JP2006249140A - Electrically conductive polymer, semiconductive composition using the same, and semiconductive member for electrophotographic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrically conductive polymer capable of being given at a low cost and excellent in both characteristics of electrical conductivity and solubility. <P>SOLUTION: The electrically conductive polymer soluble in a solvent is obtained by rendering the following component (A) electrically conductive by using the following component (B) as a dopant. The component (A) is a π-electron conjugated polymer and the component (B) is an oxyalkylene-based compound having at least either of the functional groups of a sulfonic acid group and a sulfonate group, and a fluorinated alkyl group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a conductive polymer, a semiconductive composition using the same, and a semiconductive member for an electrophotographic apparatus, and more specifically, uses a semiconductive composition containing a conductive polymer as a main component. The present invention relates to a semiconductive member for electrophotographic equipment such as a developing roll.

  Usually, a π-electron conjugated polymer such as polyaniline can be made into a conductive polymer by doping with a dopant. However, the dopant degrades the solubility of the conductive polymer in the solvent.

Therefore, when the undoped state is set to be undoped, solubility can be imparted to the polymer, the polymer becomes soluble in the solvent, and coating becomes possible. For example, when polyaniline is synthesized in a dedope state, the obtained polyaniline becomes soluble in a very high boiling point solvent such as N-methyl-2-pyrrolidone (NMP) and can be coated (for example, Patent Document 1). reference).
JP 2001-324882 A

  However, in the synthesis method described in Patent Document 1, doping with a halogen gas or the like is indispensable as a post-treatment in order to impart conductivity to the polymer, so that uniform control is difficult and the process becomes complicated. On the other hand, it is possible to impart solubility by introducing a long-chain alkyl substituent into a monomer main chain such as aniline without being in a dedope state, but since the cost of the monomer as a raw material is high, There are restrictions on the general use. Thus, it is a fact that a conductive polymer that is low in cost and excellent in both properties of conductivity and solubility has not yet been obtained, and development of such a conductive polymer is awaited.

  The present invention has been made in view of such circumstances, and has a low cost, a conductive polymer excellent in both properties of conductivity and solubility, a semiconductive composition using the same, and an electrophotographic apparatus. The purpose is to provide a semiconductive member.

In order to achieve the above object, the present invention provides a solvent-soluble conductive polymer obtained by conducting the following component (A) with a dopant, wherein the dopant is the following component (B). The first polymer is the functional polymer.
(A) π electron conjugated polymer.
(B) An oxyalkylene compound having at least one functional group of a sulfonate group and a sulfonate group and a fluorinated alkyl group.

  In addition, the present invention provides a semiconductive composition containing the conductive polymer as a main component as a second gist, and for an electrophotographic apparatus using the semiconductive composition as at least a part of the semiconductive member. A semiconductive member is a third gist.

  That is, the present inventors have conducted extensive research in order to obtain a conductive polymer that is low in cost and excellent in both properties of conductivity and solubility. Patent application for solvent-soluble conductive polymer obtained by using alkylbenzene sulfonic acid having a total of 10 to 37 carbon atoms of substituents or a salt thereof as a dopant and thereby making a π-electron conjugated polymer conductive. (Japanese Patent Application No. 2004-246802). When research was continued to further improve the contents of this Japanese Patent Application No. 2004-246802, it was found that the dopant was liberated and the π-electron conjugated polymer tended to aggregate under severe high temperature and high humidity. . Therefore, as a result of repeated studies on a dopant that is less liberated even under severe high temperature and high humidity, the present inventors have found that an oxyalkylene having at least one functional group of a sulfonic acid group and a sulfonic acid group and a fluorinated alkyl group. The present inventors have found that a desired compound can be achieved by finding a compound based on a conductive compound and using it as a dopant to make a π-electron conjugated polymer conductive. That is, the conductive polymer of the present invention obtained by conducting with an oxyalkylene compound (dopant) having at least one functional group of a sulfonic acid group and a sulfonic acid group and a fluorinated alkyl group is a π electron even in a humid heat environment. Conjugation of the conjugated polymer is hardly observed, the electric resistance is small, the conductivity is excellent, and the effect of being soluble in a general-purpose solvent is obtained.

  As described above, the conductive polymer of the present invention uses an oxyalkylene compound having at least one functional group of a sulfonic acid group and a sulfonate group and a fluorinated alkyl group as a dopant, and a π-electron conjugated polymer. It is made conductive. Therefore, the aggregation of the π-electron conjugated polymer is hardly observed even in a moist heat environment, the fluctuation of electric resistance is small, the conductivity is excellent, and a general solvent (a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone, acetone, acetic acid, The effect of being soluble in an ester solvent such as ethyl or butyl acetate) is obtained.

  When a compound having a structural unit represented by the following general formula (1) is used as the oxyalkylene compound, it can be hydrophobized as a conductive polymer, and the effect of improving the heat and moisture resistance can be obtained.

  Further, when the fluorinated alkyl group in the oxyalkylene compound is a fluorinated alkyl group having 1 to 4 carbon atoms, an effect of increasing the doping efficiency of the conductive polymer can be obtained.

  In addition, when the number average molecular weight of the oxyalkylene compound is within a range of 300 to 4500, an effect of improving compatibility with a solvent or a binder polymer such as an elastomer can be obtained.

  When the π-electron conjugated polymer is derived from at least one monomer selected from the group consisting of aniline, pyrrole, thiophene and derivatives thereof, a binder polymer such as an elastomer having stable electrical characteristics. The effect that the affinity with is increased.

  In addition, the semiconductive member for an electrophotographic apparatus using the semiconductive composition as at least a part of the semiconductive member is uniform and excellent in durability in a low temperature / low humidity and high temperature / high humidity environment. There is an effect that an image can be obtained.

  Next, an embodiment of the present invention will be described.

  The conductive polymer of the present invention is a solvent-soluble conductive polymer obtained by using a specific oxyalkylene compound (component B) as a dopant and thereby conducting a π-electron conjugated polymer (component A).

  Here, in the present invention, an oxyalkylene compound (component B) having at least one functional group of a sulfonic acid group and a sulfonic acid group and a fluorinated alkyl group is used as a dopant. It is a feature.

  The π-electron conjugated polymer (component A) refers to a polymer that can have a structure in which π-electrons can be conjugated, or a structure in which single bonds and multiple bonds are alternately linked. For example, aniline, pyrrole, thiophene And polymers derived from monomers such as derivatives thereof. In addition, the monomer includes an alkyl substituent having 1 to 4 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group) and an alkoxy substituent (for example, methoxy group, ethoxy group, propoxy group, butoxy group). Those having at least one substituent are preferred from the viewpoint of solubility. Specific examples of the π-electron conjugated polymer (component A) include polyaniline, polypyrrole, poly-3-methylpyrrole, polythiophene, poly-3-methylthiophene, poly-o-toluidine, poly-o-anisidine, and poly-o-ethyl. Examples thereof include aniline and polysec-butylaniline.

  Examples of the polymerization initiator for the π-electron conjugated polymer (component A) include chemicals such as ammonium persulfate, peroxides such as hydrogen peroxide and benzoyl peroxide, benzoquinones such as chloranil, and ferric chloride. An oxidizing agent can be used.

  Next, the specific oxyalkylene compound (component B) used together with the π-electron conjugated polymer (component A) comprises at least one functional group of a sulfonic acid group and a sulfonic acid group, and a fluorinated alkyl group. If it has, there will be no limitation in particular. Examples of the sulfonate group include metal sulfonate groups such as sodium sulfonate group and potassium sulfonate group, ammonium sulfonate group, pyridium sulfonate group, and the like.

  Examples of the specific oxyalkylene compound (component B) include compounds having a structural unit represented by the following general formula (1).

In the general formula (1), as the fluorinated alkyl group chain length represented by Rf has 1 to 8 carbon atoms, for _{example, -C n F 2n + 1 (} n = 1~8), - CH _{2 C n F 2n + 1 (} n = 1~7), - C 2 H 4 C n F 2n + 1 (n = 1~6) and the like, specifically, -CF _3, -CH ₂ CF ₃ , —CH ₂ CF ₂ CF ₃ , —CH ₂ CH ₂ C ₄ F _{9 and the} like can be mentioned.

  The number average molecular weight (Mn) of the specific oxyalkylene compound (component B) is preferably in the range of 300 to 4500, particularly preferably in the range of 600 to 2000. That is, when the number average molecular weight (Mn) of the specific oxyalkylene compound (component B) is less than 300, the solubility with a solvent or an elastomer is deteriorated. Conversely, when the number average molecular weight exceeds 4500, efficient doping occurs. This is because there is a tendency to disappear.

  Here, the molar mixing ratio between the π-electron conjugated polymer (component A) and the specific oxyalkylene compound (component B) is within the range of component A / component B = 1 / 0.01 to 1/10. It is particularly preferable that A component / B component = 1 / 0.1 to 1/2.

  The conductive polymer of the present invention can be produced, for example, as follows. That is, a mixed solvent of a monomer (for example, aniline) of the π electron conjugated polymer (component A), a specific oxyalkylene compound (component B), and an organic solvent such as hydrochloric acid, methyl ethyl ketone, methyl isobutyl ketone (MIBK) Etc. are placed in a flask in a predetermined amount, and an oxidizing agent such as ammonium persulfate is dropped over several hours (usually about 1 hour) while controlling at a predetermined temperature (about 5 to 10 ° C.). About 10 hours) Oxidative polymerization is performed to obtain a polymer. Next, the target conductive polymer can be prepared by washing and purifying the polymer with water and methanol.

  The conductive polymer of the present invention includes methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), ketone solvents such as acetone, ester solvents such as ethyl acetate and butyl acetate, aromatic solvents such as toluene, and tetrahydrofuran (THF). Soluble in ether solvents such as

  Next, the semiconductive composition of the present invention contains the conductive polymer of the present invention as a main component. In the present invention, the main component means a component that usually occupies a majority of the whole, and includes the case where the whole consists of only the main component.

  In the semiconductive composition of the present invention, a π electron non-conjugated polymer, a conductive agent and the like may be appropriately blended with the conductive polymer of the present invention as necessary.

  In the present invention, the π-electron non-conjugated polymer means a polymer other than a polymer in which single bonds and multiple bonds are alternately connected, such as the π-electron conjugated polymer (component A).

  The π-electron non-conjugated polymer is not soluble in water, but is soluble in a ketone solvent such as methyl ethyl ketone (MEK), an aromatic solvent such as toluene, and the drying rate can be controlled. It is preferable because the coatability is good.

  Examples of the π-electron nonconjugated polymer include acrylic polymers, urethane polymers, thermoplastic resin polymers, thermosetting resin polymers, rubber polymers, and thermoplastic elastomers. These may be used alone or in combination of two or more.

  The π-electron non-conjugated polymer preferably has at least one sulfonic acid functional group of a sulfonic acid group and a sulfonic acid group, but may not have one. Examples of the sulfonic acid functional group include a sulfonic acid group, a sulfonic acid group (a sulfonic acid metal base such as a sodium sulfonate base and a potassium sulfonate base, an ammonium sulfonate base, and a pyridium sulfonate base). .

  The amount of the sulfonic acid functional group in the π electron non-conjugated polymer is preferably in the range of 0.001 to 0.75 mmol / g, particularly preferably 0.02 to 0.5 mmol / g, from the viewpoint of solubility. Within range.

  The measurement of the amount of the sulfonic acid functional group is obtained, for example, by burning the π-electron non-conjugated polymer in a flask, obtaining the amount of sulfur element by ion chromatography, and converting this as the amount of sulfonic acid functional group. Can do.

  Examples of the acrylic polymer include polymethyl methacrylate (PMMA), polyethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polyhydroxy methacrylate, acrylic silicone resin, acrylic fluorine resin, and known acrylic monomers. And the like. Further, as described above, the acrylic polymer may further have a sulfonic acid functional group of at least one of a sulfonic acid group and a sulfonic acid group. As a method for introducing the sulfonic acid functional group, for example, 2 -A method of copolymerizing a vinyl monomer having a sulfonic acid group or a sulfonate group, such as acrylamido-2-methylpropanesulfonic acid (AMPS), and a radical, anion, or cation, or a diol monomer having a sulfonic acid group Examples thereof include a method of introduction by reaction or transesterification.

  The urethane polymer is not particularly limited as long as it is a resin having a urethane bond in the molecular structure. For example, ether-based, ester-based, acrylic-based, aliphatic-based urethane, silicone-based polyol or Examples include those obtained by copolymerizing fluorine-based polyols. Further, as described above, the urethane-based polymer may further have at least one sulfonic acid functional group of a sulfonic acid group and a sulfonic acid group. The urethane-based resin may have a urea bond or an imide bond in the molecular structure.

  Examples of the thermoplastic resin polymer include polyester, polycarbonate, polyvinyl chloride (PVC), vinyl acetate, polyimide, polyethersulfone, polyvinylidene fluoride (PVDF), vinylidene fluoride-tetrafluoroethylene copolymer, And vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer. Further, as described above, the thermoplastic resin polymer may further have at least one sulfonic acid functional group of a sulfonic acid group and a sulfonic acid group.

  Examples of the thermosetting resin polymer include epoxy resins, urethane resins, urea resins, polyimide resins, and the like. Further, as described above, the thermosetting resin polymer may further have at least one sulfonic acid functional group of a sulfonic acid group and a sulfonic acid group.

  Examples of the rubber-based polymer include natural rubber (NR), butadiene rubber (BR), acrylonitrile butadiene rubber (NBR), hydrogenated NBR (H-NBR), styrene butadiene rubber (SBR), isoprene rubber (IR), Examples thereof include urethane rubber, chloroprene rubber (CR), chlorinated polyethylene (Cl-PE), epichlorohydrin rubber (ECO, CO), butyl rubber (IIR), ethylene propylene diene polymer (EPDM), and fluorine rubber. Further, as described above, the rubber-based polymer may further have a sulfonic acid functional group of at least one of a sulfonic acid group and a sulfonic acid group.

  Examples of the thermoplastic elastomer include styrene-based thermoplastic elastomers such as styrene-butadiene block copolymer (SBS) and styrene-ethylene-butylene-styrene block copolymer (SEBS), and urethane-based thermoplastic elastomer (TPU). Olefin-based thermoplastic elastomer (TPO), polyester-based thermoplastic elastomer (TPEE), polyamide-based thermoplastic elastomer, fluorine-based thermoplastic elastomer, vinyl chloride-based thermoplastic elastomer, and the like. Further, as described above, the thermoplastic elastomer may further have at least one sulfonic acid functional group of a sulfonic acid group and a sulfonic acid group.

  Among the above-mentioned π-electron nonconjugated polymers, TPU having a sulfonic acid functional group, acrylic type having a sulfonic acid functional group in terms of simplicity of the synthesis process, solubility in a solvent, and physical properties (wearability, strength) A polymer is preferably used.

Next, the conductive agent is not particularly limited. For example, carbon black, c-ZnO (conductive zinc oxide), c-TiO ₂ (conductive titanium oxide), c-SnO ₂ (conductive tin oxide) , And ionic conductive agents such as compounds that dissolve in polymers such as lithium perchlorate, quaternary ammonium salts, and borate salts. These may be used alone or in combination of two or more.

  The blending ratio of the electron conductive agent is a total of 100 parts by weight (hereinafter referred to as “parts”) of the raw material (monomer) of the π-electron conjugated polymer (component A) and the specific oxyalkylene compound (component B). ) Part is preferably in the range of 5 to 80 parts, particularly preferably in the range of 8 to 20 parts.

  Further, the blending ratio of the ionic conductive agent is 0. 0 with respect to a total of 100 parts of the raw material (monomer) of the π-electron conjugated polymer (component A) and the specific oxyalkylene compound (component B). The range of 01 to 5 parts is preferable, and the range of 0.5 to 2 parts is particularly preferable.

  In addition, the semiconductive composition of the present invention may contain a crosslinking agent, a crosslinking accelerator, an anti-aging agent, and the like, if necessary, in addition to the conductive polymer, the π-electron non-conjugated polymer and the conductive agent. Absent.

  Examples of the crosslinking agent include urea resins such as sulfur, isocyanate, blocked isocyanate, and melamine, epoxy curing agents, polyamine curing agents, hydrosilyl curing agents, and peroxides. A photoinitiator that generates radicals by energy such as ultraviolet rays or electron beams may be used in combination with the crosslinking agent.

  The blending ratio of the crosslinking agent is the sum of the raw material (monomer) of the π electron conjugated polymer (component A) and the specific oxyalkylene compound (component B) from the viewpoints of physical properties, adhesion, and liquid storage. The range of 1 to 30 parts is preferable with respect to 100 parts, and the range of 3 to 10 parts is particularly preferable.

  Examples of the crosslinking accelerator include known ones such as a sulfenamide-based crosslinking accelerator, a platinum compound, an amine catalyst, and a dithiocarbamate-based crosslinking accelerator.

  The semiconductive composition of the present invention can be produced, for example, as follows. That is, first, a conductive polymer is produced according to the method described above. Next, a conductive agent is blended with the conductive polymer, and the cross-linking agent and other types of polymers are blended as necessary. And by kneading these using a kneading machine such as a roll, kneader, Banbury mixer or the like without dissolving them in a solvent, or by dissolving them in a solvent and dispersing them using a bead mill or three rolls, A semiconductive composition can be obtained.

  Examples of the solvent include organic solvents such as m-cresol, methanol, methyl ethyl ketone (MEK), toluene, tetrahydrofuran (THF), acetone, ethyl acetate, dimethylformamide (DMF), and N-methyl-2-pyrrolidone (NMP). Etc.

  As described above, the semiconductive composition of the present invention can be formed into a film by coating with a coating solution in which a conductive polymer or the like is dissolved in a solvent. However, the present invention is not limited to this. It is also possible to form a film by a molding method, an inflation molding method, or the like.

  Next, a semiconductive member for electrophotographic equipment using the semiconductive composition of the present invention will be described.

  The semiconductive member for an electrophotographic apparatus of the present invention can be obtained by using the above semiconductive composition for at least a part (all or a part) of the semiconductive member. Examples of the semiconductive member for electrophotographic equipment include conductive rolls such as developing rolls, charging rolls, transfer rolls, and toner supply rolls, and conductive belts such as intermediate transfer belts and paper feed belts. It is used for at least a part of the constituent layers. That is, when the semiconductive composition of the present invention is used for at least a part of a constituent layer of a semiconductive member for an electrophotographic apparatus, the voltage dependence of the electrical resistance of the constituent layer formed using this semiconductive composition. Since the electric current and the environmental dependency are reduced and the current flows through the semiconductor composition layer to other constituent layers, the electric resistance is less affected by the voltage dependency and the environmental dependency. As a result, the voltage dependency and environmental dependency of the electrical resistance as a whole semiconductive member for electrophotographic equipment are reduced, so that density unevenness is reduced, and good image quality without fluctuations can be obtained. As a result, an improvement in performance can be realized.

  Next, examples will be described together with comparative examples.

  First, prior to the examples and comparative examples, the following materials were prepared.

[Oxyalkylene compound a (component B)]
Oxyalkylene compound represented by the following structural formula (2) [Mn: 663]

[Oxyalkylene compound b (component B)]
Oxyalkylene compound represented by the following structural formula (3) [Mn: 1222]

[Oxyalkylene compound c (component B)]
Oxyalkylene compound represented by the following structural formula (4) [Mn: 1877]

[Oxyalkylene compound d (component B)]
Oxyalkylene compound represented by the following structural formula (5) [Mn: 4412]

  Next, examples will be described together with comparative examples.

[Example 1]
Mixing of 1 mol (93 g) of aniline [pi-electron conjugated polymer (component A)], 1 mol (663 g) of the oxyalkylene compound a (component B), 1N hydrochloric acid and methyl isobutyl ketone (MIBK) 1 ml of ammonium persulfate (oxidant) dissolved in 1000 ml of 1N hydrochloric acid while stirring at a temperature of 5 to 10 ° C. while stirring 2000 ml of the solvent [1N hydrochloric acid / MIBK = 2/1 (mixed weight ratio)]. 228.2 g) was added dropwise over 1 hour and oxidative polymerization was carried out for 10 hours to obtain a polymer. Next, this polymer was washed with water and methanol and dried to obtain a conductive polymer.

[Examples 2 to 7]
Except for changing the type of π-electron conjugated polymer (component A), oxyalkylene compound, oxidizing agent or solvent, and the mixing ratio as shown in Table 1 below, in the same manner as in Example 1, A conductive polymer was obtained.

[Comparative Example 1]
Mixed solvent of 1 mol of aniline (93 g), 1 mol (368 g) of pentadecylbenzenesulfonic acid (dopant), 1N hydrochloric acid and methyl isobutyl ketone (MIBK) [1N hydrochloric acid / MIBK = 2/1 (mixing weight ratio) Into the flask, 1 mol (228.2 g) of ammonium persulfate (oxidant) dissolved in 1000 ml of 1N hydrochloric acid was added dropwise over 1 hour while being controlled at 5 to 10 ° C. and stirred, and oxidized for 10 hours. Polymerization was carried out to obtain a polymer. Next, this polymer was washed with water and methanol and dried to obtain a conductive polymer.

[Comparative Example 2]
According to Example 4 of Unexamined-Japanese-Patent No. 2002-179911, the conductive polymer (conductive polyaniline) was obtained.

(Preparation of doped quinonediimine / phenylenediamine type conductive polyaniline by oxidative polymerization of aniline)
In a 10-liter separable flask equipped with a stirrer, a thermometer, and a straight tube adapter, 6000 g of distilled water, 360 ml of 36% hydrochloric acid, and 400 g (4.295 mol) of aniline were charged in this order to dissolve the aniline. Separately, while cooling with ice water, 434 g (4.295 mol) of 97% concentrated sulfuric acid was added to 1493 g of distilled water in a beaker and mixed to prepare an aqueous sulfuric acid solution. This sulfuric acid aqueous solution was added to the separable flask, and the whole flask was cooled to −4 ° C. in a low-temperature thermostatic bath. Next, 980 g (4.295 mol) of ammonium peroxodisulfate was added to 2293 g of distilled water in a beaker and dissolved to prepare an aqueous oxidizing agent solution. The whole flask was cooled in a low-temperature thermostatic bath, and while maintaining the temperature of the reaction mixture at −3 ° C. or lower, the aqueous solution of ammonium peroxodisulfate was transferred from the straight tube adapter to the acidic aqueous solution of aniline with stirring using a tubing pump. Was gradually added dropwise at a rate of 1 ml / min or less to obtain a polymer powder. The polymer powder was separated by filtration, washed with water, washed with acetone, and vacuum dried at room temperature to obtain 430 g of black-green quinonediimine / phenylenediamine type conductive polyaniline powder.

(Preparation of quinonediimine / phenylenediamine solvent-soluble polyaniline by dedoping of conductive organic polymer)
350 g of the doped conductive polyaniline powder was added to 4 liters of 2N ammonia water, and the mixture was stirred for 5 hours at a rotational speed of 5000 rpm using an auto homomixer. The powder was separated by filtration with a Buchner funnel and washed repeatedly with distilled water until the filtrate became neutral while stirring in a beaker, and then washed with acetone until the filtrate became colorless. Thereafter, the powder was vacuum-dried at room temperature for 10 hours to obtain 280 g of a black-brown dedoping solvent-soluble quinonediimine / phenylenediamine type polyaniline powder. Next, 1.49 g of phenylhydrazine was dissolved in 90 g of N-methyl-2-pyrrolidone, and then 10 g of the solvent-soluble quinonediimine / phenylenediamine type polyaniline was dissolved with stirring. This solution was filtered under reduced pressure using a G2 filter to obtain a polyaniline solution. Next, 0.76 g of polystyrene sulfonic acid (5.5 mmol / g) and 0.42 g of triethylamine were dissolved in 3.68 g of N-methyl-2-pyrrolidone to obtain a solution. 4.86 g of this solution and 5.0 g of the 10% by weight polyaniline solution obtained above were mixed, and the resulting mixture was defoamed to obtain a conductive polymer solution.

  Using the conductive polymers of Examples and Comparative Examples thus obtained, each characteristic was evaluated as follows. These results are shown in Tables 2 and 3 below.

〔solubility〕
Each conductive polymer was mixed with various solvents (THF, MEK, acetone, ethyl acetate) and stirred to measure the solubility in various solvents. In addition, about the comparative examples 1 and 2, the solubility with respect to what volatilized and dried the solvent was measured.

[Amount of free dopant]
The amount of free (free) dopant in each conductive polymer was measured according to thermogravimetric analysis (TGA). That is, 10 mg of the dried conductive polymer was increased at a temperature increase rate of 20 ° C./min from 30 to 750 ° C. in a nitrogen atmosphere, and then increased to 900 ° C. at a temperature increase rate of 20 ° C./min in the air. It was. And the amount of dopants (free dopant amount) which did not participate in doping was calculated | required from the heating loss at this time.

[Electric resistance]
(initial)
Each conductive polymer was mixed with THF, subjected to ultrasonic treatment, cast on a glass plate using an applicator, and dried (120 ° C. × 30 minutes) to form a coating film (thickness 5 μm). And the electrical resistance of this coating film was calculated | required by the 4 terminal method in the environment of 25 degreeC x 50% RH (Diale Instruments Inc. make, Loresta GP). In Comparative Example 2, since the solubility in THF was extremely low, or NMP was not sufficiently volatilized at 150 ° C., it was dissolved in water and cast.

(Number of fluctuation digits after ozone)
The coating film was left in an ozone environment of 50 ° C. × 80 pphm for 1 month, and the subsequent electrical resistance was measured in the same manner as described above. And the fluctuation | variation digit | number of the electrical resistance after an initial stage and after ozone was calculated | required.

[Number of fluctuation digits after wet heat]
The coating film was allowed to stand in a moist heat environment of 50 ° C. × 95% RH for 1 month, and the subsequent electrical resistance was measured in the same manner as described above. And the fluctuation | variation digit | number of the electrical resistance after an initial stage and after wet heat was calculated | required.

[Bleed]
Using each conductive polymer, a coating film was formed in the same manner as described above, and the presence or absence of bleed of the dopant from the coating film was observed visually and with a finger.

  From the above results, the example products were excellent in solubility, had small fluctuations in electrical resistance under a moist heat environment, and were excellent in conductivity.

  On the other hand, in Comparative Example 1 product, the dopant (pentadecylbenzenesulfonic acid) was liberated under a high temperature and high humidity (50 ° C. × 95% RH) environment, and the amount of free dopant was high. As a result, the polyaniline aggregated to cause bleeding. In addition, the electric resistance fluctuated greatly in a humid heat environment. The product of Comparative Example 2 was significantly inferior in solubility in a solvent.

  Next, examples of the semiconductive composition using the conductive polymer will be described together with comparative examples.

  First, prior to the examples and comparative examples, the following materials were prepared.

[Π-electron non-conjugated polymer a (carbonate TPU)]
Carbonate-based TPU that has no sulfonic acid group in its molecular structure (E980, manufactured by Nihon Milactolan)

[Π-electron non-conjugated polymer b (PMMA)]
Polymethyl methacrylate (PMMA) having no sulfonic acid group in the molecular structure (manufactured by Sumitomo Chemical Co., Ltd., LG6A)

[Π-electron non-conjugated polymer c (H-NBR)]
H-NBR having no sulfonic acid group in the molecular structure (Nippon Zeon Corporation, Zetpol 0020)

[Π-electron non-conjugated polymer d (sulfonated urethane)]
Polyol obtained by copolymerizing adipic acid / 5-sodium sulfoisophthalic acid = 4/1 (weight ratio) and ethylene glycol [weight average molecular weight (Mw): 2000], and polyethylene adipate polyol (Mw: 2000) And MDI were reacted to prepare a sulfonated urethane (sodium sulfonate group 0.01 mmol / g, Mw: 80,000).

[Π-electron non-conjugated polymer e (sulfonated acrylic fluororesin)]
Methyl methacrylate / butyl acrylate / perfluorooctyl ethylene = 8/1/1 (weight ratio) and sulfoethyl methacrylate were copolymerized to form a sulfonated acrylic fluororesin (ammonium sulfonate group 0.02 mmol / g, Mw: 40,000).

[Vulcanization accelerator a]
Sulfenamide-based cross-linking accelerator (Ouchi Shinsei Chemical Co., Ltd., Noxeller CZ)

[Vulcanization accelerator b]
Dithiocarbamate-based crosslinking accelerator (Ouchi Shinsei Chemical Co., Ltd., Noxeller BZ)

[Examples 8 to 16, Comparative Examples 3 and 4]
The components shown in Table 4 and Table 5 described below were blended in the proportions shown in the same table, and kneaded using three rolls to prepare a semiconductive composition (coating liquid).

[Electrical resistance, voltage dependence of electrical resistance]
Each semiconductive composition (coating liquid) was applied on a SUS304 plate and dried at 120 ° C. for 30 minutes to prepare a conductive coating film having a thickness of 30 μm. Next, with respect to this conductive coating film, in an environment of 25 ° C. × 50% RH, an electric resistance when a voltage of 10 V is applied (Rv = 10 V) and an electric resistance when a voltage of 100 V is applied (Rv = 100V) was measured according to SRIS 2304, respectively. Then, the voltage dependence of the electrical resistance is displayed in the number of fluctuation digits by Log (Rv = 10 V / Rv = 100 V).

[Environmental dependence of electrical resistance]
Using each semiconductive composition (coating liquid), a conductive coating film was prepared in the same manner as described above, and this conductive coating film was subjected to low temperature and low humidity (10 ° C. × 10%) under the condition of an applied voltage of 10 V. RH) electrical resistance (Rv = 10 ° C. × 10% RH) and high temperature high humidity (35 ° C. × 85% RH) electrical resistance (Rv = 35 ° C. × 85% RH) according to SRIS 2304 Each was measured. Then, the environmental dependence of the electrical resistance was displayed in terms of variable digits by Log (Rv = 10 ° C. × 10% RH / Rv = 35 ° C. × 85% RH).

[Number of electrical resistance fluctuations due to environment]
Using each semiconductive composition (coating liquid), a conductive coating film was prepared in the same manner as described above. The conductive coating film had an electrical resistance before standing (Rv = 0 days) and 50 ° C. The electrical resistance (Rv = 100 days) after standing for 100 days in an environment of × 95% RH was measured according to SRIS 2304 under the conditions of 25 ° C. × 50% RH and 10 V application. Then, the number of digits of electrical resistance variation due to the environment was determined by Log (Rv = 100 days / Rv = 0 day).

[Electric resistance fluctuation (charge up) in high voltage range]
Using each semiconductive composition (coating liquid), a conductive coating film was prepared in the same manner as described above, and a voltage of 100 V was applied to the conductive coating film in an environment of 25 ° C. × 50% RH. The electrical resistance (Rv = 0 seconds) when applied, and the electrical resistance (Rv = 600 seconds) when a voltage of 100 V is applied for 10 minutes in an environment of 25 ° C. × 50% RH, respectively, according to SRIS 2304 It was measured. Then, the electrical resistance fluctuation in the high voltage region was displayed by the number of fluctuation digits by Log (Rv = 600 seconds / Rv = 0 seconds).

[Compatibility]
The compatibility between each conductive polymer and the π-electron nonconjugated polymer was evaluated. Evaluation is that the compatibility between the two is excellent and the aggregates of 0.1 μm or more are not formed, ○, the compatibility of both is bad, the conductive polymer is aggregated and the aggregate of 0.1 μm or more is generated X. In addition, the thing of evaluation x has described the particle size of the aggregate in the lower column.

  From the above results, the products of the examples were excellent in solubility and excellent in conductivity, and the variation in electric resistance under a moist heat environment was small.

  On the other hand, the product of Comparative Example 3 had a large variation in electrical resistance under a humid heat environment. The product of Comparative Example 4 had a large voltage dependency of electrical resistance, agglomerates having a large particle size were generated, and the compatibility was poor.

  Next, examples of the charging roll using the semiconductive composition will be described.

Example 17
(Preparation of base layer material)
Silicone rubber (manufactured by Shin-Etsu Chemical Co., Ltd., KE1350AB) in which carbon black was dispersed was prepared. Using this silicone rubber, a conductive coating film was prepared in the same manner as described above. The electrical resistance (10V) was 4.5 as a result of measuring the electrical resistance and the like of the conductive coating film in the same manner as described above. × 10 ⁴ Ω · cm, electrical resistance (100V) is 3.8 × 10 ³ Ω · cm, voltage dependency of electrical resistance is 1.07 digits, environment dependency of electrical resistance is 0.03 digits, high voltage range The electrical resistance fluctuation (charge-up) was 0.13 digits.

(Preparation of intermediate layer material)
After 93 parts of urethane elastomer (manufactured by Nippon Milactolan, E980) are dissolved in 300 parts of THF, 150 parts of MEK and 100 parts of toluene, 7 parts of acetylene black (Denka Black HS100, manufactured by Denki Kagaku Kogyo Co., Ltd.) are added and three rolls Kneaded to prepare a conductive composition (coating solution). Using this conductive composition, a conductive coating film was produced in the same manner as described above, and the electrical resistance and the like of this conductive coating film were measured in the same manner as described above. 0.0 × 10 ⁶ Ω · cm, electric resistance (100V) is 9.0 × 10 ⁴ Ω · cm, voltage dependency of electric resistance is 1.82 digits, environment dependency of electric resistance is 0.05 digits, high voltage The electric resistance fluctuation (charge up) in the region was 0.09 digits.

(Preparation of surface layer material)
A semiconductive composition was prepared in the same manner as in Example 11.

(Preparation of charging roll)
The base layer material is poured into an injection mold having a shaft core (diameter 10 mm, made of SUS304), heated at 150 ° C. for 45 minutes, and then removed from the mold. A base layer was formed along the outer peripheral surface of the shaft body. Next, the intermediate layer material was applied to the outer peripheral surface of the base layer to form an intermediate layer. Next, the base layer (thickness 3 mm) is formed on the outer peripheral surface of the shaft body by applying the surface layer material to the outer peripheral surface of the intermediate layer to form the surface layer, and the intermediate layer (thickness) is formed on the outer peripheral surface. 10 μm) was formed, and a surface layer (thickness: 40 μm) was formed on the outer peripheral surface of the charging roll having a three-layer structure.

  Using the charging rolls of the examples thus obtained, each characteristic was evaluated according to the following criteria. These results are also shown in Table 6 below.

[Electrical resistance, voltage dependence of electrical resistance]
With the surface of the charging roll pressed against the SUS plate, a load of 1 kg is applied to both ends of the charging roll, and the electrical resistance between the core of the charging roll and the surface of the charging roll pressed against the SUS plate is Measured according to SRIS 2304. In addition, the electrical resistance is an electrical resistance (Rv = 10V) when a voltage of 10V is applied in an environment of 25 ° C. × 50% RH, and an electrical resistance (Rv = 100V) when a voltage of 100V is applied. It was measured. Then, the voltage dependence of the electrical resistance is displayed in the number of fluctuation digits by Log (Rv = 10 V / Rv = 100 V).

[Environmental dependence of electrical resistance]
According to the evaluation of the electrical resistance, the electrical resistance (Rv = 10 ° C. × 10% RH) at the low temperature and low humidity (10 ° C. × 10% RH) and the high temperature and high humidity (35 ° C. × 35 ° C.) The electrical resistance (Rv = 35 ° C. × 85% RH) at 85% RH was measured according to SRIS 2304. Then, the environmental dependence of the electrical resistance was displayed in terms of variable digits by Log (Rv = 10 ° C. × 10% RH / Rv = 35 ° C. × 85% RH).

[Hardness (JIS A)]
The hardness of the outermost surface of each charging roll was measured according to JIS K 6253.

(Compression set)
The compression set of each charging roll was measured according to JIS K 6262 under conditions of a temperature of 70 ° C., a test time of 22 hours, and a compression rate of 25%.

(Charging roll characteristics)
(Image unevenness)
Each charging roll was incorporated into a commercially available color printer, and images were taken out in an environment of 20 ° C. × 50% RH. In the evaluation, a case where there was no density unevenness in the halftone image and there was no fine line break or color unevenness was indicated as ◯, and a case where density unevenness occurred was indicated as x.

(Changes in image quality due to the environment)
Each charging roll is installed in a commercially available color printer, and images are taken out in an environment of 15 ° C. × 10% RH, and images are taken out in an environment of 35 ° C. × 85% RH. Evaluation of the fluctuation of In the evaluation, a solid black image was printed, and when the change was 0.1 or less with a Macbeth densitometer, ○, and when it exceeded 0.1, x.

[Concentration fluctuation due to charge-up]
Each charging roll was incorporated into a commercially available color printer, and 10,000 sheets of images were taken out in an environment of 25 ° C. × 50% RH. In the evaluation, a case where there was no density difference in a halftone image (less than 0.1 with a Macbeth densitometer) was evaluated as ◯, and a case where a density difference occurred (0.1 or more with a Macbeth densitometer) was evaluated as x.

[Number of electrical resistance fluctuations due to environment]
The electrical resistance before standing (Rv = 0 day) and the electrical resistance (Rv = June) after standing for 6 months in an environment of 50 ° C. × 95% RH are 10 V in an environment of 25 ° C. × 50% RH. And measured according to SRIS 2304. And the fluctuation | variation digit | number of the electrical resistance was calculated | required by Log (Rv = June / Rv = 0 day).

  From the above results, the product of Example 17 was excellent in all characteristics and excellent in charging roll characteristics.

  Next, examples of developing rolls using the semiconductive composition will be described.

Example 18
(Preparation of base layer material)
A silicone rubber (KE1350AB, manufactured by Shin-Etsu Chemical Co., Ltd.) in which carbon black was dispersed, similar to the base layer material of Example 17, was prepared.

(Preparation of intermediate layer material)
A semiconductive composition was prepared in the same manner as in Example 8.

(Preparation of surface layer material)
A conductive composition (coating liquid) was prepared in the same manner as the material for the intermediate layer of Example 17.

(Preparation of developing roll)
The base layer material is poured into an injection mold having a shaft core (diameter 10 mm, made of SUS304), heated at 150 ° C. for 45 minutes, and then removed from the mold. A base layer was formed along the outer peripheral surface of the shaft body. Next, the intermediate layer material was applied to the outer peripheral surface of the base layer to form an intermediate layer. Next, the surface layer material is applied to the outer peripheral surface of the intermediate layer to form a surface layer, whereby a base layer (thickness 4 mm) is formed on the outer peripheral surface of the shaft, and the intermediate layer (thickness) is formed on the outer peripheral surface. 45 μm) was formed, and a three-layer developing roll having a surface layer (thickness 5 μm) formed on the outer peripheral surface thereof was produced.

  Using the developing rolls of the examples thus obtained, each characteristic was evaluated in accordance with the evaluation criteria of the charging roll. These results are also shown in Table 7 below.

  From the above results, the product of Example 18 was excellent in all characteristics and excellent in developing roll characteristics.

  The conductive polymer of the present invention, the semiconductive composition using the same, and the semiconductive member for electrophotographic apparatus are suitably used for electrophotographic apparatus members such as a charging roll, a developing roll, a transfer roll, and an intermediate transfer belt. be able to.

Claims (8)

A conductive polymer which is a solvent-soluble conductive polymer obtained by conducting the following component (A) with a dopant, wherein the dopant is the following component (B).
(A) π electron conjugated polymer.
(B) An oxyalkylene compound having at least one functional group of a sulfonate group and a sulfonate group and a fluorinated alkyl group. The conductive polymer according to claim 1, wherein the oxyalkylene compound of the component (B) is a compound having a structural unit represented by the following general formula (1).

  The conductive polymer according to claim 1 or 2, wherein the fluorinated alkyl group in the component (B) is a fluorinated alkyl group having 1 to 4 carbon atoms.   The conductive polymer according to any one of claims 1 to 3, wherein the number average molecular weight of the oxyalkylene compound as the component (B) is in the range of 300 to 4500.   The π-electron conjugated polymer as the component (A) is derived from at least one monomer selected from the group consisting of aniline, pyrrole, thiophene, and derivatives thereof. Conductive polymer described in 1.   A semiconductive composition comprising the conductive polymer according to any one of claims 1 to 5 as a main component.   The semiconductive composition according to claim 6, wherein the semiconductive composition contains a π-electron non-conjugated polymer.   A semiconductive member for an electrophotographic apparatus, wherein the semiconductive composition according to any one of claims 1 to 7 is used for at least a part of the semiconductive member.