JP4696630B2 - Resin endless belt, method for manufacturing the same, and image forming apparatus - Google Patents

Description

  The present invention relates to a resin endless belt used in an electrophotographic apparatus such as a copying machine, a laser beam printer, a facsimile, and a composite apparatus thereof, and a method for manufacturing the same. The present invention also relates to an image forming apparatus such as an electrophotographic apparatus using the resin endless belt.

  An electrophotographic apparatus applies a uniform charge onto a photoconductor made of a conductive material, forms an electrostatic latent image with a modulated image signal using laser light, etc., and then develops the electrostatic latent image with charged toner. Thus, the toner image is obtained, and then the toner image is transferred to a recording medium such as paper directly or via an intermediate transfer member to obtain an image.

  Here, it is used in an image forming apparatus employing a so-called intermediate transfer system in which a toner image on a photosensitive member is primarily transferred to an intermediate transfer member and then a toner image on the intermediate transfer member is secondarily transferred to a recording medium such as paper. Examples of the intermediate transfer belt include polyvinylidene fluoride (see, for example, Patent Document 1), polycarbonate (see, for example, Patent Document 2), and a blend of an ethylene-tetrafluoroethylene copolymer and polycarbonate (see, for example, Patent Document 3). A conductive endless belt in which a conductive agent such as carbon black is dispersed in a thermoplastic resin has been proposed.

  Further, in recent years, a method of fixing a toner image on a recording medium by heating the intermediate transfer member, that is, an intermediate transfer and fixing method has been disclosed (for example, see Patent Document 4). In this intermediate transfer / fixing method, after the toner image is secondarily transferred to the recording medium via the intermediate transfer member, the intermediate transfer member is directly or indirectly heated to contact the intermediate transfer member. This is a method for fixing a toner image on a recording medium, and has an advantage that the apparatus can be reduced in size and cost compared with a conventional apparatus in which the intermediate transfer mechanism and the fixing mechanism are separated.

  Here, the belt material used in the intermediate transfer and fixing method is required to have a mechanical strength that can withstand the stress during driving and a heat resistance that can withstand the heat close to 200 ° C. that is applied during fixing. Because of this requirement, a thermosetting resin having both high mechanical strength and heat resistance is suitable for the belt material used in the intermediate transfer and fixing method, and in particular, the polyimide resin is excellent in both of the above characteristics.

  However, a resin belt using a thermosetting resin such as a polyimide resin has a drawback that the surface is easily damaged, and the scratch once attached remains as it is. The scratches on the surface of the resin belt appear as image quality defects when mounted on an electrophotographic apparatus. From this demand, there is a need for a resin belt material that is difficult to be scratched or that can be repaired over time and by treatment even if it is scratched.

  On the other hand, in recent years, paints capable of self-repairing scratches have been developed in hard coating agents used in the fields of furniture, home appliances, office automation equipment, and the like (see, for example, Patent Documents 5 to 10). This paint includes a composition in which a cross-linkable resin such as acrylic, polyurethane, or polyester is combined with polysilicon or the like. The hard coating agent increases the film strength by curing (crosslinking) treatment after coating, and repairs the wound by reorienting the flexible polysilicon chain against the scratch once attached. It is.

These hard coat agents have a composition in which a crosslinkable component and a soft segment are combined. As the crosslinking reaction proceeds, layer separation between the crosslinkable component and the soft segment component is promoted to form a soft segment layer. Is. For this reason, a soft segment layer cannot be formed unless a crosslinking reaction is performed, and self-repairing properties cannot be exhibited. Further, since the reaction is accompanied by a crosslinking reaction, the resin after the reaction becomes hard and brittle, and cannot be used as a belt material to which an external force such as bending, tension or shear is applied. Furthermore, since the cross-linking reaction proceeds in a very short time, the soft segment is hardly transferred to the surface layer, and the soft segment layer is confined in the cross-linked structure, so that sufficient mechanical strength as a belt is obtained. I can't.
Japanese Patent Laid-Open No. 5-200904 JP-A-6-228335 Japanese Patent Laid-Open No. 6-149083 JP-A-6-258960 Japanese Patent Application Laid-Open No. 2002-256053 Japanese Patent Laid-Open No. 2003-014906 JP 2003-302501 A Japanese Patent Laid-Open No. 2004-035599 JP 2004-035600 A JP 2004-035601 A

An object of the present invention is to solve the conventional problems and achieve the following objects.
That is, an object of the present invention is to provide a resin endless belt that is less likely to be scratched on the belt surface during manufacture, installation, and use, and that has self-healing properties against the generated scratch, a method for manufacturing the same, and a method for manufacturing the same. An image forming apparatus is provided.

  As a result of intensive studies to solve the above problems, the present inventors, as a resin material constituting the belt, in a resin endless belt such as a fixing belt, a conveyance belt, and an intermediate transfer belt used in an electrophotographic apparatus. The present invention has found that by using a resin having a block structure in which soft segments are bonded to both ends of a hard segment, it is possible to repair the scratches generated on the belt surface during handling and driving an electrophotographic apparatus. It came.

  Further, the resin endless belt manufacturing method of the present invention is a method of advancing the association of the hard segments through a step of applying a solution obtained by dissolving the resin raw material in a solvent to a cylindrical mold and a drying / firing step, and a soft The transition of the segment to the resin endless belt surface is promoted, and the self-repairing property of the resin endless belt is exhibited.

That is, the present invention
<1> main chain aromatic polyimide in at both ends of the hard segment containing structures have either the of the aromatic polyamide and aromatic polyamide-imide, a linear or branched long-chain alkyl having 8 to 22 carbon atoms A resin endless belt having a block structure in which a soft segment containing a group or a silicone is bonded, and containing a resin having a content of the soft segment in a range of 1 to 20% by mass.

<2> The resin endless belt according to <1>, wherein the polysilicon is a polysilicon having a structure represented by the following structural formula (1).

In the above formula, R1 is a hydrocarbon group having a carbon number of 1-12. p represents an integer of 0 to 12, and q represents an integer of 1 to 12, respectively.

<3> The resin endless belt according to <1> or <2>, further comprising a conductive agent.

<4><1> is an image forming apparatus characterized by obtaining Bei the resin endless belt according to any one of 1 to <3>.

<5> The image forming apparatus according to <4> , wherein the resin endless belt is provided as an intermediate transfer belt and / or a fixing belt.

<6> A method for producing a resin endless belt according to any one of <1> to <3> ,
A coating step of applying the resin solution composition to the cylindrical mold, and a drying / firing step of performing drying / firing treatment, wherein the drying / firing step is performed in an atmosphere having a water vapor content of 50% by volume or less, or A method for producing a resin endless belt, which is performed under a reduced pressure of 10 Pa or less.

  According to the present invention, it is possible to provide a resin endless belt that is less likely to be scratched on the surface of the belt, has self-repairing properties against generated scratches, and is excellent in electrical performance and the like, and a method for manufacturing the same. The resin endless belt can be suitably used as a fixing belt, an intermediate transfer belt or the like of an electrophotographic apparatus, and can exhibit good copying performance when mounted on an electrophotographic apparatus.

<Resin endless belt>
The resin endless belt of the present invention (hereinafter sometimes simply referred to as “endless belt”) contains a resin having a block structure in which soft segments are bonded to both ends of a hard segment, which has been a problem with conventional belts. It has the property of self-repairing scratches generated on the belt surface. Specifically, the resin having the block structure exhibits a mechanical strength that does not cause deformation / breakage due to the mechanical stress applied to the belt such as elongation, tension, and tear due to the effect of the hard segment.

  In addition, the hydrophobic soft segment on the belt surface is attracted to the air layer of low humidity by being manufactured through the coating, drying, and firing processes described later, so the hydrophobic soft segment on the belt surface. The layer is unevenly distributed. For this reason, the surface of the belt becomes slippery. As a result, the belt surface is less likely to be damaged even by stress such as rubbing or rubbing. Furthermore, small scratches generated on the belt surface are gradually repaired by the molecular motion of the soft segment. In self-repairing the wound, heating the belt is more effective because the time required for the repair can be shortened.

  In the resin having a block structure in the present invention, it is important that the soft segment is bonded to both ends of the hard segment because the above-described effect when an endless belt is produced can be greatly improved. For example, when an endless belt is produced by simply blending a hard segment and a soft segment, the soft segment is phase-separated on the surface of the belt, and cannot be self-repaired. Moreover, since the soft segment confined inside the endless belt causes a decrease in the mechanical strength of the endless belt, the obtained endless belt becomes fragile.

As another example, when an endless belt is produced by introducing a soft segment as a side chain instead of the end of a hard segment to produce an endless belt, the mechanical strength of the endless belt decreases for the same reason, and it becomes fragile. End up. In other words, the introduced soft segment can be used effectively even in a small amount only when the hard segment has soft segments at both ends. This is presumably because the soft segment is introduced at the end of the hard segment, so that the mobility is high and the surface transition based on the reorientation is performed quickly.
Hereinafter, the structure and synthesis method of the resin having a block structure in the present invention will be described.

(Hard segment)
The hard segment in the present invention refers to a molecular structure in a polymer having no bent structure or side chain substituent in the molecular structure. More specifically, it refers to a structure in which several aromatic rings are connected by an imide bond and / or an amide bond, and the rotational freedom degree of the polymer molecule is restricted.
In the present invention, a hard segment containing any structure of aromatic polyimide, aromatic polyamide, and aromatic polyamideimide in the main chain is used. In these, it is preferable that an aromatic polyimide structure is included.

  The aromatic polyimide refers to a resin having an aromatic structure as a constituent component of polyimide in which repeating units are connected by an imide bond. Aromatic polyimide uses aromatic polyamic acid obtained by condensation polymerization reaction of aromatic tetracarboxylic dianhydride and aromatic diamine compound as a precursor, and is dehydrated and closed by a drying / firing process after the coating process described later. It becomes an aromatic polyimide. The aromatic tetracarboxylic dianhydride and aromatic diamine compound used are appropriately selected depending on the reaction conditions.

  The aromatic polyamide refers to a resin having an aromatic structure as a constituent component of polyamide in which repeating units are connected by an amide bond. The aromatic polyamide is obtained by a reaction of an aromatic dicarboxylic acid compound or trimellitic acid compound with an aromatic diamine compound or an aromatic diisocyanate compound, or ring-opening polymerization of caprolactam. As the aromatic dicarboxylic acid compound, aromatic dicarboxylic acid or aromatic dicarboxylic acid dichloride is used, and these are appropriately selected depending on the reaction conditions.

  The aromatic polyamideimide refers to a resin having an aromatic structure as a constituent component of polyamideimide in which repeating units are connected by amide bonds and imide bonds. The aromatic polyamideimide can be obtained by a reaction between a trimellitic acid compound and an aromatic diamine compound or an aromatic diisocyanate compound. Since the aromatic polyamideimide used in the present invention needs to be dissolved in a solvent, the ratio of the polyamic acid structure to the imide structure in the molecular structure can be arbitrarily set as long as the solubility is maintained. . As the trimellitic acid compound, trimellitic acid, trimellitic anhydride chloride, or trimellitic anhydride is used, and these are appropriately selected depending on the reaction conditions.

Hereinafter, each of the aromatic polyimide, aromatic polyamide, and aromatic polyamideimide constituting the hard segment will be described in more detail.
(1) Aromatic polyimide Resin containing an aromatic polyimide structure in the hard segment in the present invention is obtained by reacting an aromatic polycarboxylic acid obtained by reacting an aromatic tetracarboxylic dianhydride with an aromatic diamine compound as a precursor. To do.

-Aromatic tetracarboxylic dianhydride-
As the tetracarboxylic dianhydride used for the production of the aromatic polyamic acid, an aromatic tetracarboxylic dianhydride is preferably used. As long as the aromatic tetracarboxylic dianhydride is used, an aliphatic tetracarboxylic dianhydride may be used in combination for the purpose of adjusting the resin properties. Generally, by using an aliphatic tetracarboxylic dianhydride in combination, the physical properties of the belt become flexible, but the strength tends to decrease.

  Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, and 3,3 ′, 4,4′-biphenylsulfone. 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-dicarboxyl) Enoxy) diphenylsulfone 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 (Triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, and the like. it can.

  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.

  Examples of the aromatic tetracarboxylic dianhydride used in the present invention include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4. '-Biphenylsulfone tetracarboxylic dianhydride is preferably used. These aromatic tetracarboxylic dianhydrides can be used alone or in combination of two or more.

-Aromatic diamine compounds-
As the diamine compound that can be used for the production of the aromatic polyamic acid, an aromatic diamine compound containing two amino groups and an aromatic ring structure in the molecular structure is preferably used. As long as an aromatic diamine compound is used, an aliphatic diamine compound may be used in combination for the purpose of adjusting resin physical properties. Generally, by using an aliphatic diamine compound in combination, the physical properties of the belt become supple, but the strength tends to decrease.

  Examples of the aromatic diamine compound include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl ether, and 4,4′-diamino. Diphenyl sulfide, 4,4′-diaminodiphenyl sulfone, 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′-trifluoromethyl Benzanilide, 3,5-diamino-4'-trifluoromethylbenzanilide, 3,4'-diamidine Diphenyl ether, 2,7-diaminofluorene, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetra Chloro-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-aminophenyl) fluorene, 4,4 '-(p-phenyleneisopropylidene) bisaniline, 4,4'-(m-phenyleneisopropylidene) bisaniline, 2,2 '-Bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-bis [4- (4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl An aromatic diamine having two amino groups bonded to an aromatic ring such as diaminotetraphenylthiophene and a hetero atom other than the nitrogen atom of the amino group.

  Examples of the aliphatic diamine compound include 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1, Aliphatic diamines such as 4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoin danylene dimethylene diamine, 4,4'-methylene bis (cyclohexylamine) and alicyclic A diamine etc. can be mentioned.

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

  The organic polar solvent used for the reaction for producing the aromatic polyamic acid is not particularly limited as long as it dissolves the aromatic polyamic acid and the aromatic polyamic acid-polyimide copolymer. For example, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, and acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide , Pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol solvents such as phenol, o-, m-, or p-cresol, xylenol, halogenated phenol, catechol, tetrahydrofuran, Examples include ether solvents such as dioxane and dioxolane, hexamethylphosphoramide, γ-butyrolactone, and aromatic hydrocarbons such as xylene and toluene. These can be used alone or as a mixture.

  The solid content concentration of the aromatic polyamic acid solution is not particularly specified, but is preferably in the range of 5 to 50% by mass, and more preferably in the range of 10 to 30% by mass. When the solid content concentration is less than 5% by mass, the polymerization degree of the aromatic 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.

  The reaction temperature during the aromatic polyamic acid polymerization is preferably in the range of 0 ° C to 80 ° C. When the reaction temperature is 0 ° C. or lower, the viscosity of the solution increases, and the reaction system may not be sufficiently stirred. On the other hand, when the reaction temperature is higher than 80 ° C., a partial imidization reaction occurs in parallel with the polymerization of the polyamic acid, so that problems are likely to occur in terms of reaction control.

  The solvent used in the aromatic polyamic acid solution composition is not particularly limited as long as it dissolves the aromatic polyamic acid as shown in the aforementioned synthesis solvent. In addition to one or two or more of these solvents, it is a poor solvent for the resin for the purpose of improving the leveling property during coating, improving the stability of the solution, improving the dispersibility of the filler, and adjusting the drying speed. A certain alcohol solvent such as methanol, ethanol and butanol, or a cellosolve solvent such as butyl cellosolve can be used by mixing with the aforementioned solvent. By mixing these poor solvents, the contact angle of the polyamic acid solution composition to the substrate can be lowered, so that a smooth coating film can be obtained and the effect of filling the micropores of the substrate can be achieved. You can also.

  The solvent may be used from the time of synthesis of the aromatic polyamic acid or may be replaced with a predetermined solvent after the synthesis. For solvent replacement, a method in which a predetermined amount of solvent is added to the resin solution for dilution, a method in which the resin is reprecipitated and then re-dissolved in the predetermined solvent, a predetermined solvent is added while gradually distilling off the solvent. Any method of adjusting the composition may be used.

(2) Aromatic polyamide The resin containing an aromatic polyamide structure in the hard segment in the present invention is a reaction of an aromatic dicarboxylic acid compound or trimellitic acid compound with an aromatic diamine compound or aromatic diisocyanate compound, or caprolactam Obtained by a ring-opening polymerization reaction. As the aromatic dicarboxylic acid compound, aromatic dicarboxylic acid or aromatic dicarboxylic acid dichloride is used, and these are appropriately selected depending on the reaction conditions.

  As the aromatic dicarboxylic acid and aromatic dicarboxylic acid dichloride, compounds having a structure in which two amino groups of the aromatic diamine compound used in the synthesis of the aromatic polyimide described above are substituted with a carboxyl group and a carboxylic acid chloride group are used. Is done. As the trimellitic acid compound, trimellitic acid, trimellitic anhydride chloride, or trimellitic anhydride is used, and these are appropriately selected depending on the reaction conditions. In addition, as the aromatic diisocyanate compound, a compound having a structure in which two amino groups of the aromatic diamine compound used in the synthesis of the aromatic polyimide described above are substituted with isocyanate groups is used. The aromatic diamine compound, the synthesis solvent, the solvent used in the resin solution composition, the reaction temperature, and the like for the reaction can be performed according to the above-described synthesis of the aromatic polyimide resin.

(3) Aromatic polyamideimide Resin containing an aromatic polyamideimide structure in the hard segment in the present invention is a reaction between an aromatic tetracarboxylic dianhydride or trimellitic acid compound and an aromatic diamine compound or aromatic diisocyanate compound. Can be obtained by: Furthermore, it is also possible to use an aromatic dicarboxylic acid compound mixed with an aromatic tetracarboxylic dianhydride or trimellitic acid compound. The resin solution used in the present invention needs to be dissolved in a solvent, and as long as the solubility is maintained, the polyamic acid structure and the imide structure in the molecular structure can be formed at an arbitrary ratio. .

  The aromatic tetracarboxylic dianhydride, trimellitic acid compound, aromatic dicarboxylic acid compound, aromatic diamine compound, aromatic diisocyanate compound and the like are the same as those described above for the aromatic polyimide and aromatic polyamide. Moreover, the synthetic solvent at the time of resin synthesis | combination, the solvent used for a resin solution composition, reaction temperature, etc. can be performed according to the above-mentioned aromatic polyimide resin synthesis.

(Soft segment)
The soft segment in the present invention refers to a molecular structure having a high degree of molecular rotational freedom in which a plurality of carbon, silicon, and oxygen atoms are connected by a single bond.

  The soft segment in the present invention comprises either a long-chain alkyl group or a polysilicone. Specifically, in the present invention, a linear or branched long-chain alkyl group having 8 to 22 carbon atoms, or Polysilicone represented by the following structural formula (1) is preferably used.

  In the above formula, R1 represents an alkyl group such as a methyl group, an ethyl group, or a propyl group, a cycloalkyl group such as a cyclohexyl group, or a hydrocarbon group having 1 to 12 carbon atoms such as an aryl group such as a phenyl group. p represents an integer of 0 to 12, and q represents an integer of 1 to 12, respectively.

  The long chain alkyl group preferably has 8 to 22 carbon atoms. The long alkyl chain may be linear or branched. When the carbon number is less than 8, the predetermined effect is not exhibited, and when the carbon number is greater than 22, the film strength at the time of belt molding is lowered.

(Resin having a block structure)
The resin having a block structure used for the resin endless belt of the present invention is a resin having a block structure in which the soft segment is bonded to both ends of the hard segment. In the resin synthesis, during polymerization of the hard segment, a monoamine compound or dicarboxylic acid monoanhydride having a long-chain alkyl group or a poly-silicone chain in the main chain structure coexists, and the long-chain alkyl group or poly-acid is present at both ends of the hard segment. This is done by introducing silicone chains.

As monoamine compounds having a long-chain alkyl group in the structure, the compounds represented by the following structural formulas (2) to (3), and as dicarboxylic acid anhydride compounds having a long-chain alkyl group in the structure, the following structural formula (4 ) Are preferably used.
In structural formulas (2) to (4), R2, R3, and R4 represent a linear or branched alkyl group having 8 to 22 carbon atoms and an alkoxy group having 8 to 22 carbon atoms.

  When the compound represented by the structural formula (3) is used, the structure has a benzene ring between the hard segment and the soft segment. Moreover, when the compound shown by Structural formula (4) is used, it becomes a structure which has a phthalimide group between a hard segment and a soft segment.

The monoamine compound having a polysilicon chain in the structure is represented by the following structural formulas (5) to (6), and the dicarboxylic acid anhydride compound having a polysilicon chain in the structure is represented by the following structural formula (7). Each of the compounds shown is used.
In the structural formulas (5) to (7), R5, R6, and R7 are alkyl groups such as a methyl group, an ethyl group, and a propyl group, a cycloalkyl group such as a cyclohexyl group, or an aryl group such as a phenyl group. A C1-C12 hydrocarbon group is shown. p is 0-12, q, r is an integer of 1-12, respectively.

  When the compound represented by the structural formula (6) is used, the structure has a benzene ring between the hard segment and the soft segment. When the compound represented by the structural formula (7) is used, a structure having a phthalimide group is provided between the hard segment and the soft segment.

  The soft segment content needs to be in the range of 1 to 20% by mass in the resin having the block structure. If the content of the soft segment is less than 1% by mass, the self-healing property of the scratch cannot be expressed, and if it exceeds 20% by mass, the belt strength is remarkably lowered. Control of the content of the soft segment to the above range is performed by adjusting the molecular composition of the hard segment and the soft segment during the synthesis of the resin having a block structure.

  The hard segment in the present invention has an aromatic ring structure as a basic unit as described above, and has high molecular planarity, so that the hard segment molecule such as a π-π bond by an aromatic ring between polymer chains is strong. Expresses intermolecular interactions. Since the intermolecular interaction between the polymer chains is not accompanied by a covalent bond, the resin endless belt containing the resin having a block structure in the present invention can exhibit a mechanical performance suitable as a hard but flexible belt material. Thus, it is essentially different from the hard coat agent described above.

  Also, regarding the repair of scratches on the surface, the self-healing property by the hard coat agent described above is merely a reorientation of the soft segment, whereas the self-healing property of the resin endless belt of the present invention is In addition to the reorientation of the soft segment, it is based not only on the dissociation and re-formation of the π-π bond in the hard segment as the main chain, so that the repairability of the flaw becomes higher.

  The resin endless belt of the present invention containing the above-described resin having a block structure can be suitably used for electrophotographic apparatuses such as electrophotographic copying machines, laser beam printers, facsimiles, and composite devices thereof. Specifically, the resin endless belt of the present invention includes a sheet conveying belt, an intermediate transfer belt whose transfer method is an intermediate transfer belt method, and a fixing device that directly or indirectly heats the belt at the time of fixing. If it is a belt, the apparatus to be incorporated is not particularly limited. For example, a monocolor electrophotographic apparatus having only a single color (usually black) in the apparatus, a color electrophotographic apparatus that sequentially repeats primary transfer of a toner image carried on a photoreceptor onto an intermediate transfer belt, and development for each color Any of tandem type color electrophotographic apparatuses in which a plurality of latent image carriers provided with a container are arranged in series on an intermediate transfer belt may be used.

  Therefore, the resin endless belt of the present invention can be used not only as an intermediate transfer belt and a fixing belt, but also as an intermediate transfer and a fixing belt. The “intermediate transfer and fixing belt” is a belt that performs an intermediate transfer process and a fixing process on the same belt.

If the difference between the maximum thickness and the minimum thickness of the resin endless belt of the present invention is too large, it will cause wrinkles. It is necessary to reduce the wrinkle of the belt as much as possible because it induces a decrease in image quality when transferring or fixing. From this point, it is desirable that the difference between the maximum thickness and the minimum thickness of the resin endless belt is 20% or less of the average thickness of the resin endless belt. The “belt thickness” refers to a thickness that can be measured with a thickness meter that measures the distance between flat plates in contact with the belt at an area of 5 mm ² or more, and has a width of 50 μm or less that exists specifically on the belt surface. The height of the protrusion is ignored.

  Further, the thickness of the resin endless belt of the present invention is preferably 10 μm or more and 250 μm or less, and more preferably 30 μm or more and 150 μm or less. If the thickness is less than 10 μm, the toughness may be too small to obtain the strength of the belt, and if it exceeds 250 μm, it is not preferable from the viewpoint of thermal conductivity, resistance value, etc., and the flexibility is impaired and used as a belt. It may not be possible.

As will be described later, when the resin endless belt of the present invention contains a conductive agent, the volume resistivity is preferably 1 × 10 ⁶ Ω · cm or more and 1 × 10 ¹² Ω · cm or less. More preferably, it is 1 × 10 ⁹ Ω · cm or more and 1 × 10 ¹² Ω · cm or less. If this volume resistivity is less than 1 × 10 ⁶ Ω · cm, the electrostatic force that holds the charge of the unfixed toner image transferred from the image carrier to the intermediate transfer member becomes difficult to work. Due to the electrostatic repulsion between the toners or the force of the fringe electric field in the vicinity of the image edge, the toner may be scattered around the image and an image with a large noise may be formed. On the other hand, if the volume resistivity is higher than 1 × 10 ¹² [Omega] cm, in order retention of charge is large, it is necessary to neutralizing mechanism for the intermediate transfer member surface by the transfer electric field at the primary transfer is charged Sometimes. Therefore, by setting the volume resistivity within the above range, it is possible to solve the problem of toner scattering and the need for a static elimination mechanism.

  The contact angle of the resin endless belt of the present invention with water is preferably in the range of 80 to 130 °, and more preferably in the range of 90 to 130 °. If the contact angle with water is less than 80 °, a cleaning defect such as toner adhering to the belt surface may occur. If the contact angle exceeds 130 °, the transfer efficiency decreases and the resulting image deteriorates. There is a case.

  The method for producing the resin endless belt of the present invention is not particularly limited as long as it is a method produced so as to include the resin having the block structure, but it is applied by applying a resin solution composition as described later. It is preferable to use a method of drying and baking under certain conditions.

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

<Method for producing resin endless belt>
The method for producing an endless resin belt according to the present invention includes a coating process for applying a resin solution composition to a cylindrical mold, and a drying / firing process for performing a drying / firing process. It is characterized by being carried out in an atmosphere where the rate is 50% by volume or less, or under a reduced pressure of 10 Pa or less.
Hereinafter, as an example of the resin endless belt manufacturing method of the present invention, a method for molding an endless belt when the hard segment of the resin having a block structure is an aromatic polyimide will be described.

  First, an aromatic tetracarboxylic dianhydride component, an aromatic diamine component, and a compound containing a long-chain alkyl group or a polysilicon chain represented by the structural formulas (2) to (7) in an organic solvent. A polymerization reaction is performed. The resin having a block structure obtained by the reaction is a resin having an aromatic polyamic acid which is a precursor of an aromatic polyimide resin in a hard segment. (Hereinafter, the resin having this block structure is simply referred to as “aromatic polyamic acid” for simplicity.)

  Next, the polymerization reaction solution is added to a poor solvent such as methanol to precipitate an aromatic polyamic acid, which is purified by reprecipitation. The precipitated aromatic polyamic acid is filtered off and then redissolved in a solvent such as N-methyl-2-pyrrolidone to obtain an aromatic polyamic acid solution composition (resin solution composition).

  Examples of the solvent for re-dissolving the aromatic polyamic acid solution composition include those shown in the aforementioned synthesis solvent. Among these, it is preferable to contain one or more solvents selected from N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, and N, N-dimethylformamide. Moreover, it is preferable that content of these solvents is 50 mass% or more in a resin solution composition from the good coating property of a resin solution composition, and the preservability. Regarding these solvents, not only aromatic polyimide but also the synthesis of aromatic polyamide and aromatic polyamideimide are the same.

  A predetermined amount of a tertiary amine, and optionally a carboxylic acid anhydride, may be added to the aromatic polyamic acid solution composition described above and dissolved by stirring.

  The tertiary amine works as a catalyst for imidization reaction. For example, tertiary amines such as pyridine, picoline, collidine, lutidine, quinoline, isoquinoline, triethylamine can be used, among which pyridine, picoline, quinoline. , Isoquinoline, or triethylamine can be suitably used.

  The initial addition amount of the tertiary amine is preferably in the range of 5 to 100 parts by mass, more preferably in the range of 10 to 40 parts by mass, and still more preferably 10 to 100 parts by mass of the aromatic polyamic acid. It is the range of -30 mass parts. When the initial addition amount of the tertiary amine exceeds 100 parts by mass, the amount remaining without being removed from the film increases, and the strength of the molded aromatic polyimide endless belt becomes weak and less than 5 parts by mass. If so, the aromatic polyimide resin may precipitate in the composition.

  The carboxylic acid anhydride serves as a dehydrating agent during the imidation reaction and promotes the imidization reaction. The carboxylic acid anhydride is not particularly limited as long as it is a monovalent carboxylic acid anhydride. Acetic anhydride, propionic anhydride, trifluoroacetic anhydride, propionic anhydride, butanoic anhydride and oxalic anhydride Of these, acetic anhydride is preferred. These may be used alone or in combination of two or more.

  The initial addition amount of the carboxylic acid anhydride is preferably in the range of 0.1 to 30 parts by mass with respect to 100 parts by mass of the aromatic polyamic acid. If the initial addition amount is less than 0.1 parts by mass, the imidization promoting effect cannot be exhibited, and if it exceeds 30 parts by mass, the stability of the aromatic polyamic acid solution composition cannot be ensured. It is.

  If necessary, a conductive agent can be added to the aromatic polyamic acid solution composition. As the conductive agent, conductive or semiconductive fine powder can be used, and there is no particular limitation as long as a desired electric resistance can be stably obtained. However, Ketjen black, acetylene black, and the surface are oxidized. Carbon black such as carbon black; Metals such as aluminum and nickel; Metal oxide compounds such as yttrium oxide and tin oxide; Ion conductive materials such as potassium titanate and LiCl; Conductive polymers such as polyaniline, polypyrrole, polysulfone and polyacetylene Materials; etc. can be illustrated. These conductive agents may be used alone or in combination. Furthermore, a processing aid such as a dispersant and a lubricant can be added to the endless belt as necessary.

  Regarding the addition amount of the conductive agent, it is 10 to 40 parts by mass for carbon black, 1 to 10 parts by mass for metal, and metal oxide with respect to 100 parts by mass of the resin having a block structure or its precursor. 5 to 20 parts by mass, 5 to 40 parts by mass for ionic conductive substances, and 5 to 30 parts by mass for conductive polymer materials are preferred. When this content is less than the above range, the uniformity of electrical resistance is lowered, and in-plane unevenness of surface resistivity and electric field dependency may increase. On the other hand, if the above range is exceeded, it may be difficult to obtain a desired resistance value. Moreover, since the strength of the belt is lowered and the toughness is inferior, the belt may not be used.

  Examples of the method for dispersing the conductive agent and disrupting the aggregate include physical methods such as stirring with a mixer or a stirrer, parallel rolls, ultrasonic dispersion, and chemical methods such as introduction of a dispersing agent. However, it is not limited to these.

  Next, the aromatic polyamic acid solution composition is applied to the inner or outer surface of the mold (coating process). As the mold, a cylindrical mold is used, and instead of the mold, molds made of various known materials such as resin, glass, and ceramic can work well as the mold in the present invention. . It is also possible to appropriately select to provide a glass coat, a ceramic coat or the like on the surface of the mold, and to use a silicone-based or fluorine-based release agent. Furthermore, by moving the film thickness control mold with the clearance adjusted to the cylindrical mold through the cylindrical mold in parallel, the excess solution is eliminated and the thickness of the solution on the cylindrical mold is made uniform. can do. If uniform thickness control is performed at the stage of applying the composition onto the cylindrical mold, it is not necessary to use a film thickness control mold.

  Next, this cylindrical mold coated with the aromatic polyamic acid solution composition is placed in a heating environment, and a drying process is performed to volatilize 30% by mass or more, preferably 50% by mass or more of the contained solvent (drying). Process). At this time, the solvent may remain in the film, and there is no problem as long as the surface of the coating film is dry and does not flow even when tilted. The drying treatment temperature is performed in a temperature range of 50 ° C to 400 ° C.

  Further, this mold is heated at 150 ° C. to 450 ° C. to perform a baking treatment for completing the imide conversion reaction (baking step). The imidation temperature varies depending on the materials used for resin synthesis, such as the types of aromatic tetracarboxylic dianhydride and aromatic diamine as raw materials.

  The above drying / firing process can be performed in a hydrophobic environment, such as when the water vapor content in the atmosphere is 50% by volume or less, or under a reduced pressure of 10 Pa or less. Is preferable because it is promoted. When treated in an environment where the water vapor content in the atmosphere exceeds 50% by volume or at a pressure exceeding 10 Pa, the transition of the soft segment to the belt surface becomes insufficient, and the self-repairing property against the resulting belt scratches is not exhibited. There is a case.

  Thereafter, the resin is removed from the mold, and the desired aromatic polyimide endless belt (resin endless belt) can be obtained. The obtained aromatic polyimide endless belt may be further subjected to slit processing, punching drilling processing, tape winding processing, or the like as necessary.

  A solution in which a resin having a block structure or a precursor thereof is dissolved in a solvent is applied onto a cylindrical mold, and dried and fired under the above processing conditions, so that it becomes hydrophobic with respect to the hard segment of the main chain. The soft segment, which is a structure, is also attracted to a hydrophobic air atmosphere, and can be slowly localized on the belt surface layer. Therefore, the endless belt obtained by the method for producing a resin endless belt according to the present invention has an effective material configuration for developing a self-healing property of a wound. Furthermore, in the present invention, since the solvent is present, the degree of freedom of molecular motion is high and the transition of the soft segment to the belt surface is likely to proceed.

  When the resin endless belt is used as an intermediate transfer belt or an intermediate transfer and fixing belt, it is necessary to include a conductive agent in the resin solution composition as described above so as to obtain a desired electric resistance. . As the conductive agent, those listed above are used. The amount of addition is as described above.

  In addition, when a resin endless belt is used as a fixing belt or intermediate transfer and fixing belt, a non-adhesive resin layer is provided on the belt surface (outer peripheral surface) in order to prevent fusion of toner adhering to the surface (outer peripheral surface). It may be formed.

  Examples of the material constituting the resin layer include fluorine resins such as polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-hexafluoropropylene copolymer (FEP). Is mentioned. In addition, the resin layer is made of carbon powder, inorganic compound powder such as titanium oxide, barium sulfate, etc. for fluororesin in order to improve wear resistance, electrostatic offset, and affinity with toner adhesion prevention oil. Other materials may be included.

In order to form, for example, a fluororesin layer on the outer peripheral surface of the resin endless belt, a method in which the aqueous dispersion is applied to the belt surface and baked is preferable. Moreover, when the adhesiveness of a fluororesin layer is insufficient, there is a method of forming a primer layer on the surface of the resin endless belt as necessary.
Examples of the material constituting the primer layer include polyphenylene sulfide, polyethersulfone, polysulfone, polyamideimide, polyimide, and derivatives thereof, and it is preferable that at least one compound selected from fluorine resins is included. The thickness of the primer layer is preferably in the range of 0.5 to 10 μm.

  In order to form the primer layer and the fluororesin layer on the outer peripheral surface of the resin endless belt, a material for forming these layers on the resin film (endless belt) (after heat treatment) formed on the outer peripheral surface of the core body is used. It can be formed by coating. Alternatively, a dispersion containing the material constituting the primer layer or the material constituting the fluororesin layer is applied on the coating film of the resin solution composition (before the heat treatment) formed on the outer peripheral surface of the core body, and then heated. Then, the resin solution composition and the fluororesin may be fired at the same time. In the latter case, even if there is no primer layer, the adhesion between the endless belt and the fluororesin layer may be sufficiently strong. In this case, it is not necessary to form a primer layer.

  As mentioned above, although the manufacturing method of the resin endless belt concerning this invention was demonstrated taking the case where a hard segment is aromatic polyimide as an example, manufacture of the resin endless belt of this invention is limited only to these aspects. However, the present invention can be carried out in a mode in which various improvements, changes and modifications are made based on the knowledge of those skilled in the art without departing from the spirit of the invention.

<Image forming apparatus>
The image forming apparatus of the present invention preferably includes the above-described resin endless belt of the present invention as an intermediate transfer member and / or a fixing member. FIG. 1 is a schematic configuration diagram of a color electrophotographic copying machine 100 which is an example of an image forming apparatus of the present invention using the above-described resin endless belt of the present invention as an intermediate transfer member.

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

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

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

  Since the resin endless belt of the present invention described above is used for the intermediate transfer member 102, it is possible to reduce defects caused by film thickness non-uniformity of the conventional endless belt.

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

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

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

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

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

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

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

<Example>
Synthesis Example 1 Preparation of Aromatic Polyamic Acid Solution 3,3 ′, 4,4′-biphenyltetracarboxylic acid was passed through a nitrogen gas dried with phosphorus pentoxide through a flask equipped with a stirrer, thermometer, and dropping funnel. 29.42 g (100 mmol) of acid dianhydride (hereinafter abbreviated as BPDA) and 117.68 g of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) were injected. After sufficiently stirring and dissolving, 19.72 g (98.5 mmol) of 4,4′-diaminodiphenyl ether (hereinafter abbreviated as ODA) and 1.00 g of p-hexadecyloxyaniline (hereinafter abbreviated as C16An) ( 3 mmol) was gradually added dropwise into a flask maintained at 10 ° C. in a solution of NMP 82.88 g, which is 4 times the amount. The solid content concentration during the reaction was 20% by mass.
After dropping the p-hexadecyloxyaniline solution, stirring and polymerization were carried out at 10 to 15 ° C. for 6 hours. The reaction solution was poured into a large amount of methanol, and reprecipitation purification was performed. The precipitated white polymer was filtered off and dried, and then redissolved in NMP to obtain a 20% by mass aromatic polyamic acid solution.

-Soft segment content-
The soft segment content of the synthesized resin was determined from the ratio of the mass of the soft segment raw material to the total mass of the resin raw material.

(Synthesis Examples 2 to 6) Preparation of aromatic polyamic acid solution Amount of amine raw material, amount of soft segment raw material, soft segment raw material (stearylamine (hereinafter abbreviated as C18A) or 3-aminopropyltrisiloxane ((CH ₃ ) ₃ Si—O—Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ — (CH ₂ ) ₃ —NH ₂ ; hereinafter abbreviated as Si ₃ C ₃ A))) A resin was synthesized in the same manner as in Synthesis Example 1 except that the aromatic polyamic acid solution was obtained.

(Synthesis Example 7) Preparation of aromatic polyamide solution 21.06 g (100 mmol) of trimellitic anhydride chloride (hereinafter abbreviated as TMAC) was used as an acid raw material, and 7.9 g (100 mmol) of pyridine was added as a catalyst during polymerization. Except that, a resin was synthesized in the same manner as in Synthesis Example 1 to obtain an aromatic polyamide solution.

Synthesis Example 8 Preparation of Aromatic Polyamideimide Solution Synthesis Example 1 except that BPDA and TMAC were used as acid raw materials in the composition shown in Table 1, and 7.9 g (100 mmol) of pyridine was added as a catalyst during polymerization. Resins were synthesized in the same manner as in -3 to obtain an aromatic polyamideimide solution.

  Table 1 shows the raw material used for resin synthesis and the soft segment content of the obtained resin for each synthesis example.

(Preparation Examples 1 to 8) Preparation of Resin Solution Compositions (A) to (H) Each resin solution prepared in Synthesis Examples 1 to 8 was filtered with a 20 μm pore fluoropore filter paper to remove insoluble parts, Aromatic polyamic acid solution compositions (A) to (F), an aromatic polyamide solution composition (G), and an aromatic polyamideimide solution composition (H) were obtained, respectively.

(Preparation Examples 9 to 16) Preparation of Carbon Black Dispersed Resin Solution Compositions (a) to (h) In each resin solution 200 g prepared in Synthesis Examples 1 to 8, dried oxidized carbon black (SPECIAL BLACK4, Degussa) Manufactured, pH: 4.0, volatile content: 14.0%) was added, and the mixture was treated with a ball mill for 6 hours. Thereafter, the aggregates are removed by filtering with a 20 μm pore fluoropore filter paper, and the carbon black-dispersed aromatic polyamic acid solution compositions (a) to (f) and the carbon black-dispersed aromatic polyamide solution composition ( g) A carbon black-dispersed aromatic polyamideimide solution composition (h) was obtained.

  Table 2 summarizes the resin solution compositions (A) to (H) and carbon black-dispersed resin solution compositions (a) to (h) prepared in Preparation Examples 1 to 16.

(Production Example 1)
The aromatic polyamic acid solution composition (A) was uniformly applied to the surface of a cylindrical SUS mold having an inner diameter of 90 mm and a length of 450 mm (coating process). The cylindrical mold was preliminarily coated with a fluorine-based release agent to improve the peelability after belt molding. Next, a drying process was performed for 30 minutes at a temperature of 120 ° C. while rotating the mold (drying step).
After the drying treatment, a mold on which an aromatic polyamic acid molded article was formed was placed in a heating furnace. The temperature in the furnace was heated to 120 ° C., and then a baking treatment was performed while increasing the temperature to 300 ° C. at a rate of 2 ° C. per minute (baking step). During firing, the water vapor content in the furnace was kept at 5% by volume or less.

-Water vapor content-
The water vapor content in the furnace in the firing step was measured in real time using an integrated zirconia high-temperature hygrometer ZR202G manufactured by Yokogawa Electric Corporation, and the average value was taken as the water vapor content.

  After finishing the firing treatment, the inside of the furnace was returned to room temperature and normal pressure, and the mold was taken out. The resin was removed from the mold to obtain the desired aromatic polyimide endless belt (resin endless belt). The obtained belt was tested as follows for belt appearance, water contact angle on the belt surface, and scratch recovery.

-Belt appearance-
The appearance of the obtained belt was visually observed and evaluated as follows.
“◯”: No conspicuous scratches are seen on the belt surface, and the uniformity of the film is excellent.
“Δ”: Scratches are seen on the belt surface, which is somewhat hindered in practical use.
“X”: A conspicuous scratch was seen on the belt surface, and it was not practical.

-Contact angle of water-
A test piece of 5 cm × 5 cm was cut out from the obtained aromatic polyimide endless belt. A contact angle meter CA-X manufactured by Kyowa Interface Science Co., Ltd. was used for measuring the contact angle. The test piece was developed and fixed horizontally on the sample stage, 20 μl of ion-exchanged water was dropped on the belt surface, and the contact angle of the water droplet was measured from the side surface to obtain the contact angle with water.

-Wound recovery test-
Ten test pieces of 5 cm × 5 cm were randomly cut out from the obtained aromatic polyimide endless belt. The surface of the belt was rubbed twice with # 1000 sandpaper in one direction to cause scratches. Thereafter, the test piece was heat-treated in a clean oven adjusted to 200 ° C. for 3 hours. The scratches on the belt surface were visually compared before and after the heat treatment. The wound self-healing property was evaluated based on the following criteria.
“◎”: Scratches were clearly reduced by heat treatment “◯”: Scratches were reduced by heat treatment “△”: Scratches were slightly reduced by heat treatment “×”: Scratches were not reduced by heat treatment

(Production Examples 2 to 16)
With respect to the resin solution compositions (B) to (H) and the carbon black dispersed resin solution compositions (a) to (h) prepared in Preparation Examples 2 to 16, resin endless belts were respectively used in the same manner as in Production Example 1. Manufactured. About the belt produced in the manufacture examples 9-16 using the resin solution composition in which carbon black is dispersed, the following volume resistance value measurement and a mounting test as an intermediate transfer belt in an electrophotographic apparatus were performed. It was.

−Volume resistance value−
A test piece of 10 × 10 cm ² was cut out from each resin endless belt, and its volume resistance value was measured with an ultra high resistance measuring device (digital ultra high resistance / microammeter R8340A) manufactured by Advantech.

-Electrophotographic equipment mounting test-
Each resin endless belt was incorporated as an intermediate transfer belt of an electrophotographic apparatus DocuCentreColor400CP manufactured by Fuji Xerox Co., Ltd., and the initial copy image quality was evaluated. As evaluation items for copy image quality, the presence / absence of printing deviation, the presence / absence of uneven printing density, the presence / absence of ghost, etc. were evaluated. Further, the image quality after the 50,000 sheet passing test was evaluated in the same manner. The scratches on the belt surface before and after the paper passing test were visually evaluated according to the following criteria.
“◎”: After passing the paper, no scratch was seen on the belt surface, and it was at a practical level.
“◯”: After the paper was passed, the belt surface was slightly scratched, but it was at a level that would not hinder practical use.
“Δ”: After passing the paper, scratches occurred on the belt surface. There is no problem in practical use.
"X": After passing the paper, the belt surface was scratched and torn and could not be used practically.
The belt characteristic evaluation results for each resin endless belt are summarized in Table 3.

  As shown in Table 3, the resin endless belt obtained in the present invention has a hydrophobic long-chain alkyl group and a poly-silicone group unevenly distributed on the surface, so that the contact angle of the film direction becomes large and scratches are hardly caused. became. In addition, it had the ability to self-repair the scratches that occurred. Further, it was confirmed that when it was mounted on an electrophotographic apparatus with excellent electrical characteristics, it had characteristics suitable as an intermediate transfer belt.

<Comparative example>
(Synthesis Examples 9 to 13) Preparation of Resin Solutions Each resin solution was obtained with the composition shown in Table 4 in the same manner as in Synthesis Examples 1 to 8.

(Preparation Examples 17 to 26) Preparation of Resin Solution Compositions (M) to (Q) and Carbon Black Dispersed Resin Solution Compositions (m) to (q) Using the resin solutions obtained in Synthesis Examples 9 to 13 In the same manner as in Preparation Examples 1 to 16, various resin solution compositions (M) to (Q) and carbon black-dispersed resin solution compositions (m) to (q) were obtained. The obtained resin solution compositions are summarized in Table 5.

(Production Examples 17 to 26)
Using each resin solution composition prepared in Preparation Examples 17 to 26, resin endless belts were manufactured in the same manner as in Production Examples 1 to 16. The obtained resin endless belts were evaluated in the same manner as in Production Examples 1 to 16. These belt characteristics are shown in Table 6.

  About the obtained resin endless belt, when the manufacture example (Table 3) of an Example and the manufacture example (Table 6) of a comparative example were compared, the resin endless belt of this invention is hard to be damaged, and it generate | occur | produces. It was also found that the wounds were self-healing. Further, it was found that when mounted on an electrophotographic apparatus, it showed good characteristics as an intermediate transfer belt and could be used in an actual machine.

  From the above results, the endless belt made of resin according to the present invention was improved only in mechanical characteristics and electrical characteristics and improved in self-repairing property against scratches. In addition, the image forming apparatus including the resin endless belt of the present invention can stably obtain high quality image quality.

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

Explanation of symbols

100 Image forming apparatus 101BK, 101Y, 101M, 101C Photosensitive drum 102 Intermediate transfer member (resinless endless belt)
103 Recording medium 105, 106, 107, 108 Developer 109, 110, 111, 112 Corona discharger 113 Tray 114 Peeling claw 115 Conveying belt 117, 118, 119, 120 Roll 121, 122, 123, 124 Transfer baffle 125 Pressure roll

Claims (6)

A linear or branched long chain alkyl group having 8 to 22 carbon atoms or a poly-silicone at both ends of a hard segment containing any structure of aromatic polyimide, aromatic polyamide and aromatic polyamideimide in the main chain A resin endless belt characterized by comprising a resin having a block structure in which soft segments containing are bonded and the content of the soft segments is in the range of 1 to 20% by mass. The resin endless belt according to claim 1, wherein the polysilicon is a polysilicon having a structure represented by the following structural formula (1).

(In the above formula, R1 is .p indicating a hydrocarbon group of carbon number 1 to 12 is an integer of 0 to 12, q represents an integer of 1 to 12, respectively.) Resin endless belt according to claim 1 or 2, characterized in that it contains a further conductive agent. An image forming apparatus comprising: a resin-made endless belt according to any one of claims 1-3. The image forming apparatus according to claim 4, wherein the resin endless belt is provided as an intermediate transfer belt and / or a fixing belt. It is a manufacturing method of a resin endless belt given in any 1 paragraph of Claims 1-3 ,
A coating step of applying the resin solution composition to the cylindrical mold, and a drying / firing step of performing drying / firing treatment, wherein the drying / firing step is performed in an atmosphere having a water vapor content of 50% by volume or less, or A method for producing a resin endless belt, which is performed under a reduced pressure of 10 Pa or less.