product, aggregation of the conductive polyaniline occurs to generate aggregates, and as a result, the electric field dependency of the conductivity (resistance) of the resin molded product becomes high. there were. The reason that the electric field dependency of the resistance is increased as described above is thought to be that the electric charge hopping conducts between the aggregates to form a conduction path of the electric charge because the aggregates are scattered in the resin molded body. Be
As the electric field dependency of the volume resistance increases, the resistance on the low electric field side increases and the resistance on the high resistance side decreases. If such a resin molded product is temporarily applied to an intermediate transfer member (intermediate transfer tubular member) for an image forming apparatus, the electric field on the low electric field side becomes high resistance, whereby the charge after secondary transfer on the surface of the intermediate transfer member is attenuated. This becomes difficult, and a phenomenon (ghost) may occur in which the density of the image portion formed in the previous image formation is increased. In addition, since the high electric field side has low resistance, an overcurrent flows through the intermediate transfer member when a high voltage is applied at the time of secondary transfer, and a phenomenon (micro white spot) in which an image of the pierced part is white occurs. Sometimes. Furthermore, if aggregates are present, unevenness may occur in the distance between the aggregates due to heating unevenness (temperature unevenness) when curing the resin during molding, and as a result, resistance unevenness occurs in the resin molded product. In addition, uneven charging of the image quality may occur due to uneven charging of the intermediate transfer member.

On the other hand, in the imide resin composition according to the present embodiment, a mixed solvent containing an aprotic polar solvent and a proton solvent is used as the solvent. By using the protic solvent, the anion of the protic solvent is solvated and stabilized with respect to the conductive polyaniline protonated by the doping treatment, and the conductive polyaniline is dissolved on the protic solvent side. As a result, the generation of aggregates of conductive polyaniline is suppressed, and the electric field dependency of the resistance is also reduced.
Also, when the amount of dopant for treating polyaniline is too high, the electric field dependency of the resistance tends to increase too, but in this embodiment, the molar amount of dopant (Ma) and the molar amount of 1 unit in polyaniline (Mb) In this respect, the electric field dependency of the resistance is also reduced because the ratio Ma / Mb of this to the above is 1.95 or less.
From the above points, the electric field dependence of the resistance of the resin molded body is suppressed in the present embodiment. Then, even when this resin molded product is applied to an intermediate transfer member for an image forming apparatus, a phenomenon (ghost) in which the density of the image portion formed in the previous time becomes high or an overcurrent when a high voltage is applied at the time of secondary transfer. Generation of a phenomenon (micro white spot) in which white spots occur in the image. Furthermore, since the occurrence of the aggregate itself is suppressed, the unevenness of the distance between the aggregates due to the heating unevenness at the time of molding is also suppressed, and the generation of the density unevenness of the image quality is also suppressed.

Furthermore, according to this embodiment, a reduction in strength when formed into a resin molded product, precipitation of aggregates on the surface of the resin molded product, high smoothness on the surface of the resin molded product, and the like are also achieved.
It is inferred that this is attributed to the fact that the formation of aggregates of conductive polyaniline is suppressed when the resin molded product is made as described above. That is, if an aggregate is present, the aggregate may become a starting point (breaking point) of crack generation, and as a result, the strength as a resin molded product may be reduced, but the generation of the aggregate itself is suppressed As a result, the generation of cracks is suppressed and the reduction in strength is also suppressed. In addition, the generation of the aggregate itself of the conductive polyaniline is suppressed, and the precipitation of the aggregate on the surface of the resin molded product is also suppressed. Further, the suppression of the generation of the aggregates indicates that the solubility of the conductive polyaniline is improved, and the smoothness of the surface of the resin molded product is improved along with the improvement of the solubility.

  Next, each component of the imide resin composition according to the present embodiment will be described in detail.

(Imide resin or its precursor)
The imide resin composition according to the present embodiment contains at least one of an imide resin and a precursor thereof as a main component. In addition, containing as a main component represents occupying 50 mass% or more with respect to the total solid contained in an imide type-resin composition.
Therefore, the imide resin composition may contain only one of the imide resin or its precursor as the main component (50% by mass or more with respect to the total solid content), or both as the main component (total content is the total solid content To 50% by mass or more).

The imide resin refers to a resin containing a structural unit having an imide bond.
The type of imide resin is not particularly limited, and examples of the imide resin include polyimide resin, polyamide imide resin, and polyether imide resin.

-Polyimide resin As a polyimide resin, the imidate of the polyamic acid (precursor of a polyimide resin) which is a polymer of tetracarboxylic dianhydride and a diamine compound is mentioned, for example. Specifically, as the polyimide resin, an equimolar amount of tetracarboxylic dianhydride and a diamine compound is polymerized in a solvent to obtain a solution of polyamic acid, which is obtained by imidizing the polyamic acid It can be mentioned.

  As a polyimide resin, resin which has a structural unit shown by following General formula (I) is mentioned, for example.

(In the general formula (I), R ¹ is a tetravalent organic group, and is an aromatic group, an aliphatic group, a cyclic aliphatic group, a combination of an aromatic group and an aliphatic group, or a substituted group thereof) R ² is a divalent organic group, and is an aromatic group, an aliphatic group, a cyclic aliphatic group, an aromatic group and a fat. A group in which group groups are combined, or a group in which they are substituted (for example, the residue of the diamine compound described later can be mentioned).

  Specific examples of the tetracarboxylic acid dianhydride include pyromellitic acid dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid. Acid dianhydride, 2,3,3 ', 4-biphenyl tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid Dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,2'-bis (3,4-dicarboxyphenyl) sulfonic acid dianhydride, perylene-3,4,9,10 -Tetracarboxylic acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, ethylene tetracarboxylic acid dianhydride etc. are mentioned.

On the other hand, as specific examples of diamine compounds, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,3'-dichlorobenzidine, 4,4'-diaminodiphenyl sulfide 3,3'-Diaminodiphenyl sulfone, 1,5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, 3,3'-dimethyl 4,4'-biphenyldiamine, benzidine, 3,3'-dimethylbenzidine 3,3'-Dimethoxybenzidine, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenylpropane, 2,4-bis (β-amino tert-butyl) toluene, bis (p-β-amino- Tert-Butylphenyl) ether, bis (p-β-methyl-δ-aminophenyl) benzene, bis p- (1,1-Dimethyl-5-amino-pentyl) benzene, 1-isopropyl-2,4-m-phenylenediamine, m-xylylenediamine, p-xylylenediamine, di (p-aminocyclohexyl) methane Hexamethylenediamine, Heptamethylenediamine, Octamethylenediamine, Nonamethylenediamine, Decamethylenediamine, Diaminopropyltetramethylene, 3-Methylheptamethylenediamine, 4,4-Dimethylheptamethylenediamine, 2,11-Diaminododecane, 1 , 2-bis-3-aminopropoxyethane, 2,2-dimethylpropylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 5-methylnonamethylenediamine, 2, 17-diaminoeicosadecane, 1,4-diaminocyclohexane, 1,10-diamino-1,10-dimethyldecane, 12-diaminooctadecane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, Piperazine, H ₂ N (CH ₂ ) ₃ O (CH ₂ ) ₂ O (CH ₂ ) NH ₂ , H ₂ N (CH ₂ ) ₃ S (CH ₂ ) ₃ NH ₂ , H ₂ N (CH ₂ ) ₃ N (CH ₃ ) ₂ (CH ₂ ) ₃ NH _{2 and the} like.

-Polyamide imide resin As polyamide imide resin, the polymer of trivalent carboxylic acid (tricarboxylic acid) which has an acid anhydride group, and an isocyanate or diamine is mentioned.

  As the tricarboxylic acid, trimellitic anhydride and derivatives thereof are preferable. In addition to tricarboxylic acids, tetracarboxylic dianhydrides, aliphatic dicarboxylic acids, aromatic dicarboxylic acids and the like may be used in combination.

  As the isocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 2,2'-dimethylbiphenyl-4,4'-diisocyanate, biphenyl-4,4'-diisocyanate, biphenyl-3,3'- Diisocyanate, biphenyl-3,4'-diisocyanate, 3,3'-diethylbiphenyl-4,4'-diisocyanate, 2,2'-diethylbiphenyl-4,4'-diisocyanate, 3,3'-dimethoxybiphenyl-4 , 4'-diisocyanate, 2,2'-dimethoxybiphenyl-4,4'-diisocyanate, naphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate and the like. As a diamine, it has a structure similar to said isocyanate, and the compound which has an amino group instead of the isocyanato group is mentioned.

-Polyether imide resin As polyether imide resin, the polymer of aromatic bis (ether dicarboxylic acid) and diamine is mentioned.
As the aromatic bis (ether dicarboxylic acid) acid, 2,2-bis [4- (2,3-dicarboxyphenoxy) phenyl] propane, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl Propane etc. are mentioned.
Examples of the diamine include 4,4'-diaminodiphenylmethane and metaphenylene diamine.

  The weight average molecular weight of the imide resin is preferably 10000 or more and 45000 or less from the viewpoint of compatibility with the conductive polyaniline, the moldability of the resin molded product, and the like.

The weight average molecular weight of the imide resin is measured by gel permeation chromatography (GPC) under the following measurement conditions.
・ Column: Tosoh TSKgel α-M (7.8 mm ID × 30 cm)
Eluent: DMF (dimethylformamide) / 30 mM LiBr / 60 mM phosphoric acid Flow rate: 0.6 mL / min
Injection volume: 60 μL
・ Detector: RI (differential refractive index detector)

(Conductive polyaniline)
The imide resin composition according to the present embodiment includes, as a conductive agent, conductive polyaniline in which polyaniline is doped with a dopant.

  In addition, it is supposed that the structural unit of the main chain of the polyaniline takes four structures of A: leuco emeraldine, B: emeraldine, C: pernigranilin, and D: emeraldine salt depending on the redox state. For example, in the air, oxidation proceeds from A: leuco emeraldine structure to B: emeraldine structure, and B: emeraldine structure to C: pernigraniline structure. In addition, B: the polyaniline having the emeraldine structure is protonated to form the D: emeraldine salt structure, which results in the conductive (doped) polyaniline (conductive polyaniline).

  In this embodiment, B: polyaniline having an emeraldine structure is subjected to a dopant treatment (protonation) to obtain D: an emeraldine salt structure, that is, a conductive (doped) polyaniline (conductive polyaniline). .

-Content ratio of dopant and polyaniline In the imide resin composition, when the molar amount of the dopant is Ma, and the molar amount of the structural unit (1 unit in polyaniline) represented by the general formula (PA) in polyaniline is Mb The ratio Ma / Mb is greater than 0 and less than 1.95.
When the ratio Ma / Mb is more than 0, conductivity can be imparted to the resin molded product formed by the imide resin composition. On the other hand, when the ratio Ma / Mb is 1.95 or less, the electric field dependency of the resistance when formed into a resin molded product is reduced.
The ratio Ma / Mb is more preferably 0.5 or more and 1.5 or less, and more preferably 0.8 or more and 1.2 or less.

As a dopant used for the doping process of polyaniline, it does not specifically limit but a well-known dopant is used, For example, acidic compounds, such as a protonic acid, are preferable.
As a protonic acid preferable as the dopant, for example, in addition to hydrochloric acid and sulfuric acid, organic acids (for example, organic sulfonic acid compounds, organic carboxylic acid compounds and the like) can be mentioned, and organic acids are more preferable.

  Among organic acids, from the viewpoint of excellent conductivity and from the viewpoint of solubility in an aprotic polar solvent, it has an alkyl group, and the alkyl group has 6 to 20 carbon atoms (more preferable). Is more preferably an organic acid having 8 to 16 carbon atoms).

Examples of organic sulfonic acid compounds include amino naphthol 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, octylbenzene sulfone Acid, nonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, octadecylbenzenesulfonic acid, diethylbenzenesulfonic acid, dipropylbenzenesulfonic acid, dibutylbenzenesulfonic acid, methyl Naphthalene sulfonic 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 Decyl naphthalene sulfonic acid, dodecyl naphthalene sulfonic acid, pentadecyl naphthalene sulfonic acid, octadecyl a Talene sulfonic acid, dimethyl naphthalene sulfonic acid, diethyl naphthalene sulfonic acid, dipropyl naphthalene sulfonic acid, dibutyl naphthalene sulfonic acid, dipentyl naphthalene sulfonic acid, dihexyl naphthalene sulfonic acid, diheptyl naphthalene sulfonic acid, dioctyl naphthalene sulfonic acid, dinonyl naphthalene sulfone Examples of the acid include trimethyl naphthalene sulfonic acid, triethyl naphthalene sulfonic acid, tripropyl naphthalene sulfonic acid, tributyl naphthalene sulfonic acid, camphor sulfonic acid, and acrylamido-t-butyl sulfonic acid.
Among these, dodecylbenzenesulfonic acid or phenolsulfonic acid is preferably used.

  Moreover, as an organic carboxylic acid compound, for example, 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, Salicylic acid, 5-aminosalicylic acid, o-methoxybenzoic acid, 1,6-dinitro-4-chlorophenol, 2,6-dinitrophenol, 2,4-dinitrophenol, p-hydroxybenzoic acid and the like.

The protic acid used as a dopant may be a polymeric acid. As such a polymeric acid, for example, polyvinyl sulfonic acid, polyvinyl sulfuric acid, polystyrene sulfonic acid, sulfonated styrene-butadiene copolymer, polyallyl sulfonic acid, polymethallyl sulfonic acid, poly-2-acrylamido-2-methyl Propane sulfonic acid or polyisoprene sulfonic acid may, for example, be mentioned.
Among these dopants, in particular, dodecylbenzenesulfonic acid or phenolsulfonic acid is preferred.

  The conductive polyaniline preferably has a weight average molecular weight of 5,000 or more and 50,000 or less, and more preferably 5,000 or more and 20,000 or less from the viewpoint of conductivity and compatibility with an imide resin.

  The content of the conductive polyaniline in the imide resin layer (the cured product obtained by curing the imide resin composition) is an excellent conductivity when used as a resin molded body with respect to 100 parts by mass of the imide resin or its precursor. From the viewpoint of the properties, 10 parts by mass or more and 30 parts by mass or less are preferable, and 20 parts by mass or more and 30 parts by mass or less are more preferable.

(Organic amine compound)
The imide resin composition preferably contains an organic amine compound from the viewpoint of promoting the imidization of the imide resin or the precursor thereof and from the viewpoint of improving the solubility in the mixed solvent.

The organic amine compound is a compound that amine-chlorides (the carboxy group of) the precursor of the imide resin to increase the solubility in the solvent and also functions as an imidization promoter. The organic amine compound is a non-surface active organic amine compound having no surface activity. Specifically, the organic amine compound may be an organic amine compound having a molecular weight of 170 or less. The organic amine compound is preferably a compound excluding a diamine compound which is a raw material of the polyimide precursor.
The organic amine compound is preferably a water-soluble compound. Here, water solubility means that at 25 ° C., the target substance dissolves in water at 1% by mass or more.

Examples of the organic amine compound include primary amine compounds, secondary amine compounds and tertiary amine compounds.
Among these, as the organic amine compound, at least one selected from secondary amine compounds and tertiary amine compounds (in particular, tertiary amine compounds) is preferable. When a tertiary amine compound or a secondary amine compound is applied as the organic amine compound (especially, a tertiary amine compound), the solubility in a solvent is enhanced, and the storage stability of the imide resin composition is likely to be improved.

  Moreover, as an organic amine compound, the bivalent or more polyvalent organic amine compound is also mentioned other than a monovalent organic amine compound. When a polyvalent organic amine compound having two or more valences is applied, a pseudo crosslinked structure is easily formed between molecules of the imide resin or a precursor thereof, and the storage stability of the imide resin composition is easily improved.

Examples of primary amine compounds include methylamine, ethylamine, n-propylamine, isopropylamine, 2-ethanolamine, 2-amino-2-methyl-1-propanol, and the like.
Examples of secondary amine compounds include dimethylamine, 2- (methylamino) ethanol, 2- (ethylamino) ethanol, morpholine and the like.
Examples of tertiary amine compounds include 2-dimethylaminoethanol, 2-diethylaminoethanol, 2-dimethylaminopropanol, triethylamine, picoline, methylmorpholine, ethylmorpholine and the like.

  Here, as the organic amine compound, an organic amine compound having a nitrogen-containing heterocyclic structure (in particular, a tertiary amine compound) is also preferable from the viewpoint of storage stability. Examples of organic amine compounds having a nitrogen-containing heterocyclic structure include isoquinolines (organic amine compounds having an isoquinoline skeleton), pyridines (organic amine compounds having a pyridine skeleton such as pyridine), pyrimidines (a pyrimidine skeleton Organic amine compound), pyrazines (organic amine compound having a pyrazine skeleton), piperazines (organic amine compound having a piperazine skeleton), piperidines (organic amine compound having a piperidine skeleton, such as N-methylpiperidine, N-ethyl) Piperidine), triazines (organic amine compound having a triazine skeleton), imidazoles (organic amine compound having an imidazole skeleton), polypyridine, polyamine and the like.

  The organic amine compound is preferably at least one selected from the group consisting of morpholines, amino alcohols and imidazoles from the viewpoint of storage stability, and N-methylmorpholine, N-ethylmorpholine, dimethylamino More preferably, it is at least one selected from the group consisting of ethanol, 1,2-dimethylimidazole, and 2-ethyl-4-methylimidazole.

  Among these, as organic amine compounds, 2-dimethylaminoethanol, 2-diethylaminoethanol, 2-dimethylaminopropanol, pyridine, triethylamine, picoline, N-methylmorpholine, N-ethylmorpholine, 1,2-dimethylimidazole, At least one selected from 2-ethyl-4-methylimidazole, N-methylpiperidine and N-ethylpiperidine is preferred.

  The organic amine compound is preferably a compound having a boiling point of 60 ° C. or more (preferably 60 ° C. or more and 200 ° C. or less, more preferably 70 ° C. or more and 150 ° C. or less). When the boiling point of the organic amine compound is 60 ° C. or more, volatilization of the organic amine compound from the imide resin composition during storage can be suppressed, and the decrease in solubility in a solvent can be easily suppressed.

  The organic amine compounds may be used alone or in combination of two or more.

The content of the organic amine compound is 30 mol% or more and 200 mol% or less (preferably 50 mol% or more and 150 mol% or less, based on the amount of carboxy (-COOH) group in the imide resin or its precursor Preferably, it is 80 mol% or more and 120 mol% or less).
By setting the content of the organic amine compound to 30 mol% or more, the solubility in the mixed solvent is easily obtained. On the other hand, when the content of the organic amine compound is 200 mol% or less, the solution stability of the organic amine compound is easily secured, and the unpleasant odor is also easily suppressed.

(Mixed solvent)
The imide resin composition according to the present embodiment contains, as a solvent, a mixed solvent containing an aprotic polar solvent and a proton solvent.

  In addition, a resin molded product (for example, a tubular body for an image forming apparatus, etc.) produced by this imide resin composition is generally coated with the imide resin composition, dried, and optionally fired (imidized) It is formed by doing. Therefore, the mixed solvent may be contained (remaining) as a residual solvent in the resin molded product.

Examples of protic solvents include water (distilled water, ion-exchanged water, ultrafiltered water, pure water etc.), alcohols (eg lower alcohols having 5 or less carbon atoms such as methanol, ethanol, isopropanol etc.), thiols (eg ethane thiol) And lower thiols having 5 or less carbon atoms such as propanethiol.
Among these, water is preferable as the protic solvent.

As the aprotic polar solvent, one having a boiling point of 150 ° C. or more and 300 ° C. or less is preferable, and a solvent having a dipole moment of 3.0 D or more and 5.0 D or less is preferable.
For example, N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N, N-diethylacetamide (DEAc), dimethylsulfoxide (DMSO), hexa Methylenephosphoramide (HMPA), N-methylcaprolactam, N-acetyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone (N, N-dimethylimidazolidinone, DMI) and the like can be mentioned.
Among these, as the aprotic polar solvent, 1,3-dimethyl-2-imidazolidinone and N-methylpyrrolidone are preferable.

The mass ratio of the non-protonic polar solvent to the protic solvent in the mixed solvent (protonic solvent / non-protonic polar solvent) is preferably in the range of 0.2 / 1 or more and 9/1 or less, and 0.3 / 1 or more and 7/1 or less are more preferable, and 0.4 / 1 or more and 6/1 or less are more preferable.
When the mass ratio (protonic solvent / non-protonic polar solvent) is 0.2 / 1 or more, the ratio of the non-protonic polar solvent in the mixed solvent is increased, and the imide resin or its precursor is excellent Solubility is enhanced. On the other hand, when the mass ratio (protonic solvent / non-protonic polar solvent) is 9/1 or less, the proportion of the protic solvent in the mixed solvent is increased, and aggregation of the conductive polyaniline is easily suppressed, and the resin It becomes easy to reduce the electric field dependence of resistance at the time of making it into a forming object.
In the mixed solvent, the non-protonic polar solvent and the protic solvent are preferably main components (that is, the total amount is 50% by mass or more), and the total amount of both solvents is 80% by mass or more More preferably, it is 90 mass% or more, and it is especially preferable that it is 100 mass% or more.

[Resin molded body and tubular body for image forming apparatus]
By curing the imide resin composition according to the present embodiment, a resin molded product is produced. For example, a tubular cured product is obtained to obtain a resin tubular body.

-Application of resin molded body As a use of the resin molded body molded by the imide resin composition according to the present embodiment, first, a tubular body in an image forming apparatus may be mentioned. Specifically, it is applied to a belt member for a transfer device (for example, an intermediate transfer belt, a recording medium conveyance belt, a primary transfer belt, a secondary transfer belt or the like), a belt member for a charging device (for example, a charge belt or the like) . The belt member may be further coated on a roll such as a metal roll or a resin roll to be used as a roll member (roll member for transfer device, roll member for charging device).
Moreover, as applications other than the tubular body for image forming apparatuses of a resin molding, the cylindrical-shaped base material for solar cells etc. are mentioned, for example.

  For example, a transfer device including the tubular body for an image forming apparatus according to the present embodiment is a transfer device that transfers a toner image formed on the surface of an image carrier to the surface of a recording medium, and is a tubular shape for the image forming apparatus. The body is provided as a belt member such as an intermediate transfer belt, a recording medium conveyance belt, a primary transfer belt, a secondary transfer belt, or a roll member such as an intermediate transfer roll, a recording medium conveyance roll, a primary transfer roll, and a secondary transfer roll.

Molding of Tubular Body for Image Forming Apparatus Here, as an example of a molding method of a resin molded body, a molding method of a tubular body for an image forming apparatus (a tubular body having a single layer structure of an imide based resin layer) will be described.
For example, an imide resin composition is applied to the outer peripheral surface (or the inner peripheral surface) of a cylindrical mold, the coated layer is dried, and if necessary, the tubular body for an image forming apparatus having a single layer configuration is baked (imide Are molded by
Examples of the coating method include usual methods such as blade coating method, wire bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method and curtain coating method.

Physical Properties of Tubular Body Preferred physical properties of the tubular body (for example, a tubular body for an image forming apparatus) which is a cured product of the imide resin composition according to the present embodiment will be described.

The tensile elongation at break of the tubular body (for example, a tubular body for an image forming apparatus) is preferably 70.0% or more, more preferably 80.0% or more, and still more preferably 85.0% or more.
When the tensile elongation at break is 70.0% or more, excellent mechanical strength can be obtained, and for example, when it is used as a tubular body in an image forming apparatus, the life can be easily extended.

The Young's modulus of the tubular body (for example, a tubular body for an image forming apparatus) is preferably 2000 MPa or more and 8000 MPa or less, more preferably 2500 MPa or more and 6500 MPa or less, and still more preferably 3000 MPa or more and 5500 MPa or less.
When the Young's modulus is 2000 MPa or more, excellent mechanical strength is obtained. For example, when it is used as a tubular body in an image forming apparatus, deformation at the time of belt walk is suppressed, and the life is easily increased. On the other hand, when the Young's modulus is 8000 MPa or less, for example, when it is used as a tubular body in an image forming apparatus, the stress when the tubular body is strained at the time of belt walk is reduced and the life is easily lengthened.

The Young's modulus (MPa) and the tensile elongation at break (%) are 80 mm × 5 mm in strip shape so that the cylindrical circumferential direction of the belt has a long side using a tensile tester (MODEL-1605N, manufactured by AICO ENGINEERING CO., LTD.) The test piece is cut out, and the length of the test piece between the chuck jigs is 40 mm, and the tensile test is performed according to the method according to JIS K7161 at a tensile speed of 20 mm / min.
Young's modulus is calculated from the slope of the region where the S-S curve is straight (Strain is 10N-38N).
The elongation at break is calculated from the length at the time of breakage in a tensile test.

The number of bending resistances of a tubular body (for example, a tubular body for an image forming apparatus) under the conditions of a sample width: 15 mm, a load: 1 kg, and a bending portion of a clamp jig: R: 0.38 is 15,000 or more. Is preferable, more than 20,000 times is more preferable, and more than 30,000 times is more preferable.
When the number of times of bending resistance is 15,000 or more, excellent mechanical strength can be obtained, and for example, when it is used as a tubular body in an image forming apparatus, the life can be easily extended.

  For the MIT test, using a MIT tester (FT-701, manufactured by Ueshima Seisakusho Co., Ltd.), a sample width of 15 mm is applied, a load of 1 kg is applied thereto, and the test is performed with R = 0.38 of the clamp jig at the broken part. The number of repetitions until breakage is the number of breakage resistance.

The ten-point average roughness Rz of a tubular body (for example, a tubular body for an image forming apparatus) defined in JIS B0601 (1994) is preferably 0.06 μm or more and 0.19 μm or less, and preferably 0.1 μm or more 15 μm or less is more preferable, and 0.1 μm or more and 0.12 μm or less is more preferable.
When the roughness Rz is 0.19 μm or less, the smoothness of the surface of the tubular body is enhanced, and for example, when used as a tubular body in an image forming apparatus, it becomes easy to form an image excellent in image quality. On the other hand, when the roughness Rz is 0.06 μm or more, for example, when used as a tubular body in an image forming apparatus, excessive adhesion with a cleaning material (cleaning blade) for cleaning the surface in contact with the tubular body is prevented. The effect of suppressing the turning up of the cleaning blade is obtained.

  The surface roughness is measured according to JIS B0601 (1994) using a surface roughness meter SURFCOM 575A (manufactured by Tokyo Seimitsu Co., Ltd.) with a measurement length of 2.5 mm, a cutoff wavelength of 0.8 mm, and a measurement speed of 0.6 mm / sec. The measurement is carried out according to a similar method, and the value of the ten-point average roughness Rz is adopted.

The tubular body for an image forming apparatus according to the present embodiment may be a tubular body formed of a single layer of an imide based resin layer which is a cured product of the imide based resin composition according to the present embodiment. It may be a tubular body of a laminate in which another layer is laminated on at least one of the outer peripheral surface side and the inner peripheral surface side by using the imide type resin layer which is a cured product of the imide resin composition as the base material. .
For example, an elastic layer (for example, a silicone rubber layer), a surface layer (for example, a fluorine-containing resin layer), and the like on the outer peripheral surface side of an imide resin layer (cured product of imide resin composition according to the present embodiment) as a substrate It may be an aspect having

[Image forming apparatus]
Next, an image forming apparatus according to the present embodiment will be described.
The image forming apparatus of the present embodiment includes an image carrier, a toner image forming unit that forms a toner image on the surface of the image carrier, and a transfer device according to the present embodiment, and the toner image is formed on the surface of a recording medium. And transcribing means for

  For example, an image carrier, an electrostatic charging means for charging the surface of the image carrier, an electrostatic latent image forming means for forming an electrostatic latent image on the surface of the charged image carrier, and a developer containing toner Developing means for developing the electrostatic latent image formed on the surface of the holding member to form a toner image, Transfer means for transferring the toner image to the surface of the recording medium, Fixing means for fixing the toner image on the recording medium , And the belt member or roll member for the transfer device may include an annular body for an image forming apparatus according to the present embodiment.

Hereinafter, an image forming apparatus according to the present embodiment will be described with reference to the drawings.
FIG. 1 is a schematic configuration view showing the configuration of the image forming apparatus according to the present embodiment. The annular member for an image forming apparatus according to the present embodiment is applied as the intermediate transfer belt.

  The image forming apparatus 100 according to the present embodiment is, for example, an intermediate transfer type image forming apparatus generally called a tandem type as shown in FIG. 1, and a plurality of toner images of respective color components are formed by electrophotography. And a primary transfer portion 10 for sequentially transferring (primary transfer) each color component toner image formed by each of the image forming units 1Y, 1M, 1C and 1K and each of the image forming units 1Y, 1M, 1C and 1K onto the intermediate transfer belt 15 A secondary transfer unit 20 for collectively transferring (secondary transfer) the superimposed toner images transferred onto the intermediate transfer belt 15 onto a sheet K serving as a recording medium, and fixing the image transferred onto the sheet K onto the sheet K And a device 60. The image forming apparatus 100 also includes a control unit 40 that controls the operation of each device (each unit).

  Each of the image forming units 1Y, 1M, 1C, and 1K of the image forming apparatus 100 includes a photosensitive member 11 that rotates in the direction of arrow A as an example of an image carrier that holds a toner image formed on the surface.

  A charger 12 for charging the photosensitive member 11 is provided around the photosensitive member 11 as an example of a charging unit, and a laser exposure unit for writing an electrostatic latent image on the photosensitive member 11 as an example of a latent image forming unit 13 (the exposure beam is indicated by a symbol Bm in the figure) is provided.

  In addition, a developing device 14 is provided around the photosensitive member 11, as an example of a developing unit, for storing each color component toner to visualize the electrostatic latent image on the photosensitive member 11 with the toner. A primary transfer roll 16 is provided to transfer the color component toner images formed thereon onto the intermediate transfer belt 15 at the primary transfer portion 10.

  Furthermore, a photosensitive body cleaner 17 is provided around the photosensitive body 11, from which residual toner on the photosensitive body 11 is removed, and the charger 12, the laser exposure unit 13, the developing unit 14, the primary transfer roll 16 and the photosensitive body cleaner Seventeen electrophotographic devices are sequentially disposed along the rotational direction of the photosensitive member 11. The image forming units 1Y, 1M, 1C, and 1K are arranged substantially linearly in the order of yellow (Y), magenta (M), cyan (C), and black (K) from the upstream side of the intermediate transfer belt 15. It is done.

The intermediate transfer belt 15, which is an intermediate transfer member, is formed to have a volume resistivity of, for example, 1 × 10 ⁶ Ωcm or more and 1 × 10 ¹⁴ Ωcm or less, and its thickness is, for example, about 0.1 mm. There is.

  The intermediate transfer belt 15 is cyclically driven (rotated) at various speeds in the direction B shown in FIG. 1 by various rolls. As the various rolls, a drive roll 31 driven by a motor (not shown) excellent in constant speed to rotate the intermediate transfer belt 15, and an intermediate transfer belt 15 extending substantially linearly along the arrangement direction of the respective photosensitive members 11 Support roller 32 that supports the belt, tension application roll 33 that functions as a correction roll that applies tension to the intermediate transfer belt 15 and prevents meandering of the intermediate transfer belt 15, back surface roll 25 provided in the secondary transfer portion 20, intermediate It has a cleaning back roll 34 provided in a cleaning section for scraping off residual toner on the transfer belt 15.

  The primary transfer portion 10 is composed of a primary transfer roll 16 disposed opposite to the photosensitive member 11 with the intermediate transfer belt 15 interposed therebetween. The primary transfer roll 16 is disposed so as to be in pressure contact with the photosensitive member 11 with the intermediate transfer belt 15 interposed therebetween, and the primary transfer roll 16 further has a voltage (primary) opposite to the charging polarity (negative polarity) of the toner. Transfer bias is applied. As a result, the toner images on the respective photosensitive members 11 are electrostatically attracted to the intermediate transfer belt 15 sequentially, and a superimposed toner image is formed on the intermediate transfer belt 15.

  The secondary transfer unit 20 is configured to include a back surface roll 25 and a secondary transfer roll 22 disposed on the toner image holding surface side of the intermediate transfer belt 15.

The back roll 25 is formed to have a surface resistivity of 1 × 10 ⁷ Ω / sq or more and 1 × 10 ¹⁰ Ω / sq or less, and a hardness of 70 ° (Asker C: manufactured by Kobunshi Keiki Co., Ltd., or less) Same as above). The back roll 25 is disposed on the back side of the intermediate transfer belt 15 to constitute a counter electrode of the secondary transfer roll 22, and a metal feed roll 26 to which a secondary transfer bias is stably applied is disposed in contact. ing.

On the other hand, the secondary transfer roll 22 is a cylindrical roll having a volume resistivity of 10 ^7.5 Ωcm or more and 10 ^8.5 Ωcm or less. The secondary transfer roll 22 is press-contacted to the back roll 25 with the intermediate transfer belt 15 interposed therebetween, and the secondary transfer roll 22 is grounded to form a secondary transfer bias with the back roll 25. The toner image is secondarily transferred onto the sheet K conveyed to the transfer unit 20.

  Further, on the downstream side of the secondary transfer portion 20 of the intermediate transfer belt 15, an intermediate transfer belt for removing the residual toner and paper powder on the intermediate transfer belt 15 after the secondary transfer and cleaning the surface of the intermediate transfer belt 15. A cleaner 35 is provided so as to be freely attachable and detachable.

  The intermediate transfer belt 15, the primary transfer portion 10 (primary transfer roll 16), and the secondary transfer portion 20 (secondary transfer roll 22) correspond to an example of the transfer unit.

  On the other hand, on the upstream side of the yellow image forming unit 1Y, a reference sensor (home position sensor) 42 that generates a reference signal serving as a reference for setting the image forming timing in each of the image forming units 1Y, 1M, 1C, and 1K. It is arranged. Further, an image density sensor 43 for adjusting the image quality is disposed downstream of the black image forming unit 1K. The reference sensor 42 recognizes a mark provided on the back side of the intermediate transfer belt 15 to generate a reference signal, and each image forming unit 1Y, 1 Y,... According to an instruction from the control unit 40 based on the recognition of the reference signal. 1M, 1C, 1K are configured to start image formation.

  Further, in the image forming apparatus according to the present embodiment, the sheet storage unit 50 for storing the sheet K and the sheet K stacked in the sheet storage unit 50 are taken out at a predetermined timing as the transport means for transporting the sheet K. Transport roller 52 for transporting the sheet K, the transport roll 52 for transporting the sheet K fed by the feed roll 51, the transport guide 53 for feeding the sheet K transported by the transport roll 52 to the secondary transfer unit 20, secondary transfer The conveyance belt 55 conveys the sheet K conveyed after being secondarily transferred by the roll 22 to the fixing device 60, and a fixing inlet guide 56 which guides the sheet K to the fixing device 60.

Next, a basic image forming process of the image forming apparatus according to the present embodiment will be described.
In the image forming apparatus according to the present embodiment, image data output from an image reading apparatus (not shown) or a personal computer (PC) (not shown) is subjected to image processing by an image processing apparatus (not shown), and then image forming unit 1Y. , 1M, 1C, and 1K perform an imaging operation.

  The image processing apparatus performs image processing such as shading correction, positional deviation correction, lightness / color space conversion, gamma correction, various types of image editing such as border deletion, color editing, movement editing etc. on the inputted reflectance data. Be done. The image data subjected to the image processing is converted into color material tone data of four colors of Y, M, C, and K, and is output to the laser exposure device 13.

  The laser exposure device 13 irradiates, for example, the exposure beams Bm emitted from the semiconductor laser to the respective photosensitive members 11 of the image forming units 1Y, 1M, 1C, and 1K according to the input color material gradation data. . In each of the photosensitive members 11 of the image forming units 1Y, 1M, 1C, and 1K, the surface is charged by the charger 12, and then the surface is scanned and exposed by the laser exposure unit 13 to form an electrostatic latent image. The formed electrostatic latent image is developed as a toner image of each color of Y, M, C and K by each of the image forming units 1Y, 1M, 1C and 1K.

  The toner images formed on the photosensitive members 11 of the image forming units 1Y, 1M, 1C, and 1K are transferred onto the intermediate transfer belt 15 at the primary transfer portion 10 where the respective photosensitive members 11 and the intermediate transfer belt 15 contact. Ru. More specifically, in the primary transfer portion 10, the primary transfer roller 16 applies a voltage (primary transfer bias) opposite to the charging polarity (minus polarity) of the toner to the base material of the intermediate transfer belt 15, thereby forming a toner image Are sequentially superimposed on the surface of the intermediate transfer belt 15 to perform primary transfer.

  After the toner image is sequentially primarily transferred to the surface of the intermediate transfer belt 15, the intermediate transfer belt 15 is moved to convey the toner image to the secondary transfer portion 20. When the toner image is conveyed to the secondary transfer unit 20, the conveyance unit rotates the paper feed roll 51 in accordance with the timing at which the toner image is conveyed to the secondary transfer unit 20, and the paper storage unit 50 A size sheet K is supplied. The sheet K supplied by the sheet supply roll 51 is conveyed by the conveyance roll 52, passes through the conveyance guide 53, and reaches the secondary transfer unit 20. Before reaching the secondary transfer portion 20, the sheet K is temporarily stopped, and the sheet K is rotated by rotation of a positioning roll (not shown) in accordance with the movement timing of the intermediate transfer belt 15 holding the toner image. The position of the toner image and the position of the toner image are aligned.

  In the secondary transfer unit 20, the secondary transfer roll 22 is pressed against the back roll 25 via the intermediate transfer belt 15. At this time, the sheet K conveyed at the same timing is nipped between the intermediate transfer belt 15 and the secondary transfer roll 22. At that time, when a voltage (secondary transfer bias) having the same polarity as the charging polarity (minus polarity) of the toner is applied from the feeding roll 26, a transfer electric field is formed between the secondary transfer roll 22 and the back roll 25. Be done. Then, the unfixed toner images held on the intermediate transfer belt 15 are collectively electrostatically transferred onto the sheet K at the secondary transfer portion 20 pressurized by the secondary transfer roll 22 and the back roll 25. Ru.

  Thereafter, the sheet K on which the toner image has been electrostatically transferred is conveyed as it is in a state of being separated from the intermediate transfer belt 15 by the secondary transfer roll 22 and conveyed on the downstream side of the secondary transfer roll 22 in the sheet conveyance direction. It is conveyed to the belt 55. The conveyance belt 55 conveys the sheet K to the fixing device 60 in accordance with the optimum conveying speed of the fixing device 60. The unfixed toner image on the sheet K conveyed to the fixing device 60 is fixed on the sheet K by receiving a fixing process by heat and pressure by the fixing device 60. Then, the sheet K on which the fixed image has been formed is conveyed to a discharge storage unit (not shown) provided in the discharge unit of the image forming apparatus.

  On the other hand, after the transfer to paper K is completed, the residual toner remaining on intermediate transfer belt 15 is conveyed to the cleaning section as the intermediate transfer belt 15 rotates, and is cleaned by cleaning back roll 34 and intermediate transfer belt cleaner 35. The intermediate transfer belt 15 is removed.

  As mentioned above, although this embodiment was described, it can not be interpreted limitedly to the said embodiment, and various modification, change, improvement are possible.

  Hereinafter, the present embodiment will be described in detail by way of examples, but the present embodiment is not limited to these examples.

Example 1
[Production of tubular body (belt)]
-Polymerization process-
In a flask equipped with a stirrer, thermometer and dropping funnel, 450 g of water as a protic solvent and 450 g of N-methylpyrrolidone (NMP) as a non-protonic polar solvent were charged. Here, 50.51 g of 4,4'-diaminodiphenyl ether (ODA) and 50.00 g of methyl morpholine (MMO) were added, and the mixture was dispersed by stirring at 20 ° C for 10 minutes. Further, 72.72 g of 3,3 ′, 4,4′-biphenyltetracarboxylic acid dianhydride (BPDA) as tetracarboxylic acid dianhydride (BPDA) is added to this solution, and the reaction temperature is maintained at 20 ° C. The solution was stirred, dissolved, and reacted to obtain a polyimide precursor solution (A).

-Preparation of coating solution-
A polyimide precursor solution (A) was prepared as a resin solution, and an NMP solution (2 mass%) of a polyaniline undoped oxide (made by Nippon Carlit Co.) as a conductive agent solution was prepared. The above two types of solutions were mixed and stirred so that the solid fraction of the polyaniline undoped oxide body was 25 phr with respect to the polyimide resin, to obtain a polyimide precursor-polyaniline mixed solution. Thereafter, an NMP solution (50% by mass) of dodecylbenzenesulfonic acid (Tokyo Chemical Industry Co., Ltd.) as a dopant is prepared for conducting treatment, and the molar amount (Ma) of the dopant (dodecylbenzenesulfonic acid) and 1 in polyaniline The mixture was added to the polyimide precursor-polyaniline mixed solution such that the ratio Ma / Mb (hereinafter simply referred to as "doping ratio") to the molar amount (Mb) of the unit was "1.0". Thereafter, by stirring, a coating solution (imide resin composition) (A) was obtained.

-Preparation of tubular body-
A silicone-based mold release agent (trade name: KS700, Shin-Etsu Chemical Co., Ltd.) on the outer peripheral surface of an aluminum cylindrical body having a diameter of 430 mm, a thickness of 6 mm, and a length of 980 mm and having a surface roughness Ra of 0.4 μm by blasting. C.) and baked at 380.degree. C. for 1 hour to prepare a mold.
While rotating this mold at 100 rpm, while moving the dispenser and scraper from the mold end face to the outer peripheral surface at a speed of 150 min / min, apply the above-mentioned coating liquid (imide resin composition) (A) with a thickness of 0.5 mm did. After that, heating at 120 ° C. for 30 minutes while rotating at 5 rpm, cooling to normal temperature (25 ° C.), heating to 300 ° C. and heating for 2 hours, solvent removal and calcination (imidization) are performed Finally, it was separated after cooling to normal temperature (25 ° C.). A tubular body (belt) A1 was obtained by cutting to a predetermined length after separation.

Example 2
A tubular body (belt) was produced in the same manner as in Example 1 except that in the preparation of the coating solution of Example 1, the doping ratio was changed to "0.1".

Example 3
A tubular body (belt) was produced in the same manner as in Example 1 except that in the preparation of the coating solution of Example 1, the doping ratio was changed to "0.5".

Example 4
A tubular body (belt) was produced in the same manner as in Example 1 except that the doping ratio in the preparation of the coating solution of Example 1 was changed to "1.5".

Example 5
A tubular body (belt) was produced in the same manner as in Example 1 except that in the preparation of the coating solution of Example 1, the doping ratio was changed to "1.9".

Example 6
In the polymerization step of Example 1, the solvent is changed to 450 g of water as a protic solvent and 450 g of 1,3-dimethyl-2-imidazolidinone (DMI) as an aprotic polar solvent, and a coating solution A tubular body (belt) was produced in the same manner as in Example 1 except that the NMP solution (2% by mass) of the polyaniline undoped oxide was changed to the DMI solution (2% by mass) in the preparation of.

Example 7
A tubular body (belt) was produced in the same manner as in Example 6, except that the doping ratio in the preparation of the coating solution of Example 6 was changed to "0.1".

Example 8
A tubular body (belt) was produced in the same manner as in Example 6, except that the doping ratio in the preparation of the coating solution of Example 6 was changed to "1.9".

Example 9
A tubular body (belt) was produced in the same manner as in Example 1 except that the solid content of polyaniline was changed to "10 phr" in the preparation of the coating solution of Example 1.

Example 10
A tubular body (belt) was produced in the same manner as in Example 1 except that in the preparation of the coating solution of Example 1, the solid content of polyaniline was changed to "30 phr".

Example 11
A tubular body (belt) was produced in the same manner as in Example 1 except that in the preparation of the coating solution of Example 1, the polyaniline solid content was changed to "35 phr".

Example 12
A tubular body (belt) was produced in the same manner as in Example 1 except that the mass ratio of the solvent was changed to “water / NMP = 0.2 / 1” in the preparation of the coating solution of Example 1.

Example 13
A tubular body (belt) was produced in the same manner as in Example 1 except that the mass ratio of the solvent was changed to "water / NMP = 9/1" in the preparation of the coating solution of Example 1.

Comparative Example 1
A tubular body (belt) was produced in the same manner as in Example 1 except that in the polymerization step of Example 1, the solvent was changed to 900 g of N-methylpyrrolidone (NMP).

Comparative Example 2
In the polymerization step of Example 1, the solvent is changed to 900 g of 1,3-dimethyl-2-imidazolidinone (DMI), and an NMP solution (2% by mass) of the polyaniline undoped oxide is DMI in the preparation of the coating solution. A tubular body (belt) was produced in the same manner as in Example 1 except that the solution (2% by mass) was used.

Comparative Example 3
In the polymerization step of Example 1, the solvent was changed to 900 g of N-methyl pyrrolidone (NMP). In addition, carbon black as a conductive agent is used without using an NMP solution (2 mass%) of a polyaniline undoped oxide prepared as a conductive agent solution and an NMP solution (50 mass%) of dodecylbenzenesulfonic acid as a dopant. A tubular body (belt) was produced in the same manner as in Example 1 except that the solid content ratio of carbon black to polyimide resin was adjusted to 29 phr using SB4, Deggusa.

Comparative Example 4
A tubular body (belt) was produced in the same manner as in Example 1 except that in the preparation of the coating solution of Example 1, the doping ratio was “0”, that is, it was changed not to add dodecylbenzenesulfonic acid.

Comparative Example 5
A tubular body (belt) was produced in the same manner as in Example 1 except that in the preparation of the coating liquid of Example 1, the doping ratio was changed to "2.0".

Comparative Example 6
A tubular body (belt) was produced in the same manner as in Example 1 except that in the preparation of the coating solution of Example 1, the doping ratio was changed to "2.5".

Comparative Example 7
Example 1 except that in the polymerization step of Example 1, the solvent was changed to 900 g of water, and in the preparation of the coating solution, the NMP solution (2 mass%) of the polyaniline undoped oxide was changed to an aqueous solution (2 mass%) A tubular body (belt) was produced in the same manner as in.

[Evaluation method, result]
Resistivity For volume resistivity (log Ω · cm), measure each belt at six points at equal intervals in the circumferential direction, three points at the center and both ends in the axial direction, at a total voltage of 10 V, 100 V, and 1000 V The average value was calculated for each voltage.
The surface resistivity (log Ω / □) was measured at a voltage of 100 V at a total of 18 points at six points at equal intervals in the circumferential direction, three points at the center and both ends in the axial direction, and the average value was calculated.
The difference between the volume resistivity at a measurement voltage of 100 V and the volume resistivity at 1000 V was calculated as an index of the electric field dependency of the volume resistivity.
The difference between the maximum value and the minimum value at three axial points was calculated as an index of the axial unevenness of the surface resistivity, and the maximum value of the difference was used as the axial unevenness value at six equally spaced points in the circumferential direction. .
An Advantest microammeter was used as a resistance measuring instrument, and a UR probe (Mitsubishi Chemical) was used as a probe.

Mechanical properties: With regard to Young's modulus (MPa) and tensile elongation at break (%), using a tensile tester (MODEL-1605N, manufactured by EIKO ENGINEERING CO., LTD.), 80 mm × 5 mm so that the circumferential direction of the belt becomes long. A strip-shaped test piece was cut out, and the test was carried out according to JIS K7161 at a tensile speed of 20 mm / min, with the length of the test piece between the chucks being 40 mm.
Young's modulus was calculated from the slope of the region where the S-S curve is a straight line (Strain is 10N-38N).
The breaking elongation was calculated from the length at the time of breaking in the tensile test.

  For the MIT test, using a MIT tester (FT-701, manufactured by Ueshima Seisakusho Co., Ltd.), a sample width of 15 mm is applied, a load of 1 kg is applied thereto, and the test is performed with R = 0.38 of the clamp jig at the broken part. The number of repetitions until breakage was the number of breakage resistance.

  The surface roughness is measured according to JIS B0601 (1994) using a surface roughness meter SURFCOM 575A (manufactured by Tokyo Seimitsu Co., Ltd.) with a measurement length of 2.5 mm, a cutoff wavelength of 0.8 mm, and a measurement speed of 0.6 mm / sec. The measurement was carried out according to the same method, and the value of ten-point average roughness Rz was adopted.

  For the endurance test in the device, a belt manufactured as an intermediate transfer belt in VersantTM 80 Press (manufactured by Fuji Xerox Co., Ltd.) was mounted, and operation was performed until breakage occurred, and the number of cycles was taken as the number of broken cycles (kcycle) .

-Image quality evaluation A belt manufactured as an intermediate transfer belt in VersantTM 80 Press (manufactured by Fuji Xerox Co., Ltd.) is mounted, an image is formed, and a ghost (phenomenon in which the density of an image portion formed in the previous time is increased), micro white spots (2 The phenomenon that white spots occur in the image at the location where the overcurrent penetrates during the next transfer) and the occurrence of uneven density were evaluated according to the following criteria.
(ghost)
A (○): Not generated B (Δ): Judgment by visual sensory evaluation, ghosting occurred but acceptable level as image C (×): Judgment by visual sensory evaluation, ghosting occurred and acceptable as an image Impossible level (micro white spot)
A (○): Not generated B (Δ): SRA 3 size paper, with halftone (HT) 30% solid printing, 10 or less micro white spots of 500 μm or less are generated C (×): SRA 3 size paper In the half-tone (HT) 30% solid printing, micro white spots of 500 μm or less occur more than 10 pieces / sheet, or micro white spots of 500 μm or more (density unevenness)
A (○): Not generated B (Δ): Judgment by visual sensory evaluation, density unevenness occurred but acceptable level as image C (×): Judgment by visual sensor evaluation, density unevenness occurred, image As unacceptable level

  From the above results, in the imide resin composition of this example and the tubular body (belt) obtained from this imide resin composition, the electric field dependency of the resistance when formed into a resin molded article is suppressed as compared with the comparative example. It can be understood that

1Y, 1M, 1C, 1K Image forming unit 10 Primary transfer portion 11 Photosensitive body 12 Charger 13 Laser exposure device 14 Developer 15 Intermediate transfer belt 16 Primary transfer roll 17 Primary body cleaner 20 Secondary transfer portion 22 Secondary transfer roll 25 Back roll 26 Power feed roll 31 Drive roll 32 Support roll 33 Tension application roll 34 Cleaning back roll 35 Intermediate transfer belt cleaner 40 Control unit 42 Reference sensor 43 Image density sensor 50 Paper storage unit 51 Feed roll 52 Transport roll 53 Transport guide 55 Transport Belt 56 fixing inlet guide 60 fixing device 100 image forming apparatus

Claims (17)

A mixed solvent containing an aprotic polar solvent and a protic solvent;
An imide resin or its precursor dissolved in the mixed solvent;
When the polyaniline is doped with a dopant, and the molar amount of the dopant is Ma, and the molar amount of the structural unit represented by the following general formula (PA) in the polyaniline is Mb, the ratio Ma / Mb is more than 0. Conductive polyaniline which is 95 or less,
An imide resin composition containing

General formula (PA)   The imide resin composition according to claim 1, wherein the ratio Ma / Mb is 0.5 or more and 1.5 or less.   The imide resin composition according to claim 1 or 2, wherein a content of the conductive polyaniline is 10 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the imide resin or the precursor thereof.   The imide resin composition according to any one of claims 1 to 3, wherein the dopant is an organic acid.   The imide resin composition according to claim 4, wherein the organic acid has an alkyl group having 6 to 20 carbon atoms.   The imide resin composition according to any one of claims 1 to 5, wherein the protic solvent is water.   The imide resin according to any one of claims 1 to 6, wherein the aprotic polar solvent is at least one selected from 1,3-dimethyl-2-imidazolidinone and N-methyl pyrrolidone. Composition.   The mass ratio (protonic solvent / non-protonic polar solvent) of the non-protonic polar solvent to the protic solvent in the mixed solvent is 0.2 / 1 or more and 9/1 or less. The imide type-resin composition of any one of these.   The imide resin composition according to any one of claims 1 to 8, further comprising an organic amine compound.   The organic amine compound is 2-dimethylaminoethanol, 2-diethylaminoethanol, 2-dimethylaminopropanol, pyridine, triethylamine, picoline, N-methylmorpholine, N-ethylmorpholine, 1,2-dimethylimidazole, 2-ethyl- The imide resin composition according to claim 9, which is at least one selected from 4-methylimidazole, N-methylpiperidine, and N-ethylpiperidine.   11. The imide resin according to claim 9, wherein the content of the organic amine compound is 30 mol% or more and 200 mol% or less with respect to the amount of carboxy group in the imide resin or the precursor thereof. Composition.   A tubular body for an image forming apparatus, which is a tubular cured product obtained by curing the imide resin composition according to any one of claims 1 to 11.   The tubular body for an image forming apparatus according to claim 12, wherein a tensile elongation at break of the tubular body for an image forming apparatus is 70.0% or more.   13. The image forming apparatus tubular body according to claim 12, wherein the number of times of bending resistance by the MIT test under the condition of sample width: 15 mm, load: 1 kg, R: 0.38 of broken part of clamp jig is 15,000 or more. Item 13. A tubular body for an image forming apparatus according to item 13.   The ten-point average roughness Rz defined in JIS B 0601 (1994) of the surface of the tubular body for an image forming apparatus is 0.06 μm or more and 0.19 μm or less. The tubular body for an image forming apparatus according to claim 1. A tubular body for an image forming apparatus according to any one of claims 12 to 15,
A transfer device for transferring a toner image formed on the surface of an image carrier to the surface of a recording medium. An image carrier,
Toner image forming means for forming a toner image on the surface of the image carrier;
A transfer unit comprising the transfer device according to claim 16, for transferring the toner image to the surface of a recording medium.
An image forming apparatus comprising: