JP2009001616A - Polyaniline composition, polyamic acid composition, polyimide molded article, its production method, endless belt, belt-stretching device, and image forming device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: a polyaniline composition which satisfies both of good storage stability and ability to efficiently impart electrical conductivity; a polyamic acid composition which satisfies both of good storage stability and excellent electrical conductivity; a polyimide molded article in which the variations of the electrical resistance value and the film thickness are satisfactorily suppressed and which has excellent quality; an endless belt in which the variations of the electrical resistance value and the film thickness are satisfactorily suppressed and which has excellent quality; and an image forming device which can form an image having excellent quality. <P>SOLUTION: The polyaniline composition contains at least a polyaniline and a thermal latent compound. The polyamic acid composition contains at least the polyaniline composition and a polyamic acid. The polyamide molded article is produced by dehydrating and imidizing the polyamic acid composition. The endless belt is obtained by forming the polyamic acid composition into a ring form by dehydrating and imidizing the polyamic acid composition. The image forming device is equipped with the polyimide molded article. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polyaniline composition, a polyamic acid composition, a polyimide molding and a method for producing the same, an endless belt, a belt stretching device, and an image forming apparatus.

  Polyaniline has characteristics such as stability in the air, reduction in manufacturing cost, and ease of control of conductivity, so that it can be used for plastic battery electrode materials, antistatic materials, display elements, electronic devices, capacitors, electromagnetic shielding materials, static electricity. Widely used for electroadsorption film, conductive paste material, etc. Furthermore, polyaniline is an additive for imparting electrical conductivity and flexibility. Polymer materials such as polyimide resin, acrylic resin, urethane resin, fluororesin, urea resin, epoxy resin, rubber-based polymer, and thermoplastic resin It is used as a mixture.

Polyimide resins are widely used from the field of electrical and electronic parts to the field of aircraft due to their heat resistance, radiation resistance, chemical resistance, mechanical strength, dimensional stability, and the like. For example, in the field of electrical and electronic components, it is widely used for flexible printed circuit boards, liquid crystal alignment films for liquid crystal display elements, insulating films or protective films for semiconductor devices, conductor coating films, and the like.
In recent years, polyimide resins have been used in parts of image forming apparatuses, such as belt members such as paper separation claws, bearings, fixing belts, transfer belts, and paper transport belts.

  Here, the image forming apparatus is formed by charging (charging) a photoconductor made of a photoconductive material, forming an electrostatic latent image by exposure with a laser or the like based on a modulated image signal, and then charging toner. Thus, the electrostatic latent image is developed into a toner image. Next, the toner image is transferred directly or via an intermediate transfer member to a recording medium such as paper, cardboard, or OHP sheet, and fixed by means of a heat and pressure fixing method (thermal fixing method) to obtain an image. It is.

  Until now, as the thermal fixing method, a two-roll fixing method in which pressure and heat are applied through a recording medium through a gap formed by two rolls has been provided. However, in recent years, a system that uses a movable roll and belt that applies heat as a fixing body (so-called free belt nip fixing system) has been provided in order to cope with higher speeds of machines and energy saving for environmental considerations. (For example, see Patent Documents 1 and 2). In this method, the contact area between the recording medium and the fixing member is large, and the roll is thin. Therefore, compared to the conventional two-roll fixing method, high-speed fixing and energy saving (such as shortening the heating time of the fixing member). It has the advantage that it can be operated.

As a material for the transfer belt, paper conveyance belt, fixing belt and the like, as described above, polyimide resin is suitable because of its heat resistance, dimensional stability, and mechanical strength. When used as the transfer belt, paper transport belt, etc., the belt is semiconductive (the above “semiconductive” means that the volume resistivity is 10 ⁶ Ω · cm or more and 10 ¹³ Ω · cm or less. It is necessary to be semiconductive even when used as the fixing belt, but the polyimide resin itself is generally insulative (the above-mentioned “insulation”). “Resistivity” means that the volume resistivity exceeds 10 ¹³ Ω · cm, and is common in this specification. Therefore, various conductive materials (polyaniline, polyacetylene, polythiol, polypyrrole) with respect to the polyimide resin are used. , Poly-p-phenylene, carbon black, graphite, metal particles, indium oxide, etc.) are mixed to control the electrical resistance value. Among these, a polyimide resin mixed with a conductive polymer such as polyaniline is favorably used from the viewpoint of flexibility (for example, see Patent Documents 3 and 4).

  Polyamic acid compositions are used as paints and other adhesives for producing polyimide moldings such as belts made of polyimide resin. In general, polyimide resin is insoluble in a solvent, so its precursor. A polyimide molded product is obtained by molding a polyamic acid solution, which is a body, and heating after drying the solvent to perform a dehydration imidization reaction of the amic acid group. From the viewpoint of suitably proceeding with the dehydrating imidation reaction, a catalyst is generally added to the polyamic acid composition (see, for example, Patent Documents 5 and 6).

  When mixing the polyaniline as a conductive agent into the polyamic acid composition, a dopant that imparts conductivity to the polyaniline is dispersed and mixed together with the polyaniline to obtain a polyimide molding from the polyamic acid composition. In that case, since acidic compounds, such as sulfonic acids, are generally used as the dopant, the acidic compound (dopant) can also have a function as a catalyst for causing the dehydration imidization reaction to proceed appropriately.

Even when polyaniline is used alone as an electrode material or an antistatic material for the above-described plastic battery, sulfonic acids and the like are added as a dopant, mixed and dispersed in a solvent, etc., and then used by molding and drying by heating. (For example, Patent Documents 7 and 8).
JP-A-2005-37678 JP 2003-107936 A JP 2001-109277 A JP-T-2-500288 Publication JP 2002-283366 A JP 2004-287005 A JP-A-8-41321 Japanese Patent Application Laid-Open No. 2005-10056

  However, in the conventional polyaniline composition and polyamic acid composition, it is difficult to obtain good storage stability, and from the viewpoint of providing a polyimide molded product excellent in quality, good storage stability and excellent conductivity It was desired to achieve both.

  That is, the object of the present invention is to provide a polyaniline composition having both good storage stability and efficient conductivity, a polyamic acid composition having both good storage stability and excellent conductivity, and electrical resistance. In addition, the polyimide molded product excellent in quality by suppressing the variation in film thickness and the production method of the polyimide molded product capable of easily producing the polyimide molded product, the electrical resistance value and the variation in film thickness are suppressed well. It is possible to form an endless belt with excellent quality, a belt stretching device that suppresses variations in electric resistance value and film thickness, and exhibits excellent quality even for circular driving, and an image with excellent quality. An object is to provide an image forming apparatus.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by using a polyaniline composition containing a thermal latent compound, and have completed the present invention.

  That is, the invention according to claim 1 is a polyaniline composition containing at least polyaniline and a heat latent compound.

  The invention according to claim 2 is a polyaniline composition in which the basic compound which is the dissociation product of the heat latent compound according to claim 1 has a boiling point equal to or lower than the dissociation temperature of the heat latent compound.

  The invention according to claim 3 is a polyamic acid composition containing at least the polyaniline composition according to claim 1 or 2 and a polyamic acid.

  The invention according to claim 4 is a polyimide molded product produced by dehydrating and imidizing the polyamic acid composition according to claim 3.

  The invention according to claim 5 uses the polyamic acid composition according to claim 3, a drying molding step of molding and drying with a molding machine, and an imidization step of dehydrating and imidizing the molded polyamic acid composition; , A method for producing a polyimide molded product having

  The invention according to claim 6 is an endless belt formed by dehydrating and imidizing the polyamic acid composition according to claim 3 into a ring shape.

  The invention according to claim 7 is a belt stretching device comprising: the endless belt according to claim 6; and a plurality of stretching members that rotatably stretch the endless belt from the inner peripheral surface side. .

  The invention according to claim 8 is an image holding member, a latent image forming unit that forms an electrostatic latent image on the image holding member, a developing unit that develops the latent image with toner and forms a toner image, 5. An image forming apparatus comprising a polyimide molding product according to claim 4, comprising transfer means for transferring the toner image to a recording medium and fixing means for fixing the toner image transferred to the recording medium. is there.

  According to the invention which concerns on Claim 1, compared with the case where a heat | fever latent compound is not contained, favorable storage stability and efficient provision of electroconductivity can be made compatible.

  According to the invention which concerns on Claim 2, compared with the case where the boiling point of the basic compound which is a dissociation product of a thermal latent compound is not considered, more efficient provision of electroconductivity is realizable.

  According to the invention which concerns on Claim 3, compared with the case where the polyaniline composition which has a thermal latent compound is not contained, favorable storage stability and the outstanding electroconductivity can be made compatible.

  According to the invention which concerns on Claim 4, compared with the case where the polyaniline composition which has a heat | fever latent compound is not used, the variation in an electrical resistance value and a film thickness can be suppressed favorably, and quality can be improved.

  According to the invention which concerns on Claim 5, compared with the case where the polyaniline composition which has a heat | fever latent compound is not used, the polyimide molding which suppressed the electrical resistance value and the dispersion | variation in film thickness well, and improved quality is easy. Can be manufactured.

  According to the invention which concerns on Claim 6, compared with the case where the polyaniline composition which has a heat | fever latent compound is not used, the variation in an electrical resistance value and a film thickness can be suppressed favorably, and quality can be improved.

  According to the seventh aspect of the invention, compared to a case where an endless belt using a polyaniline composition having a thermal latent compound is not provided, variation in electric resistance value and film thickness can be suppressed well, and circular driving can be achieved. In contrast, the quality can be improved.

  According to the invention which concerns on Claim 8, compared with the case where the endless belt using the polyaniline composition which has a thermal latent compound is not provided, the image excellent in quality can be formed.

<Polyaniline composition>
First, the polyaniline composition according to the first embodiment which is a preferred aspect will be described in detail.
The polyaniline composition according to the first embodiment contains at least polyaniline and a heat latent compound.

  Moreover, the polyaniline composition according to the first embodiment can further contain a solvent, an additive and the like in addition to the polyaniline and the heat latent compound. Details of the polyaniline and thermal latent compound used are shown below.

-Polyaniline-
In general, polyaniline can be obtained by polymerizing monomers of anilines. As the polyaniline used in the polyaniline composition according to the first embodiment, polyaniline having a quinonediimine structural unit and a phenylenediamine structural unit represented by the following general formula (I) as main repeating units is preferably used.

(In the above general formula (I), m and n respectively represent the molar fractions of the quinonediimine structural unit and the phenylenediamine structural unit in the repeating unit, and 0 <m <1, 0 <n <1, m + n = 1. .)

  Examples of anilines used as a raw material (monomer) for polymerizing polyaniline include aniline, toluidine, xylidine, anisidine, phenetidine, cresidine, pseudocumidine, mesidine, cumidine, planidin, juridin, isoduridine, semizine, benzidine, tolidine and dianisidine. .

The number average molecular weight of polyaniline is preferably 4,000 or more and 400,000 or less. In the present specification, the number average molecular weight can be measured under the following conditions.
Measuring instrument: HLC-8120GPC (manufactured by TOSOH)
Detector: UV8020 (manufactured by TOSOH), wavelength 254 nm
Column: TSK guard column Super HL, TSK Super H3000, TSK Super H2500, TSK Super H2000 (above, manufactured by TOSOH) are connected in series in this order. Flow rate: 0.4 ml / min
Solvent: THF (tetrahydrofuran)
Column temperature: 40 ° C
Molecular weight reference material: Standard polystyrene (manufactured by TOSOH)

-Thermal latent compounds-
The heat latent compound used in the polyaniline composition according to the first embodiment is a compound that does not show activity under normal temperature conditions (about 0 ° C. or more and about 30 ° C. or less) and shows activity when heated as an external stimulus. In this specification, “a compound having a dissociation temperature of 50 ° C. or higher” is defined as a thermal latent compound.

Here, a method for measuring the dissociation temperature will be described.
In this specification, “dissociation temperature” means the release of molecules contained in a polymer by the temperature change, the desorption of molecules distributed and adsorbed on pore compounds, the dissociation of salts, It causes a change in molecular structure such as the generation of reactive groups that exhibit activity and the dissociation of complexes.

The dissociation temperature can be determined by preparing a DSC exothermic curve using a differential scanning calorimetry method by a reaction using an appropriate reaction system, for example, a polyamic acid composition containing the thermal latent compound. . Specifically, an input-compensated differential scanning calorimeter (Diamond DSC, manufactured by PerkinElmer Japan Co., Ltd.) whose sensitivity does not depend on temperature can be used, and 10 mg of a sample can be measured under certain measurement conditions (heating rate). : 40 ° C./min, reference material: α-alumina), the temperature at the endothermic peak is read from the chart of temperature (° C.) on the horizontal axis and heat flow rate (J / s) on the vertical axis. The “dissociation temperature” can be determined.
In addition, in this specification, regarding the thermal latent compound as a commercial product, the value of the dissociation temperature or the value corresponding thereto is preferentially used, and the value is used preferentially. The value measured by the above method was used.

  For example, when the polyaniline composition according to the first embodiment is used for a polyimide molded product described later, the dissociation temperature of the thermal latent compound is equal to or higher than the boiling point of the organic solvent in the drying step of the polyimide molded product production method. And since it is preferable in terms of quality to specify a drying temperature at which the imidization reaction of the polyamic acid composition does not occur, it is preferably 90 ° C. or higher, and particularly preferably 120 ° C. or higher. In addition, the upper limit of the dissociation temperature is preferably 180 ° C. or less, particularly preferably 150 ° C. or less, since it is preferable in terms of quality and production cost to perform a quick reaction in the imidization process. preferable.

Moreover, when the said thermal latent compound produces | generates a basic compound as a dissociation product, it is preferable that this basic compound has a boiling point below the dissociation temperature of the said thermal latent compound. Furthermore, it is more preferably 5 ° C. or more lower than the dissociation temperature of the heat latent compound, and particularly preferably 10 ° C. or more. The lower limit of the boiling point is preferably 40 ° C. or higher.
In addition, it can confirm that the boiling point of the said basic compound is below the dissociation temperature of the said thermal latent compound by the weight reduction measurement by differential thermogravimetric analysis (Derivative Thermogravimetry). Specifically, a DTG measuring device (Thermal Analyzer DT-40, Shimadzu Corporation) can be used, and 10 mg of a sample can be measured under certain measurement conditions (heating rate: 40 ° C./min, reference material: α− Measure the temperature under (Alumina) and read the temperature at the peak of weight loss due to vaporization of the basic compound from the chart with temperature (° C) on the horizontal axis and sample weight (mg) on the vertical axis. Can do.

Examples of the heat latent compound include the following.
(A) a microcapsule in which a protonic acid and / or a protonic acid derivative is encapsulated with a polymer; (b) a protonic acid and / or a protonic acid derivative adsorbed on a pore compound such as zeolite; and (c) a protonic acid and // Protonic acid derivative blocked with base (thermal latent protonic acid compound)
(D) Protic acid and / or proton acid derivative esterified with primary or secondary alcohol (e) Protic acid and / or proton acid derivative blocked with vinyl ethers and / or vinyl thioethers (f) Boron trifluoride monoethylamine complex (g) Boron trifluoride pyridine complex Among these, from the viewpoint of activity, storage stability, availability, and cost, (c) a protonic acid and / or a protonic acid derivative with a base What was blocked (thermal latent protonic acid compound) is particularly preferred.

(A) Microcapsules in which protonic acid and / or protonic acid derivative are encapsulated in polymer particles Protonic acid includes sulfuric acid, hydrochloric acid, butyric acid, formic acid, nitric acid, phosphoric acid, borohydrofluoric acid, hydrophosphoric acid, persulfate Chloric acid, monocarboxylic acid, polycarboxylic acids, propionic acid, oxalic acid, acrylic acid, methacrylic acid, itaconic acid, phthalic acid, maleic acid, pentadecafluorooctanoic acid, acetic acid, pentafluoroacetic acid, trifluoroacetic acid, trichloroacetic acid , Dichloroacetic acid, monofluoroacetic acid, monobromoacetic acid, monochloroacetic acid, cyanoacetic acid, acetylacetic acid, nitroacetic acid, triphenylacetic acid, benzoic acid, o, m, p-bromobenzoic acid, o, m, p-chlorobenzoic acid, o, m, p-nitrobenzoic acid, dinitrobenzoic acid, picric acid, trimethylbenzoic acid, o, m P-cyanobenzoic acid, thymol blue, salicylic acid, 5-aminosalicylic acid, o-methoxybenzoic acid, 1,6-dinitro-4-chlorophenol, 2,6-dinitrophenol, 2,4-dinitrophenol, p- Oxybenzoic acid, bromophenol blue, mandelic acid, phthalic acid, isophthalic acid, maleic acid, fumaric acid, malonic acid, tartaric acid, citric acid, lactic acid, succinic acid, α-alanine, β-alanine, glycine, glycolic acid, thio Glycolic acid, ethylenediamine-N, N′-diacetic acid, ethylenediamine-N, N, N ′, N′-tetraacetic acid, sulfonic acid, aminonaphtholsulfonic acid, metanilic acid, sulfanilic acid, allylsulfonic acid, laurylsulfuric acid, xylene Sulfonic acid, chlorobenzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, 1 -Propanesulfonic acid, 1-butanesulfonic acid, 1-hexanesulfonic acid, 1-heptanesulfonic acid, 1-octanesulfonic acid, 1-nonanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, benzenesulfonic acid , Styrenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, ethylbenzenesulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, pentylbenzenesulfonic acid, hexylbenzenesulfonic acid, heptylbenzenesulfonic acid, octylbenzenesulfonic acid, nonyl Benzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, octadecylbenzenesulfonic acid, diethylbenzenesulfonic acid, di Propylbenzenesulfonic acid, dibutylbenzenesulfonic acid, methylnaphthalenesulfonic acid, ethylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, pentylnaphthalenesulfonic acid, hexylnaphthalenesulfonic acid, heptylnaphthalenesulfonic acid, octylnaphthalenesulfonic acid Nonylnaphthalenesulfonic acid, decylnaphthalenesulfonic acid, undecylnaphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, pentadecylnaphthalenesulfonic acid, octadecylnaphthalenesulfonic acid, dimethylnaphthalenesulfonic acid, diethylnaphthalenesulfonic acid, dipropylnaphthalenesulfonic acid, dibutyl Naphthalenesulfonic acid, dipentylnaphthalenesulfonic acid, dihexylnaphthalenesulfonic acid, Tylnaphthalenesulfonic acid, dioctylnaphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, trimethylnaphthalenesulfonic acid, triethylnaphthalenesulfonic acid, tripropylnaphthalenesulfonic acid, tributylnaphthalenesulfonic acid, camphorsulfonic acid, acrylamide-t-butylsulfonic acid, ethane Disulfonic acid, propanedisulfonic acid, butanedisulfonic acid, pentanedisulfonic acid, hexanedisulfonic acid, heptanedisulfonic acid, octanedisulfonic acid, nonanedisulfonic acid, decanedisulfonic acid, benzenedisulfonic acid, naphthalenedisulfonic acid, toluenedisulfonic acid, ethylbenzenedisulfonic acid , Propylbenzene disulfonic acid, butylbenzene disulfonic acid, dimethylbenzene disulfonic acid, diethylbenzene Disulfonic acid, dipropylbenzene disulfonic acid, dibutylbenzene disulfonic acid, methyl naphthalene disulfonic acid, ethyl naphthalene disulfonic acid, propyl naphthalene disulfonic acid, butyl naphthalene disulfonic acid, pentyl naphthalene disulfonic acid, hexyl naphthalene disulfonic acid, heptyl naphthalene disulfonic acid, octyl Naphthalene disulfonic acid, nonyl naphthalene disulfonic acid, dimethyl naphthalene disulfonic acid, diethyl naphthalene disulfonic acid, dipropyl naphthalene disulfonic acid, dibutyl naphthalene disulfonic acid, naphthalene trisulfonic acid, naphthalene tetrasulfonic acid, anthracene disulfonic acid, anthraquinone disulfonic acid, phenanthrene disulfonic acid Acid, fluorenone disulfonic acid, carbazole dis Phosphonic acid, diphenylmethane disulfonic acid, biphenyl disulfonic acid, terphenyl disulfonic acid, terphenyl trisulfonic acid, naphthalene sulfonic acid-formalin condensate, phenanthrene sulfonic acid-formalin condensate, anthracene sulfonic acid-formalin condensate, fluorene sulfonic acid- Formalin condensate, carbazole sulfonic acid-formalin condensate, polyvinyl sulfonic acid, polyvinyl sulfuric acid, polystyrene sulfonic acid, sulfonated styrene-butadiene copolymer, polyallyl sulfonic acid, polymethallyl sulfonic acid, poly-2-acrylamide-2 -Methylpropanesulfonic acid, polyhalogenated acrylic acid, polyisoprenesulfonic acid, N-sulfoalkylated polyaniline, nuclear sulfonated polyaniline and the like.

  Examples of the proton acid derivative include neutralized products such as alkali metal salts or alkaline earth metal salts of proton acids such as sulfonic acid and phosphoric acid.

  Further, as a polymer monomer enclosing the above protonic acid and / or protonic acid derivative, methacrylic compounds such as acrylic acid ester, methacrylic acid ester, itaconic acid ester, crotonic acid ester, styrene, α-methylstyrene, chloride Monofunctional monomers such as vinyl, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, divinylbenzene, bisphenol A di (meth) acrylate, methylenebis And polyfunctional monomers such as (meth) acrylamide.

  As an example of a method for microencapsulating the protonic acid and / or protonic acid derivative and the polymer, a capsule material in which the protonic acid and / or the protonic acid derivative and the polymer monomer are dispersed is given. Further, a microcapsule in which the protonic acid and / or protonic acid derivative is encapsulated in the polymer can be obtained by adding a dispersing agent and a polymerization accelerator as additives, dispersing and mixing, and performing a heat polymerization reaction. This method is based on a general suspension polymerization method or emulsion polymerization method.

(B) Protonic acid and / or protonic acid derivative adsorbed on a porous material such as zeolite Examples of the porous material include zeolites, mesoporous materials, clay, activated carbon and the like.

  Examples of the protonic acid to be adsorbed include sulfuric acid, hydrochloric acid, butyric acid, formic acid, nitric acid, phosphoric acid, borohydrofluoric acid, phosphorous hydrofluoric acid, perchloric acid, monocarboxylic acid, polycarboxylic acids, propionic acid, oxalic acid, Acrylic acid, methacrylic acid, itaconic acid, phthalic acid, maleic acid, pentadecafluorooctanoic acid, acetic acid, pentafluoroacetic acid, trifluoroacetic acid, trichloroacetic acid, dichloroacetic acid, monofluoroacetic acid, monobromoacetic acid, monochloroacetic acid, cyanoacetic acid, Acetylacetic acid, nitroacetic acid, triphenylacetic acid, benzoic acid, o, m, p-bromobenzoic acid, o, m, p-chlorobenzoic acid, o, m, p-nitrobenzoic acid, dinitrobenzoic acid, picric acid, Trimethylbenzoic acid, o, m, p-cyanobenzoic acid, thymol blue, salicylic acid, 5-aminosalicyl O-methoxybenzoic acid, 1,6-dinitro-4-chlorophenol, 2,6-dinitrophenol, 2,4-dinitrophenol, p-oxybenzoic acid, bromophenol blue, mandelic acid, phthalic acid, isophthalic acid , Maleic acid, fumaric acid, malonic acid, tartaric acid, citric acid, lactic acid, succinic acid, α-alanine, β-alanine, glycine, glycolic acid, thioglycolic acid, ethylenediamine-N, N′-diacetic acid, ethylenediamine-N , N, N ′, N′-tetraacetic acid, sulfonic acid, aminonaphthol sulfonic acid, metanilic acid, sulfanilic acid, allyl sulfonic acid, lauryl sulfuric acid, xylene sulfonic acid, chlorobenzene sulfonic acid, methane sulfonic acid, ethane sulfonic acid, 1 -Propanesulfonic acid, 1-butanesulfonic acid, 1-hexanesulfone 1-heptanesulfonic acid, 1-octanesulfonic acid, 1-nonanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, benzenesulfonic acid, styrenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, ethylbenzene Sulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, pentylbenzenesulfonic acid, hexylbenzenesulfonic acid, heptylbenzenesulfonic acid, octylbenzenesulfonic acid, nonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecyl Benzenesulfonic acid, pentadecylbenzenesulfonic acid, octadecylbenzenesulfonic acid, diethylbenzenesulfonic acid, dipropylbenzenesulfonic acid, dibutylbenzenesulfonic acid, methylna Talensulfonic acid, ethylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, pentylnaphthalenesulfonic acid, hexylnaphthalenesulfonic acid, heptylnaphthalenesulfonic acid, octylnaphthalenesulfonic acid, nonylnaphthalenesulfonic acid, decylnaphthalenesulfonic acid, un Decylnaphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, pentadecylnaphthalenesulfonic acid, octadecylnaphthalenesulfonic acid, dimethylnaphthalenesulfonic acid, diethylnaphthalenesulfonic acid, dipropylnaphthalenesulfonic acid, dibutylnaphthalenesulfonic acid, dipentylnaphthalenesulfonic acid, dihexylnaphthalenesulfone Acid, diheptylnaphthalenesulfonic acid, dioctylnaphthalenesulfonic acid, dinoni Lunaphthalenesulfonic acid, trimethylnaphthalenesulfonic acid, triethylnaphthalenesulfonic acid, tripropylnaphthalenesulfonic acid, tributylnaphthalenesulfonic acid, camphorsulfonic acid, acrylamide-t-butylsulfonic acid, ethanedisulfonic acid, propanedisulfonic acid, butanedisulfonic acid, Pentane disulfonic acid, hexane disulfonic acid, heptane disulfonic acid, octane disulfonic acid, nonane disulfonic acid, decanedisulfonic acid, benzene disulfonic acid, naphthalene disulfonic acid, toluene disulfonic acid, ethylbenzene disulfonic acid, propylbenzene disulfonic acid, butylbenzene disulfonic acid, Dimethylbenzene disulfonic acid, diethylbenzene disulfonic acid, dipropylbenzene disulfonic acid, dibutylbenzene Sulfonic acid, methyl naphthalene disulfonic acid, ethyl naphthalene disulfonic acid, propyl naphthalene disulfonic acid, butyl naphthalene disulfonic acid, pentyl naphthalene disulfonic acid, hexyl naphthalene disulfonic acid, heptyl naphthalene disulfonic acid, octyl naphthalene disulfonic acid, nonyl naphthalene disulfonic acid, dimethyl naphthalene Disulfonic acid, diethyl naphthalene disulfonic acid, dipropyl naphthalene disulfonic acid, dibutyl naphthalene disulfonic acid, naphthalene trisulfonic acid, naphthalene tetrasulfonic acid, anthracene disulfonic acid, anthraquinone disulfonic acid, phenanthrene disulfonic acid, fluorenone disulfonic acid, carbazole disulfonic acid, diphenylmethane Disulfonic acid, biphenyl disulfonic acid, -Phenyl disulfonic acid, terphenyl trisulfonic acid, naphthalene sulfonic acid-formalin condensate, phenanthrene sulfonic acid-formalin condensate, anthracene sulfonic acid-formalin condensate, fluorene sulfonic acid-formalin condensate, carbazole sulfonic acid-formalin condensate , Polyvinylsulfonic acid, polyvinylsulfuric acid, polystyrenesulfonic acid, sulfonated styrene-butadiene copolymer, polyallylsulfonic acid, polymethallylsulfonic acid, poly-2-acrylamido-2-methylpropanesulfonic acid, polyhalogenated acrylic acid , Polyisoprene sulfonic acid, N-sulfoalkylated polyaniline, and nuclear sulfonated polyaniline.

  Examples of the proton acid derivative include neutralized products such as alkali metal salts or alkaline earth metal salts of proton acids such as sulfonic acid and phosphoric acid.

(C) Protic acid and / or proton acid derivative blocked with a base (thermal latent proton acid compound)
Examples of the protonic acid in the heat latent protonic acid compound include sulfuric acid, hydrochloric acid, butyric acid, formic acid, nitric acid, phosphoric acid, borohydrofluoric acid, phosphorous hydrofluoric acid, perchloric acid, monocarboxylic acid, polycarboxylic acids, propionic acid, Oxalic acid, acrylic acid, methacrylic acid, itaconic acid, phthalic acid, maleic acid, pentadecafluorooctanoic acid, acetic acid, pentafluoroacetic acid, trifluoroacetic acid, trichloroacetic acid, dichloroacetic acid, monofluoroacetic acid, monobromoacetic acid, monochloroacetic acid, Cyanoacetic acid, acetylacetic acid, nitroacetic acid, triphenylacetic acid, benzoic acid, o, m, p-bromobenzoic acid, o, m, p-chlorobenzoic acid, o, m, p-nitrobenzoic acid, dinitrobenzoic acid, Picric acid, trimethylbenzoic acid, o, m, p-cyanobenzoic acid, thymol blue, salicylic acid, 5 Aminosalicylic acid, o-methoxybenzoic acid, 1,6-dinitro-4-chlorophenol, 2,6-dinitrophenol, 2,4-dinitrophenol, p-oxybenzoic acid, bromophenol blue, mandelic acid, phthalic acid, Isophthalic acid, maleic acid, fumaric acid, malonic acid, tartaric acid, citric acid, lactic acid, succinic acid, α-alanine, β-alanine, glycine, glycolic acid, thioglycolic acid, ethylenediamine-N, N′-diacetic acid, ethylenediamine -N, N, N ', N'-tetraacetic acid, sulfonic acid, aminonaphthol sulfonic acid, metanylic acid, sulfanilic acid, allyl sulfonic acid, lauryl sulfuric acid, xylene sulfonic acid, chlorobenzene sulfonic acid, methane sulfonic acid, ethane sulfonic acid 1-propanesulfonic acid, 1-butanesulfonic acid, 1-hex Sulfonic acid, 1-heptanesulfonic acid, 1-octanesulfonic acid, 1-nonanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, benzenesulfonic acid, styrenesulfonic acid, o, m, p-toluenesulfonic acid , Naphthalenesulfonic acid, ethylbenzenesulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, pentylbenzenesulfonic acid, hexylbenzenesulfonic acid, heptylbenzenesulfonic acid, octylbenzenesulfonic acid, nonylbenzenesulfonic acid, decylbenzenesulfonic acid, un Decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, octadecylbenzenesulfonic acid, diethylbenzenesulfonic acid, dipropylbenzenesulfonic acid, dibutylbenzene Sulfonic acid, methylnaphthalenesulfonic acid, ethylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, pentylnaphthalenesulfonic acid, hexylnaphthalenesulfonic acid, heptylnaphthalenesulfonic acid, octylnaphthalenesulfonic acid, nonylnaphthalenesulfonic acid, decylnaphthalene Sulfonic acid, undecylnaphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, pentadecylnaphthalenesulfonic acid, octadecylnaphthalenesulfonic acid, dimethylnaphthalenesulfonic acid, diethylnaphthalenesulfonic acid, dipropylnaphthalenesulfonic acid, dibutylnaphthalenesulfonic acid, dipentylnaphthalenesulfonic acid Dihexyl naphthalene sulfonic acid, diheptyl naphthalene sulfonic acid, dioctyl naphthalate Sulfonic acid, dinonylnaphthalenesulfonic acid, trimethylnaphthalenesulfonic acid, triethylnaphthalenesulfonic acid, tripropylnaphthalenesulfonic acid, tributylnaphthalenesulfonic acid, camphorsulfonic acid, acrylamide-t-butylsulfonic acid, ethanedisulfonic acid, propanedisulfonic acid, Butanedisulfonic acid, pentanedisulfonic acid, hexanedisulfonic acid, heptanedisulfonic acid, octanedisulfonic acid, nonanedisulfonic acid, decanedisulfonic acid, benzenedisulfonic acid, naphthalenedisulfonic acid, toluenedisulfonic acid, ethylbenzenedisulfonic acid, propylbenzenedisulfonic acid, butyl Benzene disulfonic acid, dimethylbenzene disulfonic acid, diethylbenzene disulfonic acid, dipropylbenzene disulfone , Dibutylbenzene disulfonic acid, methyl naphthalene disulfonic acid, ethyl naphthalene disulfonic acid, propyl naphthalene disulfonic acid, butyl naphthalene disulfonic acid, pentyl naphthalene disulfonic acid, hexyl naphthalene disulfonic acid, heptyl naphthalene disulfonic acid, octyl naphthalene disulfonic acid, nonyl naphthalene disulfonic acid , Dimethyl naphthalene disulfonic acid, diethyl naphthalene disulfonic acid, dipropyl naphthalene disulfonic acid, dibutyl naphthalene disulfonic acid, naphthalene trisulfonic acid, naphthalene tetrasulfonic acid, anthracene disulfonic acid, anthraquinone disulfonic acid, phenanthrene disulfonic acid, fluorenone disulfonic acid, carbazole disulfone Acid, diphenylmethane disulfonic acid, bif Nyldisulfonic acid, terphenyl disulfonic acid, terphenyl trisulfonic acid, naphthalene sulfonic acid-formalin condensate, phenanthrene sulfonic acid-formalin condensate, anthracene sulfonic acid-formalin condensate, fluorene sulfonic acid-formalin condensate, carbazole sulfonic acid -Formalin condensate, polyvinyl sulfonic acid, polyvinyl sulfuric acid, polystyrene sulfonic acid, sulfonated styrene-butadiene copolymer, polyallyl sulfonic acid, polymethallyl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, poly Examples thereof include halogenated acrylic acid, polyisoprene sulfonic acid, N-sulfoalkylated polyaniline, and nuclear sulfonated polyaniline.

  Examples of the proton acid derivative include neutralized products such as alkali metal salts or alkaline earth metal salts of proton acids such as sulfonic acid and phosphoric acid.

  Of these protonic acids and protonic acid derivatives, sulfonic acids and phosphoric acids are preferable, and benzenesulfonic acids such as benzenesulfonic acid, o, m, p-toluenesulfonic acid, styrenesulfonic acid, and dodecylbenzenesulfonic acid are particularly suitable. Yes.

  Examples of basic compounds that block protonic acids include amines. Amines are classified into primary, secondary, or tertiary amines, and any polyaniline composition according to the first embodiment can be used without any particular limitation.

  Examples of the primary amine include methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, isobutylamine, t-butylamine, hexylamine, 2-ethylhexylamine, secondary butylamine, allylamine, and methylhexylamine.

  Secondary amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-t-butylamine, dihexylamine, di (2-ethylhexyl) amine, and N-isopropyl. -N-isobutylamine, di (2-ethylhexyl) amine, disecondary butylamine, diallylamine, N-methylhexylamine, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5- Examples include lupetidine, morpholine, N-methylbenzylamine and the like.

Tertiary amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-t-butylamine, trihexylamine, tri (2-ethylhexyl) amine, N -Methylmorpholine, N, N-dimethylallylamine, N-methyldiallylamine, triallylamine, N, N-dimethylallylamine, N, N, N ', N'-tetramethyl-1,2-diaminoethane, N, N, N ′, N′-tetramethyl-1,3-diaminopropane, N, N, N ′, N′-tetraallyl-1,4-diaminobutane, N-methylpiperidine, pyridine, 4-ethylpyridine, N-pyro Pyrdiallylamine, 3-dimethylaminopropanol, 2-ethylpyrazine, 2,3-di Tilpyrazine, 2,5-dimethylpyrazine, 2,4-lutidine, 2,5-lutidine, 3,4-lutidine, 3,5-lutidine, 2,4,6-collidine, 2-methyl-4-ethylpyridine, 2-methyl-5-ethylpyridine, N, N, N ′, N′-tetramethylhexamethylenediamine, N-ethyl-3-hydroxypiperidine, 3-methyl-4-ethylpyridine, 3-ethyl-4-methyl Pyridine, 4- (5-nonyl) pyridine, imidazole, N-methylpiperazine and the like can be mentioned.
Among these amines, as described above, those having a boiling point equal to or lower than the dissociation temperature when used as a thermal latent compound, more preferably a tertiary amine having a boiling point equal to or lower than the dissociation temperature, specifically, Triethylamine, 2,5-lutidine, imidazole and N, N-dimethylallylamine are particularly preferred.

  Commercially available products of the above (c) thermal latent protonic acid compound include “NACURE2501” (toluenesulfonic acid dissociation, methanol / isopropanol solvent, pH 6.0 to 7.2, dissociation temperature 80 ° C.) manufactured by King Industries, NACURE2107 ”(p-toluenesulfonic acid dissociation, isopropanol solvent, pH 8.0 to 9.0, dissociation temperature 90 ° C.),“ NACURE2500 ”(p-toluenesulfonic acid dissociation, isopropanol solvent, pH 6.0 to 7.0, dissociation) 65 ° C), “NACURE2530” (p-toluenesulfonic acid dissociation, methanol / isopropanol solvent, pH 5.7-6.5, dissociation temperature 65 ° C), “NACURE2547” (p-toluenesulfonic acid dissociation, aqueous solution, pH 8. 0-9.0, dissociation temperature 107 ° C.), “NAC “RE2558” (p-toluenesulfonic acid dissociation, ethylene / glycol solvent, pH 3.5 to 4.5, dissociation temperature 80 ° C.), “NACUREXP-357” (p-toluenesulfonic acid dissociation, methanol solvent, pH 2.0 to 4 0.0, dissociation temperature 65 ° C.), “NACUREXP-386” (p-toluenesulfonic acid dissociation, aqueous solution, pH 6.1-6.4, dissociation temperature 80 ° C.), “NACUREXC-2211” (p-toluenesulfonic acid dissociation) , PH 7.2 to 8.5, dissociation temperature 80 ° C.), “NACURE 5225” (dodecylbenzene sulfonic acid dissociation, isopropanol solvent, pH 6.0 to 7.0, dissociation temperature 120 ° C.), “NACURE 5414” (dodecyl benzene sulfonic acid) Dissociation, xylene solvent, dissociation temperature 120 ° C), "NACURE 5528" Rubenzenesulfonic acid dissociation, isopropanol solvent, pH 7.0-8.0, dissociation temperature 120 ° C.), “NACURE5925” (dodecylbenzenesulfonic acid dissociation, isopropanol solvent, pH 7.0-7.5, dissociation temperature 130 ° C.), “NACURE1323” (dinonylnaphthalenesulfonic acid dissociation, xylene solvent, pH 6.8 to 7.5, dissociation temperature 150 ° C.), “NACURE1419” (dinonylnaphthalenesulfonic acid dissociation, xylene / methylisobutylketone solvent, dissociation temperature 150 ° C. ), “NACURE1557” (dinonylnaphthalenesulfonic acid dissociation, butanol / 2-butoxyethanol solvent, pH 6.5 to 7.5, dissociation temperature 150 ° C.), “NACUREX49-110” (dinonylnaphthalenedisulfonic acid dissociation, isobutanol /I Sopropanol solvent, pH 6.5 to 7.5, dissociation temperature 90 ° C.), “NACURE 3525” (Dinonyl naphthalene disulfonic acid dissociation, isobutanol / isopropanol solvent, pH 7.0 to 8.5, dissociation temperature 120 ° C.), “ NACUREXP-383 "(dinonylnaphthalenedisulfonic acid dissociation, xylene solvent, dissociation temperature 120 ° C)," NACURE3327 "(dinonylnaphthalenedisulfonic acid dissociation, isobutanol / isopropanol solvent, pH 6.5-7.5, dissociation temperature 150 ° C ), “NACURE 4167” (phosphate dissociation, isopropanol / isobutanol solvent, pH 6.8 to 7.3, dissociation temperature 80 ° C.), “NACUREXP-297” (phosphate dissociation, water / isopropanol solvent, pH 6.5 to 7) .5, dissociation temperature 90 ° C.), “NAC RE4575 "(phosphoric acid dissociation, methanol / butanol solvent, pH 7.0-8.0, dissociation temperature 110 ° C.), and the like.

(D) Protic acids and / or protonic acid derivatives esterified with primary or secondary alcohols Specific examples and preferred examples of the above-mentioned protonic acids and protonic acid derivatives are preferably those listed in (c) above. Can be used.

  Examples of the primary or secondary alcohol include methanol, ethanol, propanol, butanol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, and propylene glycol.

(E) Protic acids and / or proton acid derivatives blocked with vinyl ethers and / or vinyl thioethers Specific examples and preferred examples of the above proton acids and proton acid derivatives are preferably those listed in (c) above. Can be used.

  Examples of vinyl ethers include aliphatic vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, 2,3-dihydrofuran, 3,4-dihydrofuran, 2,3-dihydro- 2H-pyran, 3,4-dihydro-2H-pyran, 3,4-dihydro-2-methoxy-2H-pyran, 3,4-dihydro-4,4-dimethyl-2H-pyran, 3,4-dihydro- Cyclic vinyl ethers such as 4,4-dimethyl-2H-pyran-2-one, 3,4-dihydro-2-ethoxy-2H-pyran, sodium 3,4-dihydro-2-pyran-2-carboxylate, etc. Can be mentioned.

  Examples of the vinyl thioethers include vinyl thioether compounds corresponding to the above vinyl ethers.

These thermal latent compounds can be used alone or in combination of two or more.
The blending amount of the heat latent compound in the polyaniline composition according to the first embodiment is preferably 100% by mass or more and 300% by mass or less, particularly 150% by mass or more and 200% by mass with respect to the polyaniline compounding amount. Less than mass% is suitable.

-Solvent-
When the polyaniline composition according to the first embodiment is obtained using the above materials, it can be prepared without a solvent, but it is preferably prepared in the following organic polar solvent.
Examples of the organic polar solvent include sulfoxide solvents dimethyl sulfoxide, diethyl sulfoxide, etc., formamide solvents N, N-dimethylformamide, N, N-diethylformamide, etc., acetamide solvents N, N-dimethylacetamide, N, N -Diethylacetamide, etc., pyrrolidone solvents N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, etc., phenol solvents pyrrolidonephenol, o-, m- or p-cresol, xylenol, halogenated phenol, catechol And the like, and ether solvents such as tetrahydrofuran, dioxane, dioxolane, hexamethylphosphoramide, γ-butyrolactone, and the like.

  These organic polar solvents can be used singly or in combination of two or more, and can also be used by mixing with other solvents. When used as a mixture, aromatic hydrocarbons such as xylene and toluene can also be used.

  When the polyaniline composition according to the first embodiment is prepared in the solvent, the solid content concentration of the polyaniline solution is not particularly limited, but is preferably 5% by mass or more and 50% by mass or less, particularly 10% by mass. % Or more and 30% by mass or less is preferable.

  Moreover, it is preferable to perform the heat drying temperature of a polyaniline composition above the dissociation temperature of a heat-latent compound.

  The polyaniline composition according to the first embodiment can be used for plastic battery electrode materials, antistatic materials, display elements, electronic devices, capacitors, electromagnetic shielding materials, electrostatic adsorption films, conductive paste materials, and the like. Addition to impart conductivity and flexibility to be mixed with polymer materials such as polyimide resin, acrylic resin, urethane resin, fluororesin, urea resin, epoxy resin, rubber polymer, thermoplastic resin, etc. It can be used as an agent.

<Polyamic acid composition>
Next, the polyamic acid composition according to the second embodiment will be described in detail.
As described above, the polyamic acid composition according to the second embodiment contains a polyaniline composition containing polyaniline and a thermal latent compound, and a polyamic acid, and further contains additives and the like. be able to. The polyamic acid composition can be produced by various methods.

  In general, polyamic acid is obtained by reacting tetracarboxylic dianhydride and diamine. In addition, the dispersion of the polyaniline composition in the polyamic acid composition according to the second embodiment is performed by polymerizing the polyamic acid by dissolving (i) tetracarboxylic dianhydride and diamine in an organic polar solvent. A method of obtaining a polyamic acid composition by dispersing a polyaniline composition containing polyaniline and a heat latent compound in the prepared polyamic acid solution, (ii) comprising a polyaniline and a heat latent compound in an organic polar solvent After dispersing the polyaniline composition, it is possible to use a method of dissolving the tetracarboxylic dianhydride and the diamine and polymerizing the polyamic acid to obtain the polyamic acid composition.

-Polyamic acid-
As mentioned above, polyamic acid is generally obtained by reacting tetracarboxylic dianhydride and diamine. The polyamic acid may be a polyimide-polyamic acid copolymer containing a polyimide structure in a part thereof.

  Examples of the tetracarboxylic dianhydride used include the following, which can be used from the viewpoint of obtaining desired characteristics.

The tetracarboxylic dianhydrides are broadly classified into three types: aromatic tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides, and alicyclic tetracarboxylic dianhydrides.
As aromatic tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic Acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetra Carboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilane tetracarboxylic dianhydride, 1,2, 3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfo Dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3' , 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthal Acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, and the like.

  Aliphatic tetracarboxylic dianhydrides include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane. Tetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbonane-2-acetic acid Anhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, And bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride.

  Examples of the alicyclic tetracarboxylic dianhydride include 1,3,3a, 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-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3- Examples include dione.

  These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

  When a polyamic acid composition according to the second embodiment is used to produce a polyimide endless belt used as a belt (an intermediate transfer belt, a conveyance belt, a fixing belt, etc.) in an image forming apparatus, the above The tetracarboxylic dianhydride is preferably an aromatic tetracarboxylic dianhydride from the viewpoint of strength, and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is particularly suitable.

  Moreover, the following are mentioned as diamine to be used, It can use from a viewpoint of obtaining a desired characteristic.

The diamines are broadly classified into three types: aromatic diamines, aliphatic diamines, and alicyclic diamines.
Examples of aromatic diamines include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenylsulfone, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4′-diaminobiphenyl, 5-amino-1- (4′-aminophenyl) -1,3,3- Trimethylindane, 6-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 4,4′-diaminobenzanilide, 3,5-diamino-3′-trifluoromethylbenzanilide, 3,5-diamino-4′-trifluoromethylbenzanilide, 3,4′-diaminodiphenyl ether, 2,7- Aminofluorene, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4' -Diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diamino-2, 2′-bis (trifluoromethyl) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1 , 4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) -biphenyl, 1,3′-bis (4-aminophenoxy) benzene, 9,9-bis (4- Minophenyl) fluorene, 4,4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-(m-phenyleneisopropylidene) bisaniline, 2,2′-bis [4- (4-amino-2-trifluoro) Methylphenoxy) phenyl] hexafluoropropane, 4,4′-bis [4- (4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl and the like, and other than the nitrogen atom of the amino group Examples of the aromatic diamine having a hetero atom include diaminotetraphenylthiophene.

Aliphatic diamines and alicyclic diamines include 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, octamethylenediamine, nonamethylenediamine, and 4,4-diaminoheptamethylene. Diamine, 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiethylene diamine, hexahydro-4,7-methanoin danylene dimethylene diamine, tricyclo [6,2,1,02.7] -undecylenedimethyl diamine, 4,4′-methylenebis (cyclohexylamine) and the like.
These diamines can be used alone or in combination of two or more.

  When a polyamic acid composition according to the second embodiment is used to produce an endless belt made of polyimide used as a belt (an intermediate transfer belt, a conveyance belt, a fixing belt, etc.) in an image forming apparatus, From the viewpoint of the strength of the polyimide molded product, an aromatic diamine is preferable, and 4,4′-diaminodiphenyl ether is particularly suitable.

-Polyaniline composition-
The addition amount of the polyaniline composition containing the polyaniline and the heat latent compound added to the polyamic acid composition according to the second embodiment is preferably 3% by mass or more and 45% by mass or less, particularly 20% by mass. % To 35% by mass is suitable.

-Solvent-
When the polyamic acid composition according to the second embodiment is obtained using the above material, it can be prepared without a solvent, but it is preferably prepared in an organic polar solvent mentioned below.
The organic polar solvent is not particularly limited as long as it dissolves polyamic acid and polyamic acid-polyimide copolymer.

  Examples of the organic polar solvent include sulfoxide solvents dimethyl sulfoxide, diethyl sulfoxide, etc., formamide solvents N, N-dimethylformamide, N, N-diethylformamide, etc., acetamide solvents N, N-dimethylacetamide, N, N -Diethylacetamide, etc., pyrrolidone solvents N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, etc., phenol solvents pyrrolidonephenol, o-, m- or p-cresol, xylenol, halogenated phenol, catechol And the like, and ether solvents such as tetrahydrofuran, dioxane, dioxolane, hexamethylphosphoramide, γ-butyrolactone, and the like.

  These organic polar solvents can be used singly or in combination of two or more, and can also be used by mixing with other solvents. When used as a mixture, aromatic hydrocarbons such as xylene and toluene can also be used.

  When the polyamic acid composition according to the second embodiment is prepared in the solvent, the solid content concentration of the polyamic acid solution is not particularly limited, but is preferably 5% by mass or more and 50% by mass or less, particularly 10 mass% or more and 30 mass% or less are suitable.

-Additives-
Moreover, when manufacturing a polyimide molding using the polyamic acid composition which concerns on 2nd Embodiment, you may mix other electroconductive substances as an additive from a viewpoint of giving mechanical strength.
The additive used in the polyamic acid composition according to the second embodiment is preferably carbon black having conductivity because the electrical resistance value can be easily adjusted. In particular, the dispersion stability and electrical resistance can be improved. Oxidized carbon black having a pH of 5.0 or less that has been subjected to oxidation treatment is suitable from the viewpoint of stability.

  Oxidized carbon black is a carbon black having a carboxyl group, a quinone group, a lactone group, a hydroxyl group, etc. added to the surface of the carbon black by oxidation treatment. Examples of the oxidation treatment include an air oxidation method in which a reaction is caused by contact with air in a high temperature (about 270 ° C. to about 400 ° C.) atmosphere, a temperature oxidation method at room temperature (about 20 ° C.), a contact method, and a furnace black method. is there.

Examples of the carbon black include ketchen black and acetylene black. If a predetermined electrical resistance can be obtained, semiconductive carbon black and other conductive or semiconductive particles can be used. Examples of other conductive or semiconductive particles include metals such as aluminum and nickel, metal oxide compounds such as yttrium oxide and tin oxide, and potassium titanate. Further, an ion conductive material such as LiCl, or a conductive polymer material such as polyaniline, polypyrrole, polysulfone, or polyacetylene can be added.
These can be used alone or in combination of two or more.

  The polymerization temperature of the polyamic acid composition according to the second embodiment is preferably performed in the range of 0 ° C. or higher and 80 ° C. or lower.

<Polyimide molding and its manufacturing method>
Next, the polyimide molded product according to the third embodiment will be described in detail.
The polyimide molding according to the third embodiment is produced by dehydrating and imidizing a polyamic acid composition containing polyaniline and a polyamic acid containing a thermal latent compound and a polyamic acid. More specifically, (1) using the polyamic acid composition, a drying molding step of molding and drying in a molding machine, and (2) an imidization step of dehydrating and imidizing the polyamic acid composition after molding. Are manufactured by a manufacturing method having

  The polyimide molded product according to the third embodiment is suitably used for belt members such as a fixing belt, a transfer belt, and a paper transport belt, which are parts of an image forming apparatus, for example. In addition, in the field of electrical and electronic parts, it can be used for flexible printed circuit boards, liquid crystal alignment films for liquid crystal display elements, insulating or protective films for semiconductor devices, conductor coating films, and the like.

  In the method for producing a polyimide molded product, the shape to be molded and the molding method are not particularly limited, and a shape and molding method suitable for each member to be applied can be taken. For example, when used as a belt member of an image forming apparatus as described above, it is preferably a seamless endless belt, and an example of a method for manufacturing an endless belt will be described below.

  Endless belts are: (0) raw material blend (preparation of polyamic acid composition) and outer mold (mold) preparation process, (1) dry molding process, (2) imidization process, (3) cut It is manufactured through an inspection process.

(0) Raw material blending and outer mold preparation step The polyamic acid composition in the raw material blending step is prepared by mixing each material in the polyamic acid composition according to the second embodiment in a preferred amount.
In the outer mold preparation process, a cylindrical outer mold, in which both the inner wall surface and the outer wall surface are formed concentrically, manufactured from a stable heat-resistant material such as SUS, iron, aluminum, and fluororesin. Is prepared. In addition, it is preferable that the process which forms a mold release agent layer is given to the inner wall of an outer type | mold.

(1) Dry molding process In the dry molding process, as shown in FIGS. 1 (A) and (B), an outer mold prepared by preparing the polyamic acid composition 11A prepared in the raw material blending process in the outer mold preparing process. The inside of 12 is injected as it is and sealed. Next, as shown in FIGS. 2A and 2B, the outer mold 12 is air-dried or heated by a heater or the like while being rotated on the two shafts 13 rotated in the same direction as seen in a roll mill device or the like. (Preferably 50 ° C. or more and 200 ° C. or less), and the solvent contained in the polyamic acid composition 11A is preferably volatilized by 30% by mass or more, more preferably 50% by mass or more, and the polyamic acid composition 11A is centrifuged. .

  The polyamic acid composition 11A is molded so as not to cause an imidization reaction by adjusting the heating conditions, particularly when dried by heating with a heater or the like as described above. It is extracted from the inner wall surface of the outer mold 12. Moreover, in the said manufacturing method of an endless belt, it is preferable to suppress generation | occurrence | production of a dehydration imidation reaction by drying below the dissociation temperature of a heat | fever latent compound.

(2) Imidation Step As shown in FIG. 4, a cylindrical inner mold 14 is inserted into the molded polyamic acid composition 11 </ b> A extracted from the outer mold 12. Thereafter, the polyamic acid composition 11A is put together with the inner mold 14 in a high-temperature heating apparatus such as an oven furnace, and heated and fired to be dehydrated and imidized. In addition, the temperature (calcination temperature) of the dehydrating imidation reaction of the polyamic acid composition in the method for producing an endless belt is preferably in the range of 150 ° C. or higher and 450 ° C. or lower, and higher than the dissociation temperature of the thermal latent compound used. It is preferable to set to. By this imidization step, the polyamic acid composition 11A shrinks and fits to the outer wall of the inner mold 14, and is converted into an imide to form an endless belt 11B.

(3) Cut Inspection Process As shown in FIG. 5, the endless belt 11B that has been dehydrated and imidized is removed from the inner mold 14, and then cut into a desired length. After an inspection process, an endless polyimide molding ( An endless belt is obtained.

<Image forming apparatus>
Next, an image forming apparatus according to the fourth embodiment will be described in detail.
An image forming apparatus according to the fourth embodiment forms an image carrier, latent image forming means for forming an electrostatic latent image on the image carrier, and developing the latent image with toner to form a toner image. A polyaniline composition having a developing means, a transfer means for transferring the toner image to a recording medium, and a fixing means for fixing the toner image transferred to the recording medium, and containing polyaniline and a thermal latent compound; And a polyimide molded product produced by dehydrating imidation of a polyamic acid composition containing polyamic acid.

  As an aspect in which the polyimide molding is applied to the image forming apparatus according to the fourth embodiment, the intermediate transfer belt of the intermediate transfer member, the fixing belt of the fixing device, and the batch having no intermediate transfer member in the image forming device are used. Examples thereof include a belt member such as a paper conveyance belt in the transfer method, and particularly, it can be suitably used as an intermediate transfer belt or a paper conveyance belt.

Hereinafter, an example of an image forming apparatus according to the fourth embodiment will be described.
FIG. 6 is a schematic configuration diagram of an image forming apparatus having an intermediate transfer device and a fixing device. The image forming apparatus includes an intermediate transfer belt 2 and a fixing belt 52, and the polyimide molding is applied to both.

  The image forming apparatus includes an image carrier (photosensitive member) 1 that is a toner image carrier, a developing device 6 that supplies toner to the image carrier 1, and circulates toner on the image carrier 1 from a primary transfer position. The intermediate transfer belt 2 transported to the secondary transfer position, the conductive roll 25 serving as a transfer electrode for transferring the toner on the image carrier 1 to the intermediate transfer belt 2 at the primary transfer position, and the intermediate transfer belt 2 at the secondary transfer position. Bias roll 3 which is a transfer electrode installed on the surface side where the toner image is held, backup roll 22 arranged so that bias roll 3 is opposed to the intermediate transfer belt 2, and the backup roll 22 are pressed against and rotated. The recording medium storage for supplying the electrode roll 26, the supporting rolls 21, 23, 24, the recording medium 41, and the recording medium 41 that support the intermediate transfer belt 2 and guide the circulation of the intermediate transfer belt 2. A fixing device 5 including a unit 4, a feed roll 42 that feeds the recording medium 41 from the recording medium storage unit 4, a conveyance path 43 that is a path through which the recording medium 41 to which the toner image is transferred, and a fixing belt 52. Have. The intermediate transfer belt 2 is stretched by a backup roll 22 and support rolls 21, 23, and 24 to form a belt stretching device 28.

The operation of this image forming apparatus will be described below.
The image carrier 1 rotates in the direction of arrow A, and the surface is charged by a charging device (not shown). The charged image carrier 1 is irradiated with a laser by an image writing device (not shown) to form an electrostatic latent image.

  This electrostatic latent image is visualized by the toner supplied by the developing device 6, and a toner image T is formed. The toner image T reaches the primary transfer position where the conductive roll 25 is disposed by the rotation of the image carrier 1, and a voltage having a polarity opposite to the charge of the toner of the toner image T is applied from the conductive roll 25. Then, it is electrostatically attracted to the intermediate transfer belt 2. Since the intermediate transfer belt 2 moves in the direction of arrow B while being in contact with the surface of the image carrier 1 at the primary transfer position, the toner image T on the image carrier 1 is sequentially adsorbed onto the intermediate transfer belt 2 with the movement. Primary transcription. The toner image transferred onto the intermediate transfer belt 2 is conveyed to the secondary transfer position where the bias roll 3 is installed by circulation of the intermediate transfer belt 2.

  The recording medium 41 is fed from the recording medium storage unit 4 to an area formed by the intermediate transfer belt 2 and the bias roll 3 at the secondary transfer position at a predetermined timing by the feed roll 42. The intermediate transfer belt 2 on which the toner image is placed is pressed against the recording medium 41 by the bias roll 3 and the backup roll 22 at the secondary transfer position, and has the same polarity as the polarity of the toner image from the electrode roll 26 through the backup roll 22. Is applied, the toner image is attracted to the recording medium 41. Since the intermediate transfer belt 2 moves so as to circulate in the direction of the arrow B together with the recording medium 41 at the secondary transfer position, the toner images on the intermediate transfer belt 2 are sequentially attracted to the recording medium 41 along with the movement and become secondary. Transcribed.

  The recording medium 41 to which the toner image has been transferred is conveyed to the fixing device 5 through the conveyance path 43. The toner image on the recording medium 41 is fixed on the recording medium 41 by being pressed / heated by the fixing device 5 as will be described in detail with reference to FIG.

FIG. 7 is an enlarged schematic configuration diagram showing the fixing device of the image forming apparatus shown in FIG.
The fixing device 5 includes a hollow roll having a heat source therein (for example, an aluminum hollow roll having a heat source composed of a halogen lamp) 51a, and an elastic layer (for example, a liquid layer laminated on the surface of the hollow roll 51a). An arrow composed of silicon rubber (an elastic layer made of liquid silicone rubber) 51b and a heat-resistant release oil-resistant layer (for example, a heat-resistant release oil-resistant layer in which fluorine rubber is applied to the surface of the elastic layer 51b) 51c. A fixing roll 51 driven to rotate in the C direction, a fixing belt 52 driven to circulate in the direction of arrow D as the fixing roll 51 is driven, and a wide contact width by pressing the fixing belt 52 against the fixing roll 51. A pressure pad (for example, a pressure pad formed by integrally molding silicon rubber on a metal base) A first support roll 54 that supports the belt 52, a second support that preliminarily heats the fixing belt 52 by supporting the fixing belt 52 that is located upstream from the contact region N in the circulation of the fixing belt 52 and having a heating unit. A roll 55, a pressure roll 53 that supports the fixing belt 52 located downstream of the circulation of the fixing belt 52 from the contact area N, and a paper separation claw 59 that separates the recording medium 41 that has passed through the contact area N from the fixing roll 52. . The portion of the fixing belt 52 that contacts the contact region N is stretched between a second support roll 55 and a pressure roll 53, and the pressure roll 53 is pressurized toward the center of the fixing roll 51 by a coil spring (not shown). .

  In addition, the fixing device 5 includes a cleaning unit 57 that contacts the fixing roll 51 to wipe off residual toner on the surface of the fixing roll 51, and a release agent application unit that contacts the fixing roll 51 upstream of the fixing contact and applies a release agent. 58.

The operation of the fixing device 5 will be described below.
The recording medium 41 on which the unfixed toner is placed is conveyed onto the second support roll 55 of the fixing belt 52 via the conveyance path 43 in FIG. The recording medium 41 is preheated by the second support roll 55 together with unfixed toner. The fixing belt 2 has a horizontally extending portion from the second support roll 55 to the contact area N, and the recording medium 41 is conveyed to the contact area N in the direction of arrow E by the horizontally extending portion. When the recording medium 41 to which the unfixed toner image is attached passes through the contact area N, the fixing roll 51 fixes the unfixed toner image on the recording medium 41 by heating and pressurizing the unfixed toner image. Since the release agent is applied to the fixing roll 51 by the release agent application unit 58, the unfixed toner image is efficiently fixed to the recording medium 41, but the fixing roll 51 is not fixed to the recording medium 41. If there is toner attached to the surface, the toner is wiped off by the cleaning means 57. The recording medium 41 on which the toner is fixed passes through the contact area N and is then transported to the position of the paper separation claw 59. The recording medium 41 is separated from the fixing belt 52 by the paper separation claw 59. Discharged to the department.

  Next, FIG. 8 is a schematic configuration diagram of an image forming apparatus having an intermediate transfer fixing device. The image forming apparatus includes an intermediate transfer fixing belt 61 that functions as both an intermediate transfer belt and a fixing belt, and the polyimide molding is applied as the intermediate transfer fixing belt 61.

  In the image forming apparatus, the intermediate transfer fixing belt 61 is suspended by a drive roll 62, guide rolls 63 and 64, a tension roll 65, and a heating roller 66 to form a belt stretching apparatus 70. In the area formed by the drive roll 62 and the heating roller 66, four photosensitive drums 67A, 67B, 67C, 67D on which different color toner images are formed are in contact with each other, and the transfer units 68A, 68B, 68C and 68D are disposed, and a pressure roller 69 is in pressure contact with the heating roller 66.

  In the above configuration, the toner images of the respective colors are primarily transferred from the four photosensitive drums 67A, 67B, 67C, 67D to the intermediate transfer fixing belt 61, and the recording medium P is sent between the heating roller 66 and the pressure roller 69. Thus, the multicolor toner image on the intermediate transfer fixing belt 61 is secondarily transferred onto the recording medium P and fixed by heating.

  Hereinafter, an example is shown and it demonstrates more concretely. However, it is not limited to these examples.

-Preparation of polyamic acid solution (1)-
2966.4 g of N-methyl-2-pyrrolidone was injected into an eggplant flask (5000 ml) equipped with a stirring bar, a thermometer, and a dropping funnel while passing nitrogen gas dried with phosphorus pentoxide. After heating the solution temperature to 60 ° C., 300.3 g (1.5 mol) of 4,4′-diaminodiphenyl ether was added and dissolved. While maintaining the solution temperature at 60 ° C., 441.3 g (1.5 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added and dissolved by stirring. Furthermore, stirring was continued while maintaining the solution temperature at 60 ° C., and a polymerization reaction to polyamic acid was performed for 24 hours to obtain 3708.0 g of a polyamic acid solution (1) having a solid content concentration of 20% by mass.

[Example 1]
-Preparation of polyaniline composition (1-1)-
Thermally latent compound (NACURE 5225, manufactured by King Industries, Inc.) in 21.8 g of polyaniline (manufactured by Panipol, trade name: Panipol PA, number average molecular weight: 100,000) and dissociation products are sulfonic acid and / or its derivative and amine , Dodecylbenzenesulfonic acid dissociation, isopropanol solvent, pH 6.0 to 7.0, dissociation temperature 120 ° C., basic compound (amine: oxazolidine boiling point 110 ° C.) 32.7 g, and N-methyl-2-pyrrolidone It was made to melt | dissolve in 218.2g and the polyaniline composition (1-1) was obtained.

-Preparation of polyamic acid composition (1-1)-
To the polyamic acid solution (1) 618.0 g, 272.7 g of the polyaniline composition (1-1) was added and dissolved to obtain a polyamic acid composition (1-1).

-Manufacture of endless belts-
The obtained polyamic acid composition (1-1) was injected into a cylindrical SUS mold (outer mold) and sealed. The cylindrical mold was preliminarily coated with a fluorine-based release agent to improve the peelability after belt molding.
While rotating the cylindrical mold, a dry molding step was performed for 30 minutes under the condition of a temperature of 100 ° C., and 60% by mass or more of the solvent contained in the polyamic acid composition was volatilized and centrifugally molded. The polyamic acid composition after centrifugal molding is extracted from the outer mold, and then a cylindrical mold (inner mold) is inserted into the extracted polyamic acid composition, placed in a clean oven furnace, and subjected to a dehydration imidization reaction at 200 ° C. for 30 minutes. went. After the reaction, the polyamic acid composition (that is, the polyimide molding) is allowed to cool at room temperature (about 20 ° C.) while being fitted to the cylindrical mold (inner mold), and then removed from the cylindrical mold (inner mold). Through the cutting step, an endless belt (1-1) having an inner diameter of 68 mm and a width of 340 mm was obtained.

  The endless belt was manufactured under conditions prepared so that the film thickness would be 75 μm as long as a film thickness without variation was obtained on the entire belt surface.

(Evaluation of endless belt)
(I) Belt film thickness measurement (film thickness variation)
Ten test pieces each having a length of 10 cm and a width of 10 cm were randomly cut from the obtained endless belt (1-1). Using a film thickness meter (manufactured by TECLOCK CORPORATION, constant pressure thickness measuring instrument PG-02), the thickness of five points at the center and four corners is measured for one test piece, and the average value of the five points is measured for one test piece. The thickness was taken. The endless belt has a film thickness of 75 μm as a reference value, and the variation in the belt film thickness was evaluated by measuring the largest error from the reference value among the ten test pieces.

(II) Measurement of imidization rate A test piece was cut out from the obtained endless belt (1-1), and IR spectrum was measured by FT-IR (manufactured by Horiba, Ltd., microscopic FT-IR spectrometer FT-530). It was. Based on the vibration peak of the aromatic ring of 1500 cm ⁻¹ appearing in the IR spectrum, the ratio of the stretching peak of the carbonyl group derived from the imide group of 1776 cm ⁻¹ was obtained, and the peak ratio of the 400 ° C. baked polyimide film was determined as the imide The imidization rate of polyimide was determined with a conversion rate of 100%.

(III) Measurement of surface resistivity The obtained endless belt (1-1) was made up of a circular electrode (UR probe of Hiresta IP manufactured by Mitsubishi Yuka Co., Ltd .: outer diameter Φ16mm of cylindrical electrode, ring-shaped electrode part The inner diameter Φ30 mm and the outer diameter Φ40 mm) were applied under a 22 ° C./55% RH environment, and a voltage of 100 V was applied, and the resistance values were measured for 30 milliseconds and 10 seconds after the application. From the measured values, the common logarithm value (ρs (30 msec)) of the surface resistivity of 30 milliseconds after application and the common logarithm value (ρs (10 sec)) of the surface resistivity of 10 seconds are calculated, and the equation Δ = | ρs (30 msec) ) -Ρs (10 sec) |

-Manufacture of image forming apparatus-
The obtained endless belt (1-1) was applied as an intermediate transfer belt to produce the image forming apparatus shown in FIG.

(Evaluation of image forming apparatus)
(IV) Printing misalignment and density unevenness Toner (Fuji Xerox Co., Ltd., trade name: DocuCentreColor 400CP toner cartridge (black)) is set in the image forming apparatus, and plain paper (Fuji Xerox Co., C2 paper) is short. In the mode of conveying in the direction, a 5000 sheet image (black 50% halftone image) was formed on the paper, and the density unevenness was evaluated by the following evaluation criteria using the 50th halftone image of the 5000th sheet. Further, as the 5001st sheet, a square black image was formed so as to be at a specific position with respect to the paper, and the printing deviation was evaluated from the positional relationship between the paper and the black image by the following evaluation criteria.
• Print misalignment ○: Print misalignment is not confirmed.
Δ: Although slight printing misalignment was confirmed, it was at a level with no problem.
X: Printing deviation can be clearly confirmed.

-Density unevenness ○: Concentration unevenness is not confirmed.
(Triangle | delta): Although the density nonuniformity was confirmed a little, it is a level without a problem.
X: Density unevenness can be clearly confirmed.

[Example 2]
-Preparation of polyaniline composition (1-2) and polyamic acid composition (1-2)-
The polyaniline composition (1-1) and the polyamic acid composition (1-1) obtained in Example 1 were each allowed to stand at 25 ° C. for 14 days, and the polyaniline composition (1-2) and the polyamic acid composition (1- 2) was obtained.

(V) Measurement of Viscosity Change Rate For the polyaniline composition (1-2) and the polyamic acid composition (1-2), the viscosity before standing for 14 days (V ′ (Pa · s)) and the viscosity after standing ( V (Pa · s)) was measured. The measurement was performed using a constant-speed viscosity measuring apparatus (manufactured by HAKKE, E-type PK100) with 50 g sealed in a sample bottle. The shape of the applicator of the constant speed viscosity measuring apparatus was a 2 ° cone type and a diameter of 30 mm. The viscosity change rate (γ) was calculated from the measured viscosity before and after standing by the following formula.
(Formula) γ = V / V ′

-Manufacture of polyimide moldings and image forming devices-
A polyimide molded product and an image forming apparatus were produced by the method described in Example 1, except that the polyamic acid composition (1-1) used in Example 1 was changed to the polyamic acid composition (1-2). And evaluated.

[Example 3]
-Preparation of polyaniline composition (1-3) and polyamic acid composition (1-3)-
The polyaniline composition (1-1) and the polyamic acid composition (1-1) obtained in Example 1 were each allowed to stand at 40 ° C. for 14 days, and the polyaniline composition (1-3) and the polyamic acid composition (1- 3) was obtained.
Moreover, the viscosity before and behind standing of the obtained polyaniline composition (1-3) and polyamic acid composition (1-3) was measured by the method as described in Example 2, and viscosity change rate ((gamma)) was computed.

-Manufacture of polyimide moldings and image forming devices-
A polyimide molded product and an image forming apparatus were produced by the method described in Example 1, except that the polyamic acid composition (1-1) used in Example 1 was changed to the polyamic acid composition (1-3). And evaluated.

[Example 4]
-Preparation of polyaniline composition (2-1)-
Thermal latent compound in which polyaniline (manufactured by Panipol, trade name: Panipol PA, number average molecular weight: 100,000) is 21.8 g, and the dissociation product is phosphoric acid and / or a derivative thereof and an amine (polymer of melamine compound) (NACURE 4167, manufactured by King Industries, Inc., isopropanol / isobutanol solvent, pH 6.8 to 7.3, dissociation temperature 80 ° C., basic compound (amine: polymer of melamine compound) boiling point 75 ° C.) 32.7 g was added. , N-methyl-2-pyrrolidone was dissolved in 218.2 g to obtain a polyaniline composition (2-1).

-Preparation of polyamic acid composition (2-1)-
To the polyamic acid solution (1) 618.0 g, 272.7 g of the polyaniline composition (2-1) was added and dissolved to obtain a polyamic acid composition (2-1).

-Manufacture of polyimide moldings and image forming devices-
Except having changed the polyamic acid composition (1-1) used in Example 1 into the polyamic acid composition (2-1), a polyimide molded product and an image forming apparatus were produced by the method described in Example 1. And evaluated.

[Example 5]
-Preparation of polyaniline composition (2-2) and polyamic acid composition (2-2)-
The polyaniline composition (2-1) and the polyamic acid composition (2-1) obtained in Example 4 were each allowed to stand at 25 ° C. for 14 days, and the polyaniline composition (2-2) and the polyamic acid composition (2- 2) was obtained.
Moreover, the viscosity before and behind standing of the obtained polyaniline composition (2-2) and polyamic acid composition (2-2) was measured by the method as described in Example 2, and viscosity change rate ((gamma)) was computed.

-Manufacture of polyimide moldings and image forming devices-
Except having changed the polyamic acid composition (1-1) used in Example 1 into the polyamic acid composition (2-2), a polyimide molded product and an image forming apparatus were produced by the method described in Example 1. And evaluated.

[Example 6]
-Preparation of polyaniline composition (2-3) and polyamic acid composition (2-3)-
The polyaniline composition (2-1) and the polyamic acid composition (2-1) obtained in Example 4 were each left at 40 ° C. for 14 days, and the polyaniline composition (2-3) and the polyamic acid composition (2- 3) was obtained.
Moreover, the viscosity before and behind standing of the obtained polyaniline composition (2-3) and polyamic acid composition (2-3) was measured by the method as described in Example 2, and viscosity change rate ((gamma)) was computed.

-Manufacture of polyimide moldings and image forming devices-
Except that the polyamic acid composition (1-1) used in Example 1 was changed to the polyamic acid composition (2-3), a polyimide molded product and an image forming apparatus were produced by the method described in Example 1. And evaluated.

[Example 7]
-Preparation of polyaniline composition (3-1)-
21.8 g of polyaniline (manufactured by Panipol, trade name: Panipol PA, number average molecular weight: 100,000) and methylbenzoate (thermal latent compound, Wako Jun) whose dissociation products are benzoic acid and / or its derivatives and methyl alcohol 32.7 g of Yakuhin Co., Ltd., trade name: methyl benzoate, dissociation temperature 60 ° C.) was added and dissolved in 218.2 g of N-methyl-2-pyrrolidone to obtain a polyaniline composition (3-1).

-Preparation of polyamic acid composition (3-1)-
To the polyamic acid solution (1) 618.0 g, 272.7 g of the polyaniline composition (3-1) was added and dissolved to obtain a polyamic acid composition (3-1).

-Manufacture of polyimide moldings and image forming devices-
Except having changed the polyamic acid composition (1-1) used in Example 1 into the polyamic acid composition (3-1), a polyimide molded product and an image forming apparatus were produced by the method described in Example 1. And evaluated.

[Example 8]
-Preparation of polyaniline composition (3-2) and polyamic acid composition (3-2)-
The polyaniline composition (3-1) and the polyamic acid composition (3-1) obtained in Example 7 were allowed to stand at 25 ° C. for 14 days, respectively, and the polyaniline composition (3-2) and the polyamic acid composition (3- 2) was obtained.
Moreover, the viscosity before and behind standing of the obtained polyaniline composition (3-2) and polyamic acid composition (3-2) was measured by the method as described in Example 2, and viscosity change rate ((gamma)) was computed.

-Manufacture of polyimide moldings and image forming devices-
A polyimide molded product and an image forming apparatus were produced by the method described in Example 1, except that the polyamic acid composition (1-1) used in Example 1 was changed to the polyamic acid composition (3-2). And evaluated.

[Example 9]
-Preparation of polyaniline composition (3-3) and polyamic acid composition (3-3)-
The polyaniline composition (3-1) and the polyamic acid composition (3-1) obtained in Example 7 were allowed to stand at 40 ° C. for 14 days, respectively, and the polyaniline composition (3-3) and the polyamic acid composition (3- 3) was obtained.
Moreover, the viscosity before and behind standing of the obtained polyaniline composition (3-3) and polyamic acid composition (3-3) was measured by the method as described in Example 2, and viscosity change rate ((gamma)) was computed.

-Manufacture of polyimide moldings and image forming devices-
Except having changed the polyamic acid composition (1-1) used in Example 1 into the polyamic acid composition (3-3), a polyimide molded product and an image forming apparatus were produced by the method described in Example 1. And evaluated.

[Example 10]
-Preparation of polyaniline composition (4-1)-
21.8 g of polyaniline (manufactured by Panipol, trade name: Panipol PA, number average molecular weight: 100,000), 1-isobutoxyethyl-trichloroacetate (heat) whose dissociated product is trichloroacetic acid and / or a derivative thereof and isobutyl vinyl ether (Latent compound, dissociation temperature 70 ° C.) 32.7 g was added and dissolved in 218.2 g of N-methyl-2-pyrrolidone to obtain a polyaniline composition (4-1).

-Preparation of polyamic acid composition (4-1)-
To the polyamic acid solution (1) 618.0 g, 272.7 g of the polyaniline composition (4-1) was added and dissolved to obtain a polyamic acid composition (4-1).

-Manufacture of polyimide moldings and image forming devices-
Except having changed the polyamic acid composition (1-1) used in Example 1 into the polyamic acid composition (4-1), a polyimide molded product and an image forming apparatus were produced by the method described in Example 1. And evaluated.

[Example 11]
-Preparation of polyaniline composition (4-2) and polyamic acid composition (4-2)-
The polyaniline composition (4-1) and the polyamic acid composition (4-1) obtained in Example 10 were allowed to stand at 25 ° C. for 14 days, respectively, and the polyaniline composition (4-2) and the polyamic acid composition (4- 2) was obtained.
Moreover, the viscosity before and behind standing of the obtained polyaniline composition (4-2) and polyamic acid composition (4-2) was measured by the method as described in Example 2, and viscosity change rate ((gamma)) was computed.

-Manufacture of polyimide moldings and image forming devices-
Except having changed the polyamic acid composition (1-1) used in Example 1 into the polyamic acid composition (4-2), a polyimide molded product and an image forming apparatus were produced by the method described in Example 1. And evaluated.

[Example 12]
-Preparation of polyaniline composition (4-3) and polyamic acid composition (4-3)-
The polyaniline composition (4-1) and the polyamic acid composition (4-1) obtained in Example 10 were each left at 40 ° C. for 14 days, and the polyaniline composition (4-3) and the polyamic acid composition (4- 3) was obtained.
Moreover, the viscosity before and behind standing of the obtained polyaniline composition (4-3) and polyamic acid composition (4-3) was measured by the method as described in Example 2, and viscosity change rate ((gamma)) was computed.

-Manufacture of polyimide moldings and image forming devices-
Except having changed the polyamic acid composition (1-1) used in Example 1 into the polyamic acid composition (4-3), a polyimide molded article and an image forming apparatus were produced by the method described in Example 1. And evaluated.

[Comparative Example 1]
-Preparation of polyaniline composition (5-1)-
Polyaniline composition was prepared by adding 32.7 g of dodecylbenzenesulfonic acid to 21.8 g of polyaniline (manufactured by Panipol, trade name: Panipol PA, number average molecular weight: 100,000) and dissolving in 218.2 g of N-methyl-2-pyrrolidone. A product (5-1) was obtained.

-Preparation of polyamic acid composition (5-1)-
To the polyamic acid solution (1) 618.0 g, 272.7 g of the polyaniline composition (5-1) was added and dissolved to obtain a polyamic acid composition (5-1).

-Manufacture of polyimide moldings and image forming devices-
Except having changed the polyamic acid composition (1-1) used in Example 1 into the polyamic acid composition (5-1), a polyimide molded article and an image forming apparatus were produced by the method described in Example 1. And evaluated.

[Comparative Example 2]
-Preparation of polyaniline composition (5-2) and polyamic acid composition (5-2)-
The polyaniline composition (5-1) and the polyamic acid composition (5-1) obtained in Comparative Example 1 were allowed to stand at 25 ° C. for 14 days, respectively, and the polyaniline composition (5-2) and the polyamic acid composition (5- 2) was obtained.
Moreover, the viscosity before and behind standing of the obtained polyaniline composition (5-2) and polyamic acid composition (5-2) was measured by the method as described in Example 2, and viscosity change rate ((gamma)) was computed.

-Manufacture of polyimide moldings and image forming devices-
Except having changed the polyamic acid composition (1-1) used in Example 1 into the polyamic acid composition (5-2), a polyimide molded product and an image forming apparatus were produced by the method described in Example 1. And evaluated.

[Comparative Example 3]
-Preparation of polyaniline composition (5-3) and polyamic acid composition (5-3)-
The polyaniline composition (5-1) and the polyamic acid composition (5-1) obtained in Comparative Example 1 were allowed to stand at 40 ° C. for 14 days, respectively, and the polyaniline composition (5-3) and the polyamic acid composition (5- 3) was obtained.
Moreover, the viscosity before and behind standing of the obtained polyaniline composition (5-3) and polyamic acid composition (5-3) was measured by the method as described in Example 2, and viscosity change rate ((gamma)) was computed.

-Manufacture of polyimide moldings and image forming devices-
A polyimide molded article and an image forming apparatus were produced by the method described in Example 1, except that the polyamic acid composition (1-1) used in Example 1 was changed to the polyamic acid composition (5-3). And evaluated.

[Comparative Example 4]
-Preparation of polyaniline composition (6-1)-
To 21.8 g of polyaniline (manufactured by Panipol, trade name: Panipol PA, number average molecular weight: 100,000), 32.7 g of p-toluenesulfonic acid is added, and dissolved in 218.2 g of N-methyl-2-pyrrolidone. A composition (6-1) was obtained.

-Preparation of polyamic acid composition (6-1)-
To the polyamic acid solution (1) 618.0 g, 272.7 g of the polyaniline composition (6-1) was added and dissolved to obtain a polyamic acid composition (6-1).

-Manufacture of polyimide moldings and image forming devices-
Except having changed the polyamic acid composition (1-1) used in Example 1 into the polyamic acid composition (6-1), a polyimide molded product and an image forming apparatus were produced by the method described in Example 1. And evaluated.

[Comparative Example 5]
-Preparation of polyaniline composition (6-2) and polyamic acid composition (6-2)-
The polyaniline composition (6-1) and the polyamic acid composition (6-1) obtained in Comparative Example 4 were allowed to stand at 25 ° C. for 14 days, respectively, and the polyaniline composition (6-2) and the polyamic acid composition (6- 2) was obtained.
Moreover, the viscosity before and behind standing of the obtained polyaniline composition (6-2) and polyamic acid composition (6-2) was measured by the method as described in Example 2, and viscosity change rate ((gamma)) was computed.

-Manufacture of polyimide moldings and image forming devices-
Except that the polyamic acid composition (1-1) used in Example 1 was changed to the polyamic acid composition (6-2), a polyimide molded product and an image forming apparatus were produced by the method described in Example 1. And evaluated.

[Comparative Example 6]
-Preparation of polyaniline composition (6-3) and polyamic acid composition (6-3)-
The polyaniline composition (6-1) and the polyamic acid composition (6-1) obtained in Comparative Example 4 were each allowed to stand at 40 ° C. for 14 days, and the polyaniline composition (6-3) and the polyamic acid composition (6- 3) was obtained.
Moreover, the viscosity before and behind standing of the obtained polyaniline composition (6-3) and polyamic acid composition (6-3) was measured by the method as described in Example 2, and viscosity change rate ((gamma)) was computed.

-Manufacture of polyimide moldings and image forming devices-
Except that the polyamic acid composition (1-1) used in Example 1 was changed to the polyamic acid composition (6-3), a polyimide molded product and an image forming apparatus were produced by the method described in Example 1. And evaluated.

  The evaluation results of these examples and comparative examples are described in the following table.

Below, the preferable aspect of this invention is shown. First, the polyaniline composition of the present invention is
<1> A polyaniline composition containing at least polyaniline and a heat latent compound. By setting it as this structure, compared with the case where a thermal-latency compound is not contained, favorable storage stability and efficient provision of electroconductivity can be made compatible.
<2> The polyaniline composition according to <1>, wherein the basic compound which is a dissociation product of the thermal latent compound has a boiling point equal to or lower than the dissociation temperature of the thermal latent compound. By adopting such a configuration, it is possible to realize more efficient conductivity as compared with the case where the boiling point of the basic compound, which is the dissociation product of the thermal latent compound, is not taken into consideration.

The polyamic acid composition of the present invention is
<3> A polyamic acid composition containing at least the polyaniline composition according to <1> or <2> and a polyamic acid. By setting it as this structure, compared with the case where the polyaniline composition which has a heat | fever latent compound is not contained, favorable storage stability and the outstanding electroconductivity can be made compatible.

Moreover, the polyimide molding of the present invention is
<4> A polyimide molded product produced by dehydrating imidization of the polyamic acid composition according to <3>. By setting it as this structure, compared with the case where the polyaniline composition which has a heat | fever latent compound is not used, the variation in an electrical resistance value and a film thickness can be suppressed favorably and quality can be improved.

Moreover, the manufacturing method of the polyimide molding of this invention is as follows.
<5> A polyimide having the polyamic acid composition according to the above <3>, a dry molding step of molding and drying with a molding machine, and an imidization step of dehydrating and imidizing the molded polyamic acid composition. It is a manufacturing method of a molding. By adopting such a structure, it is possible to easily produce a polyimide molded product that can suppress the variation of the electric resistance value and the film thickness and improve the quality as compared with the case where the polyaniline composition having the heat latent compound is not used. be able to.

The endless belt of the present invention is
<6> An endless belt formed by dehydrating and imidating the polyamic acid composition according to <3> above into a ring shape. By setting it as this structure, compared with the case where the polyaniline composition which has a heat | fever latent compound is not used, the variation in an electrical resistance value and a film thickness can be suppressed favorably and quality can be improved.

The belt stretcher of the present invention is
<7> A belt stretching apparatus comprising: the endless belt according to <6>; and a plurality of stretching members that rotatably stretch the endless belt from the inner peripheral surface side. By adopting such a configuration, compared with a case where an endless belt using a polyaniline composition having a thermal latent compound is not provided, variation in electric resistance value and film thickness is suppressed well, and even for circular driving. Quality can be improved.

Furthermore, the image forming apparatus of the present invention includes:
<8> Image carrier, latent image forming unit for forming an electrostatic latent image on the image carrier, developing unit for developing the latent image with toner to form a toner image, and recording the toner image The image forming apparatus includes a transfer unit that transfers to a medium and a fixing unit that fixes a toner image transferred to a recording medium, and includes the polyimide molding according to the above <4>. By adopting such a configuration, an image having excellent quality can be formed as compared with a case where an endless belt using a polyaniline composition having a heat latent compound is not provided.
<9> The <8>, wherein the endless belt according to the above <6> is used as at least one selected from an intermediate transfer belt or a sheet conveying belt used for the transfer unit and a fixing belt used for the fixing unit. > Is an image forming apparatus.

  Since the polyaniline composition and the polyamic acid composition of the present invention have good storage stability and excellent conductivity at the time of molding, they can be widely used as conductive materials. In addition, when the polyamic acid composition is formed into a polyimide molded product, it is possible to satisfactorily suppress variations in electrical resistance values and film thicknesses during film formation, and thus the field of electrical and electronic components that require high quality. Available in In particular, it is suitable for an intermediate transfer belt, a paper transport belt, etc. of recent image forming apparatuses.

(A) is a side view which shows the outer mold | type in which the polyamic acid composition was inject | poured in the method to manufacture the polyimide molding which concerns on 3rd Embodiment, (B) is the perspective view. (A) is a side view which shows a dry molding process in the method to manufacture the polyimide molding which concerns on 3rd Embodiment, (B) is the perspective view. It is a perspective view which shows a mode that the polyamic acid composition dry-molded is extracted from an outer mold | type in the method of manufacturing the polyimide molded product which concerns on 3rd Embodiment. It is a perspective view which shows a mode that an inner mold | type is inserted in the polyamic acid composition dry-molded in the method of manufacturing the polyimide molded product which concerns on 3rd Embodiment. It is a perspective view which shows a mode that an endless belt is removed from an inner mold | type in the method to manufacture the polyimide molding which concerns on 3rd Embodiment. FIG. 10 is a schematic configuration diagram illustrating an image forming apparatus according to a fourth embodiment in which a polyimide molding is applied as an intermediate transfer belt and a fixing belt. FIG. 7 is an enlarged schematic configuration diagram illustrating a fixing device of an image forming apparatus according to a fourth embodiment illustrated in FIG. 6. It is a schematic block diagram which shows the image forming apparatus which concerns on 4th Embodiment which applied the polyimide molding as an intermediate transfer fixing belt.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Image carrier 2 Intermediate transfer belt 3 Bias roll 4 Recording medium storage part 5 Fixing apparatus 6 Developing apparatus 11A Polyamic acid composition 11B Endless belt 12 Outer mold 13 Shaft 14 Inner molds 21, 23, 24 Support roll 22 Backup roll 25 Conductive roll 26 Electrode rolls 28, 70 Belt stretcher 41, P Recording medium 42 Feed roll 43 Conveying path 51 Fixing roll 51a Hollow roll 51b Elastic layer 51c Heat-resistant release oil-resistant layer 53 Pressure roll 54 First support roll 55 Second support roll 56 Pressure pad 57 Cleaning means 58 Release agent application means 59 Paper separation claw 61 Intermediate transfer fixing belt 62 Drive roll 63, 64 Guide roll 65 Tension roll 66 Heating rollers 67A, B, C, D Photoconductor Drum 68A, B, C, D Transfer device 69 Pressure roller

Claims (8)

  A polyaniline composition containing at least polyaniline and a heat latent compound.   The polyaniline composition according to claim 1, wherein the basic compound, which is a dissociation product of the thermal latent compound, has a boiling point equal to or lower than the dissociation temperature of the thermal latent compound.   A polyamic acid composition containing at least the polyaniline composition according to claim 1 or 2 and a polyamic acid.   A polyimide molded product produced by dehydrating and imidizing the polyamic acid composition according to claim 3.   Production of a polyimide molding having the dry molding step of molding and drying with a molding machine using the polyamic acid composition according to claim 3 and the imidization step of dehydrating imidization of the molded polyamic acid composition. Method.   An endless belt formed by dehydrating and imidizing the polyamic acid composition according to claim 3 into a ring shape.   A belt stretching apparatus comprising: the endless belt according to claim 6; and a plurality of stretching members that rotatably stretch the endless belt from the inner peripheral surface side.   An image carrier, a latent image forming unit for forming an electrostatic latent image on the image carrier, a developing unit for developing the latent image with toner to form a toner image, and transferring the toner image to a recording medium An image forming apparatus comprising: the polyimide molding product according to claim 4, further comprising: a transferring unit that fixes the toner image transferred to the recording medium.

Images