JP4089667B2 - Semiconductive member for electrophotographic equipment - Google Patents

Description

The present invention relates to semi-conductive member for electrophotography apparatus and, more particularly, to a semi-conductive member for electronic photographic apparatus such as a charging roller.

  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, the polymer can be provided with solubility, 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).

  However, in the synthesis method described in Patent Document 1, doping with a halogen gas or the like is essential 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.

Therefore, as a result of intensive studies to solve such problems, the present inventor has used a dopant having an alkyl group repeating unit of 12 to 15 such as dodecylbenzenesulfonic acid to give conductivity to the polymer. Thus, it has been found that the solubility can also be imparted, and a patent application has already been filed for a semiconductive composition containing a conductive polymer using such a dopant (Japanese Patent Application No. 2002-348350).
JP 2001-324882 A

  However, as a result of further research on the semiconductive composition described in Japanese Patent Application No. 2002-348350, the present inventor has a tendency that the compatibility between the conductive polymer and the non-conjugated polymer is slightly inferior. As a result, it was found that the electrical resistance tends to increase with time.

The present invention has been made in view of such circumstances, and is excellent in compatibility between a conductive polymer and a non-conjugated polymer, has a small change in electrical resistance over time, and has excellent conductivity controllability. providing sexual member and an object.

To achieve the above object, the semi-conductive member for electrophotography apparatus of the present invention is a semi-conductive member for electrophotography apparatus according to (A) and (B) as essential components the following, the above (A the weight of) is taken as 100%, constituting as free amount of dopant in was determined by thermogravimetric analysis (a) is less than 30 wt%, and is electrical resistance 100 [Omega · cm or more (a) the door Ru.
(A) A solvent-soluble conductive polymer obtained by conducting a π-electron conjugated polymer with a dopant, and the monomer constituting the π-electron conjugated polymer is aniline, thiophene, pyrrole, o-toluidine, at least one selected from the group consisting of o-anisidine, 2-ethylaniline, 2-propylaniline, 2-sec-butylaniline and derivatives thereof, and the dopant has two or more alkyl substituents. And an alkylbenzene sulfonic acid having a total of 10 to 37 carbon atoms in the alkyl substituent or a salt thereof.
(B) A non-conjugated polymer having a structure of a sulfonic acid group or a salt thereof, which is at least one selected from the group consisting of acrylic resins, urethane resins, and thermoplastic elastomers .

That is, the present inventors have earnestly pursued to obtain a semiconductive member for an electrophotographic apparatus having excellent compatibility between a conductive polymer and a non-conjugated polymer, a small change in electrical resistance with time, and excellent conductivity control. Repeated research. As a result, paying attention to a solvent-soluble conductive polymer obtained by conducting a π-electron conjugated polymer with a dopant, the amount of free dopant in the conductive polymer is less than 30% by weight, and the electrical resistance of the conductive polymer When it was 100 Ω · cm or more, it was found that the composition was excellent in compatibility with the non-conjugated polymer, the change in electrical resistance with time was small, and the conductivity was excellent, and the present invention was achieved.

In the semiconductive composition according to the semiconductive member for electrophotographic equipment of the present invention, the amount of free dopant in the conductive polymer is less than 30% by weight, and the electric resistance of the conductive polymer is 100 Ω · cm or more. Because it has a special conductive polymer (component A) and a specific non-conjugated polymer (component B) as essential components, it has excellent compatibility between them, has little change in electrical resistance over time, and conductance control There is an effect that it is excellent in nature.

  In addition, as a dopant for the special conductive polymer (component A), alkylbenzene sulfonic acid or a salt thereof having two or more alkyl substituents and having a total of 10 to 37 carbon atoms in the alkyl substituents is used. , It is not necessary to use an excessive amount of dopant, and conductivity and solubility are improved.

  Moreover, since the semiconductive member for an electrophotographic apparatus of the present invention uses the semiconductive composition as at least a part of the semiconductive member for an electrophotographic apparatus, an electrophotographic apparatus member such as a charging roll. The image quality is uniform and the long-term durability is improved.

  Next, embodiments of the present invention will be described in detail.

The semiconductive composition used in the present invention can be obtained using a special conductive polymer (component A) and a specific non-conjugated polymer (component B).

  In the present invention, the amount of free dopant in the conductive polymer (component A) is less than 30% by weight, and the electrical resistance of the conductive polymer (component A) is 100 Ω · cm or more. It is.

  The special conductive polymer (component A) is a solvent-soluble conductive polymer obtained by conducting a π-electron conjugated polymer with a dopant.

  As monomers constituting the π-electron conjugated polymer, aniline, thiophene, pyrrole, o-toluidine, o-anisidine, 2-ethylaniline, 2-propylaniline, 2-sec-butylaniline and derivatives thereof are used. It is done. These may be used alone or in combination of two or more. Among these, o-toluidine is preferably used in terms of solubility and reactivity during polymerization.

  In addition, as the dopant, alkylbenzene sulfonic acid or a salt thereof having two or more alkyl substituents and the total number of carbon atoms of the alkyl substituents being 10 to 37 is preferably used. Is an alkylbenzene sulfonic acid having a total of 12 to 24 or a salt thereof. That is, if the total number of carbon atoms of the alkyl substituents is less than 10, an excessive amount is necessary to obtain sufficient solubility, and fluctuations in electrical resistance due to moisture absorption and excessive dopants appear on the surface, causing bleeding. This is because when the total number of carbon atoms exceeds 37, the resulting conductive polymer becomes waxy and difficult to dissolve in the solvent. Moreover, as for carbon number of one alkyl substituent, 2-18 are preferable, Most preferably, it is 4-15.

  The alkylbenzene sulfonic acid or salt thereof preferably has at least one alkyl substituent having 4 to 18 carbon atoms from the viewpoint of reactivity, solubility, and compatibility with elastomers.

  The alkylbenzene sulfonic acid or a salt thereof may be a mixture of two or more of those having two or more alkyl substituents and the total number of carbon atoms of the alkyl substituents being 10 to 37. Specifically, it may be a mixture of two or more selected from the group consisting of the following alkylbenzene sulfonic acids or salts (a1) to (a7) thereof.

a1: Alkylbenzenesulfonic acid having two pentyl groups (—C ₅ H ₁₁ ) or a salt thereof (the total number of carbon atoms of the alkyl substituent is 10)
a2: an alkylbenzenesulfonic acid having two hexyl groups (—C ₆ H ₁₃ ) or a salt thereof (the total number of carbon atoms of the alkyl substituent is 12)
a3: an alkylbenzenesulfonic acid having 3 pentyl groups (—C ₅ H ₁₁ ) or a salt thereof (the total number of carbon atoms of the alkyl substituent is 15)
a4: alkylbenzenesulfonic acid or salt thereof having two pentyl groups (—C ₅ H ₁₁ ) and one hexyl group (—C ₆ H ₁₃ ) (the total number of carbon atoms of the alkyl substituents is 16)
a5: an alkylbenzenesulfonic acid having 3 hexyl groups (—C ₆ H ₁₃ ) or a salt thereof (the total number of carbon atoms of the alkyl substituent is 18)
a6: alkylbenzenesulfonic acid or salt thereof having one decyl group (—C ₁₀ H ₂₁ ) and one dodecyl group (—C ₁₂ H ₂₅ ) (the total number of carbon atoms of the alkyl substituents is 22)
a7: alkylbenzenesulfonic acid or salt thereof having one methyl group (—CH ₃ ) and _three dodecyl groups (—C ₁₂ H ₂₅ ) (the total number of carbon atoms of the alkyl substituents is 37)

  The alkyl substituent is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, and a tridecyl group. Group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group and the like. These alkyl substituents may have a branch, but a straight chain is preferred from the viewpoint of effects. These may be used alone or in combination of two or more. Among these, a C2-C18 alkyl substituent is preferable.

  The salt of the alkylbenzene sulfonic acid is not particularly limited, and examples thereof include metal salts such as sodium salt, calcium salt, barium salt, ammonium salt, pyridinium salt, and the like. Of these, metal salts are preferably used.

  The specific alkylbenzenesulfonic acid or salt thereof used as the dopant can be produced, for example, as follows. That is, after olefin having 2 to 24 carbon atoms is alkylated to benzene or alkylbenzene by Friedel-Crafts reaction, unreacted substances are removed by distillation, and then sulfur trioxide gas is added at a constant flow rate to obtain a specific alkylbenzene. Sulfonic acid can be obtained. Moreover, the salt of a specific alkylbenzenesulfonic acid can be obtained by making sodium hydroxide, calcium hydroxide, etc. react with the obtained alkylbenzenesulfonic acid. The specific alkylbenzene sulfonic acid or salt thereof used as the dopant can also be obtained by sulfonation using a petroleum fraction as a raw material.

  In addition, as said dopant, the thing etc. which have an ether group and ester group in a molecular structure can be used.

In addition, as a dopant used for the semiconductive composition which concerns on this invention , a well-known dopant may be used together with the said specific alkylbenzenesulfonic acid or its salt. In this case, it is preferable to use a known dopant in a proportion within 50 mol% of the entire dopant.

Examples of the known dopant include halogens, Lewis acids, proton acids, transition metals, halides, transition metal salts, organic compounds, acceptor ions (ClO ₄ ⁻ , BF ₄ ⁻ ), and the like, and functional groups thereof. The compound containing is used.

  The specific conductive polymer (component A) is obtained, for example, by a chemical oxidative polymerization method such as oxidative polymerization of a monomer constituting a π-electron conjugated polymer and a dopant in water in the presence of an oxidizing agent. In addition, it can also be obtained by an electrolytic polymerization method. The specific conductive polymer (component A) can also be obtained by polycondensation of the monomer constituting the π-electron conjugated polymer and then doping, or in a mixture of an organic solvent and water. Thus, the monomer constituting the π-electron conjugated polymer and the dopant are emulsified, and the dopant is introduced into the monomer, and then the monomer is polymerized. It can also be obtained by doping the π-electron conjugated polymer constituting the A component with a dopant after making it undope.

  The oxidizing agent is not particularly limited, and examples thereof include ammonium persulfate (APS), peroxides such as hydrogen peroxide, ferric chloride, and the like.

  The mixing ratio of the monomer constituting the π-electron conjugated polymer and the dopant is preferably a molar ratio, preferably in the range of π-electron conjugated polymer / dopant = 1 / 0.03 to 1/3, particularly preferably. Is in the range of π-electron conjugated polymer / dopant = 1 / 0.05 to 1/2. That is, when the molar ratio of the dopant is low, the compatibility and dispersibility with the π-electron conjugated polymer tend to be reduced. Conversely, when the molar ratio of the dopant is high, the reactivity is deteriorated or the ionic conductivity is decreased. This is because the effect of contributing to the property becomes too strong, and there is a tendency to reduce the electronic conductivity of the conductive polymer (component A).

  As described above, the conductive polymer (component A) thus obtained was tetrahydrofuran (THF), diethyl ether, acetone, methyl ethyl ketone, ethyl acetate, m-cresol, N-methyl-2-pyrrolidone ( NMP) and soluble in solvents such as toluene.

  This specific conductive polymer (component A) preferably has a solubility in a solvent having a boiling point of 100 ° C. or lower of 1.5% or more, particularly preferably 3% or more. Such solubility is preferable in terms of coating properties and film thickness controllability when blended with other polymers. Examples of the solvent having a boiling point of 100 ° C. or lower include diethyl ether, tetrahydrofuran (THF), dipropyl ether, tetrahydropyran, acetone, methyl ethyl ketone, and ethyl acetate.

  The conductive polymer (component A) requires that the amount of free dopant in the conductive polymer (component A) be less than 30% by weight, and preferably less than 5% by weight. That is, when the amount of the free dopant is 30% by weight or more, it absorbs moisture in the air, so that the conductive mechanism of the conductive polymer in the composition is cut and it becomes difficult for electricity to flow.

  In the present invention, the amount of free dopant refers to the amount of a compound such as sulfonic acid that is not involved in doping and that is not ionically bonded to the conductive polymer. And this free dopant amount can be measured according to a thermogravimetric analysis (TGA), for example.

The conductive polymer (component A) needs to have an electric resistance of 100 Ω · cm or more, preferably in the range of 10 ² to 10 ⁸ Ω · cm. That is, if the electrical resistance is less than 100 Ω · cm, it is disadvantageous for controlling the electrical resistance of the composition.

  In addition, the said electrical resistance can be measured as follows, for example. That is, the conductive polymer (component A) is mixed with a solvent such as THF, subjected to ultrasonic treatment, and then centrifuged to take out the supernatant. And this supernatant is cast on a SUS board using an applicator, and it dries (for example, 100 degreeC x 30 minutes), and forms a coating film (thickness 5 micrometers). The electrical resistance of the coating film is measured according to SRIS 2304 by applying a voltage of 1 V in an environment of 25 ° C. × 50% RH.

  The number average molecular weight (Mn) of the conductive polymer (component A) is preferably in the range of 1,000 to 100,000, particularly preferably in the range of 3,000 to 20,000.

Next, a specific non-conjugated polymer (component B) used together with the specific conductive polymer (component A) will be described.

As the specific non-conjugated polymer (B component) from the viewpoint of excellent compatibility with the conductive polymer, acrylic resins, urethane resins, thermoplastic elastomers are needed use.

Moreover, the specific non-conjugated polymer (B component) in terms of compatibility with the conductive polymer (A component), in the molecular structure, which have a sulfonic acid group or sulfonate structure. Examples of the sulfonate structure include a sulfonic acid metal salt structure, an ammonium sulfonate structure, and a pyridinium sulfonate structure as described above.

In this case, the content of the sulfonic acid group or sulfonate structure (sulfonic acid group amount) in the specific non-conjugated polymer is preferably in the range of 0.001 to 1 mmol / g, particularly preferably 0.01. Within the range of ~ 0.2 mmol / g. That is, when the amount of the sulfonic acid group is less than 0.001 mmol / g, the compatibility with the conductive polymer (component A) tends to be deteriorated. This is because a decrease and expression of ionic conductivity are observed.

Examples of the acrylic resin 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 an acrylic oligomer for photocrosslinking and the like. These are in the molecular structure, a sulfonic acid group or sulfonate structure that has been introduced. Examples of the method for introducing a sulfonic acid group include a method of copolymerizing a vinyl monomer having a sulfonic acid group or a sulfonate with a radical, anion, or cation, or a diol monomer having a sulfonic acid group, a urethane reaction, Examples thereof include a method of introducing by transesterification.

Examples of the urethane resin include ether resins, ester resins, acrylic resins, aliphatic resins, and the like, and those obtained by copolymerizing a silicone polyol or a fluorine polyol. The urethane-based resin may have a urea bond or an imide bond in the molecular structure. These are in the molecular structure, a sulfonic acid group or sulfonate structure that has been introduced.

Examples of the thermoplastic elastomer include styrene-based thermoplastic elastomers such as styrene-butadiene-styrene block copolymer (SBS) and styrene-ethylene-butylene-styrene block copolymer (SEBS), and urethane-based thermoplastic elastomers. (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. These may be used alone or in combination of two or more. Among these, TPU is preferably used in terms of simplicity of the synthesis process and solubility in a solvent. These are in the molecular structure, a sulfonic acid group or sulfonate structure that has been introduced.

  The number average molecular weight (Mn) of such a non-conjugated polymer (component B) is preferably in the range of 500 to 2,000,000, particularly preferably in the range of 2,000 to 800,000.

  The conductive polymer (component A) and the non-conjugated polymer (component B) are mixed and made into a semiconductive composition as described later, but the raw material of the conductive polymer (component A) [π electron The total amount of the conjugated polymer and the dopant] and the mixing ratio of the non-conjugated polymer (component B) are in a weight ratio, and the raw material of component A / component B = 1/99 to 40/60. Particularly preferably, the raw material of component A / component B = 4/96 to 35/65. That is, when the weight ratio of the component A raw material is less than 1, there is a tendency that the effect on conductivity is reduced. Conversely, when the weight ratio of the component A raw material exceeds 40, the resulting composition is hard. This is because the composition tends to be brittle and the physical properties of the composition tend to decrease.

In addition to the conductive polymer (component A) and non-conjugated polymer (component B), the semiconductive composition used in the present invention may optionally contain an ionic conductive agent, an electronic conductive agent, a crosslinking agent, and the like. It doesn't matter.

  Examples of the ionic conductive agent include compounds that ionically dissociate 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 such an ionic conductive agent is 100 parts by weight (hereinafter abbreviated as “part”) of the total of the raw material of the conductive polymer (component A) and the non-conjugated polymer in terms of physical properties and electrical characteristics The content is preferably in the range of 0.01 to 5 parts, particularly preferably in the range of 0.5 to 2 parts.

Examples of the electron conductive agent include carbon black, c-ZnO (conductive zinc oxide), c-TiO ₂ (conductive titanium oxide), c-SnO ₂ (conductive tin oxide), graphite, and the like. .

  The blending ratio of such an electronic conductive agent is 5 to 30 with respect to a total of 100 parts of the raw material of the conductive polymer (A component) and the non-conjugated polymer (B component) in terms of physical properties and electrical characteristics. Within the range of parts, particularly preferably within the range of 8 to 20 parts.

  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. In addition to the crosslinking agent, a photoinitiator that is crosslinked by energy such as ultraviolet rays or electron beams may be used in combination.

  The blending ratio of such a crosslinking agent is 1 with respect to a total of 100 parts of the raw material for the conductive polymer (component A) and the non-conjugated polymer (component B) from the viewpoint of physical properties, adhesion, and liquid storage. It is preferably within the range of -30 parts, particularly preferably within the range of 3-10 parts.

The semiconductive composition used in the present invention may contain a crosslinking accelerator, an anti-aging agent, etc., if necessary, in addition to the above components.

  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 used in the present invention can be produced, for example, as follows. That is, first, a conductive polymer (component A) is produced according to the method described above. Next, the conductive polymer (component A) is blended with a non-conjugated polymer (component B) and, if necessary, an ionic conductive agent, an electronic conductive agent, a crosslinking agent, and the like. These are kneaded using a kneader such as a roll, kneader, Banbury mixer, etc., dissolved in a solvent to form a solution, and dispersed using a bead mill or three rolls, thereby achieving the intended 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 used in the present invention can be formed into a film by coating a coating solution obtained by dissolving a conductive polymer (component A) or a non-conjugated polymer (component B) in a solvent. However, the present invention is not limited to this, and it is also possible to form a film by an extrusion molding method, an injection molding method, an inflation molding method, or the like.

The semiconductive composition used in the present invention preferably has an electric resistance described later in the range of 10 ⁷ to 10 ¹¹ Ω · cm, particularly preferably in the range of 10 ⁸ to 10 ¹⁰ Ω · cm. That is, if the electrical resistance is less than 10 ⁷ Ω · cm, the electrical resistance is too low, so that there are few advantages for images as an electrophotographic apparatus member in terms of charge supply to the toner and chargeability to the photoreceptor. On the other hand, if it exceeds 10 ¹¹ Ω · cm, the electrical resistance is too high, so that charge-up occurs and control as an electrophotographic apparatus member tends to be difficult.

[Electric resistance]
The semiconductive composition (coating solution) used in the present invention is applied on a SUS304 plate to produce a conductive coating film having a thickness of 100 μm. Next, the electrical resistance when a voltage of 10 V is applied to the conductive coating film in an environment of 25 ° C. × 50% RH is measured.

Moreover, it is preferable that the semiconductive composition used in the present invention has an electrical resistance fluctuation digit number of 1 digit or less, which will be described later. That is, if the number of digits of electrical resistance variation due to the environment exceeds one digit, it tends to be difficult to control image quality as a member for an electrophotographic apparatus.

[Number of electrical resistance fluctuations due to environment]
Using the semiconductive composition used in the present invention , a conductive coating film is prepared in the same manner as described above. Next, with respect to this conductive coating film, 10 V was applied in an environment of 25 ° C. × 50% RH, and the electrical resistance before and after being left for 100 days in an environment of 50 ° C. × 95% RH was measured according to SRIS 2304. . Then, the number of digits of electrical resistance variation due to the environment is obtained by Log (Rv = 100 days / Rv = 0 day).

In the semiconductive composition used in the present invention , the size of the aggregate of the conductive polymer (component A) in the non-conjugated polymer (component B) is preferably 0.4 μm or less, particularly preferably 0. .3 μm or less. That is, when the size of the aggregate exceeds 0.4 μm, the compatibility between the two is poor, and white spots and uneven density tend to occur. The size of the aggregate can be measured using a laser diffraction particle size distribution meter, a crush gauge, an optical microscope, 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, the semi-conductive composition, with at least a portion of the structure layer of semi-conductive member for electrophotography apparatus, the voltage dependence of the electrical resistance of the structure layer formed by using the semi-conductive composition and Since the environmental dependency is reduced, the other component layers are less susceptible to the voltage dependency and environmental dependency of the electrical resistance. 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, the performance can be improved.

  Next, examples will be described together with comparative examples.

  First, prior to Examples and Comparative Examples, conductive polymers shown below were prepared.

[Conductive polymer 1]
1 mol of o-toluidine which is a monomer constituting a π-electron conjugated polymer, and an alkylbenzenesulfonic acid sodium salt represented by the following formula (1) which is a dopant (having two alkyl substituents, alkyl substituents The total number of carbon atoms of 22) 1 mol, 1N hydrochloric acid, toluene and methyl ethyl ketone (MEK) mixed solvent (mixing ratio: hydrochloric acid / toluene / MEK = 4/1/1) 1800 ml was placed in a flask, While controlling at 15 to 20 ° C., 1.2 mol of ammonium persulfate as an oxidizing agent was dropped over 1 hour and oxidative polymerization was performed for 10 hours to obtain a polymer. Subsequently, this polymer was washed with water, methanol and acetone, respectively, and purified to obtain a conductive polymer.

[Conductive polymer 2]
A conductive polymer was obtained in the same manner as the conductive polymer 1 except that 2-sec-butylaniline was used instead of 1 mol of o-toluidine.

[Conductive polymer 3]
1 mol of 2-propylaniline which is a monomer constituting a π-electron conjugated polymer and an alkylbenzenesulfonic acid sodium salt represented by the following formula (2) which is a dopant (having two alkyl substituents and alkyl substitution) The total number of carbon atoms in the group is 10) 1 mol, 1N hydrochloric acid, toluene and methyl ethyl ketone (MEK) mixed solvent (mixing ratio: hydrochloric acid / toluene / MEK = 4/1/1) 1800 ml are placed in a flask. While controlling at 10 to 15 ° C., 1.2 mol of ammonium persulfate as an oxidizing agent was dropped over 1 hour, and oxidative polymerization was performed for 10 hours to obtain a polymer. Subsequently, this polymer was washed with water, methanol and acetone, respectively, and purified to obtain a conductive polymer.

[Conductive polymer 4]
In place of the alkylbenzenesulfonic acid sodium salt represented by the above formula (2), the alkylbenzenesulfonic acid sodium salt represented by the following formula (3) (having three alkyl substituents, A conductive polymer was obtained in the same manner as the conductive polymer 3 except that the total was 37).

[Conductive polymer a]
1 mol of aniline as a monomer constituting a π-electron conjugated polymer, 1 mol of dodecylbenzenesulfonic acid as a dopant, and a mixed solvent of 1N hydrochloric acid, toluene and MEK (mixing ratio: hydrochloric acid / toluene / MEK = 4/1 / 1) 1800 ml was placed in a flask, and 1.2 mol of ammonium persulfate as an oxidizing agent was dropped over 1 hour while controlling at 5 to 10 ° C., and oxidative polymerization was performed for 10 hours. Next, toluene was directly added to the synthesis solution, and the mixed and stirred solution was centrifuged, and the solution-soluble phase from which the aqueous phase and conductive polymer aggregates were removed was designated as conductive polymer a.

[Conductive polymer b]
A conductive polymer was obtained in the same manner as the conductive polymer 1 except that 1 mol of dodecylbenzenesulfonic acid was used instead of 1 mol of the alkylbenzenesulfonic acid sodium salt represented by the above formula (1).

[Conductive polymer c]
1 mol of aniline was used instead of 1 mol of o-toluidine, and 1 mol of pentadecylbenzenesulfonic acid was used instead of 1 mol of sodium alkylbenzenesulfonate represented by the above formula (1). The polymer was washed with water and alcohol only. Other than that was carried out similarly to the conductive polymer 1, and obtained the conductive polymer.

  Each characteristic was evaluated as follows using each conductive polymer thus obtained. These results are shown in Tables 1 and 2 below.

[Amount of free dopant]
The amount of free dopant in each conductive polymer was measured according to the thermogravimetric analysis (TGA) described above. 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 free dopants was calculated | required from the heat loss at this time.

〔solubility〕
The solubility of the conductive polymer in THF, diethyl ether, m-cresol and NMP was measured. In addition, about the conductive polymer a, the solubility with respect to what volatilized and dried toluene was measured.

[Electric resistance]
(initial)
The conductive polymer was mixed with THF, subjected to ultrasonic treatment, and centrifuged (20000 rpm), and the supernatant was taken out. The supernatant was cast on a glass plate using an applicator and dried (150 ° C. × 30 minutes) to form a coating film (thickness 5 μm). The electrical resistance of this coating film was measured according to SRIS 2304 by applying a voltage of 1 V in an environment of 25 ° C. × 50% RH. In addition, about the conductive polymer a, casting was performed in the state of the toluene solution.

(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. Then, the number of fluctuation digits of the electric resistance was obtained.

(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. Then, the number of fluctuation digits of the electric resistance was obtained.

  Next, using the conductive polymer, a conductive composition was prepared as follows.

[ Reference Example 1]
After 85 parts of TPU (E980, manufactured by Nippon Milactolan), which is a non-conjugated polymer, was dissolved in 300 parts of THF, 150 parts of MEK, and 100 parts of toluene, 15 parts of conductive polymer 1 was added as a THF solution (5%). A conductive composition (coating liquid) was prepared by kneading using three rolls.

[ Reference Example 2]
Reference Example 1 except that 80 parts of polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd., LG6A) is used instead of 85 parts of TPU which is a non-conjugated polymer, and the blending amount of the conductive polymer 1 is changed to 20 parts. Similarly, a conductive composition (coating liquid) was produced.

[ Reference Example 3]
80 parts of non-conjugated polymer H-NBR (manufactured by ZEON Corporation, Zetpol 0020), 1 part of crosslinking agent (sulfur), and sulfenamide-based crosslinking accelerator (Ouchi Shinsei Chemical Industry Co., Ltd., Noxeller CZ) ) 2 parts and 2 parts of a dithiocarbamate-based crosslinking accelerator (Ouchi Shinsei Chemical Co., Ltd., Noxeller BZ) are kneaded using two rolls and dissolved in 300 parts of THF, 150 parts of MEK and 100 parts of toluene. Then, 20 parts of the conductive polymer 1 in THF solution (5%) was added to prepare a conductive composition (coating liquid).

[ Reference Example 4]
Reference Example, except that 80 parts of urethane silicone (X22-2756, manufactured by Shin-Etsu Chemical Co., Ltd.) is used instead of 85 parts of TPU which is a non-conjugated polymer, and the blending amount of the conductive polymer 1 is changed to 20 parts. In the same manner as in Example 1, a conductive composition (coating solution) was produced.

[ Reference Example 5]
Reference Example 1 except that 90 parts of an acrylic fluororesin (manufactured by Soken Chemical Co., Ltd., LFB4015) is used instead of 85 parts of TPU which is a non-conjugated polymer, and the blending amount of the conductive polymer 1 is changed to 10 parts. Similarly, a conductive composition (coating liquid) was produced.

Example 1
Instead of 85 parts of TPU which is a non-conjugated polymer, 80 parts of TPU (Nippon Polyurethane Industry Co., Ltd., NIPPOLAN 3312) having 0.05 mmol / g sulfonic acid Na group in the molecular structure is used, and conductive polymer 1 A conductive composition (coating solution) was prepared in the same manner as in Reference Example 1 except that the amount of was changed to 20 parts.

[Example 2 ]
(Production of sulfonated urethane silicone)
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) Then, a silicone polyol (Mw: 2000) and MDI were reacted to prepare sulfonated urethane silicone (sodium sulfonate group 0.01 mmol / g, silicone component 10%, Mw: 80,000).

(Preparation of conductive composition)
In the same manner as in Reference Example 1, except that 83 parts of the sulfonated urethane silicone is used instead of 85 parts of TPU which is a non-conjugated polymer, and the blending amount of the conductive polymer 1 is changed to 17 parts. A composition (coating solution) was prepared.

[Example 3 ]
(Preparation of 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: 4). Million).

(Preparation of conductive composition)
In the same manner as in Reference Example 1, except that 90 parts of the sulfonated acrylic fluororesin is used instead of 85 parts of TPU which is a non-conjugated polymer, and the blending amount of the conductive polymer 1 is changed to 10 parts. Composition (coating solution) was prepared.

[ Reference Example 6 ]
After dissolving 70 parts of TPU which is a non-conjugated polymer (manufactured by Nihon Milactolan, E980) in 300 parts of THF, 150 parts of MEK and 100 parts of toluene, 30 parts of conductive polymer 2 is added as a THF solution (5%). A conductive composition (coating liquid) was prepared by kneading using three rolls.

[ Reference Example 7 ]
75 parts of non-conjugated polymer TPU (manufactured by Nippon Milactolan, E980) is dissolved in 300 parts of THF, 150 parts of MEK and 100 parts of toluene, and then 25 parts of conductive polymer 3 is added as a THF solution (5%). A conductive composition (coating liquid) was prepared by kneading using three rolls.

[ Reference Example 8 ]
After dissolving 60 parts of TPU which is a non-conjugated polymer (manufactured by Nippon Milactolan, E980) in 300 parts of THF, 150 parts of MEK and 100 parts of toluene, 40 parts of conductive polymer 4 is added as a THF solution (5%). A conductive composition (coating liquid) was prepared by kneading using three rolls.

[Comparative Example 1]
After dissolving 70 parts of TPU which is a non-conjugated polymer (manufactured by Nippon Milactolan, E980) in 300 parts of THF, 150 parts of MEK and 100 parts of toluene, 30 parts of conductive polymer a is added as a THF solution (5%). A conductive composition (coating liquid) was prepared by kneading using three rolls.

[Comparative Example 2]
A conductive composition (coating liquid) was prepared in the same manner as in Comparative Example 1 except that 20 parts of the conductive polymer b was used instead of 30 parts of the conductive polymer a.

[Comparative Example 3]
A conductive composition (coating liquid) was produced in the same manner as in Comparative Example 1 except that 30 parts of the conductive polymer c was used instead of 30 parts of the conductive polymer a.

  Each characteristic was evaluated according to the following reference | standard using the electrically conductive composition obtained in this way. These results are shown in Tables 3 to 5 below.

[Electrical resistance, voltage dependence of electrical resistance]
Each conductive composition (coating solution) 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, an electric resistance (Rv = 10 V) when a voltage of 10 V is applied in an environment of 25 ° C. × 50% RH and an electric resistance (Rv = 100 V) when a voltage of 100 V is applied. ) Were 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 conductive composition (coating solution), 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 (15 ° C. × 10% RH) under the condition of an applied voltage of 10 V. ) Electrical resistance (Rv = 15 ° C. × 10% RH) and electrical resistance (Rv = 35 ° C. × 85% RH) at high temperature and high humidity (35 ° C. × 85% RH) according to SRIS 2304, respectively. It was measured. Then, the environmental dependency of the electrical resistance was displayed by the number of fluctuation digits by Log (Rv = 15 ° C. × 10% RH / Rv = 35 ° C. × 85% RH).

[Number of electrical resistance fluctuations due to environment]
Using each conductive composition (coating solution), a conductive coating film was prepared in the same manner as described above. The conductive coating film was subjected to electricity before and after being left for 100 days in an environment of 50 ° C. × 95% RH. Resistance was measured according to SRIS 2304 under the conditions of 25 ° C. × 50% RH and 10 V application, respectively. Then, the number of digits of electrical resistance fluctuation 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 conductive composition (coating solution), 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. Electrical resistance (Rv = 0 seconds) and 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 did. 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).

[Agglomerate size]
The size of the conductive polymer aggregate in the non-conjugated polymer was measured using a laser diffraction particle size distribution meter.

  From the above results, the products of the examples were excellent in both the voltage dependency of the electric resistance and the environment dependency of the electric resistance, and the electric resistance variation due to the environment was small. In addition, the increase in electrical resistance (charge up) in the high voltage region was very small. In addition, it replaced with the alkylbenzenesulfonic acid sodium salt which is the dopant of the said conductive polymer 1, and also about the Example using the alkylbenzenesulfonic acid ammonium salt and the alkylbenzenesulfonic acid pyridinium salt, the same outstanding effect as another Example was carried out. Obtained.

  In contrast, the product of Comparative Example 1 had a very large variation in electrical resistance due to the environment. The product of Comparative Example 2 had a large variation in electrical resistance due to the environment, and the product of Comparative Example 3 was inferior in voltage dependency of electrical resistance.

  Next, using the conductive composition, a charging roll was produced as follows.

[ Reference Example 9 ]
(Preparation of base layer material)
Silicone rubber (manufactured by Shin-Etsu Chemical Co., Ltd., KE1350AB) in which carbon black was dispersed was prepared.

(Preparation of surface layer material)
A conductive composition was produced in the same manner as in Reference Example 5.

(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 surface layer material is applied to the outer peripheral surface of the base layer, the base layer (thickness 3 mm) is formed on the outer peripheral surface of the shaft body, and the surface layer (thickness 50 μm) is formed on the outer peripheral surface. A charging roll having a two-layer structure was produced.

[Example 4 ]
(Preparation of intermediate layer material)
A conductive composition was prepared in the same manner as in Example 1 .

(Preparation of surface layer material)
After dissolving 93 parts of TPU which is a non-conjugated polymer (E980, manufactured by Nihon Miractran Co., Ltd.) in 300 parts of THF, 150 parts of MEK and 100 parts of toluene, 7 parts of carbon black (Denka Black, manufactured by Denki Kagaku) And dispersed to prepare a conductive composition (coating liquid).

(Preparation of charging roll)
A base layer (thickness 3 mm) is formed on the outer peripheral surface of the shaft body, and an intermediate layer (thickness 45 μm) is formed on the outer peripheral surface in the same manner as in Reference Example 9 except that the intermediate layer material and the surface layer material are used. Further, a charging roll having a three-layer structure in which a surface layer (thickness: 5 μm) was formed on the outer peripheral surface was prepared.

[ Reference Example 10 ]
(Preparation of intermediate layer material)
A conductive composition was produced in the same manner as in Reference Example 8 .

(Preparation of surface layer material)
A conductive composition was produced in the same manner as the surface layer material of Example 4 .

(Preparation of charging roll)
A base layer (thickness 3 mm) is formed on the outer peripheral surface of the shaft body, and an intermediate layer (thickness 35 μm) is formed on the outer peripheral surface in the same manner as in Reference Example 9 except that the intermediate layer material and the surface layer material are used. Further, a charging roll having a three-layer structure in which a surface layer (thickness: 15 μm) was formed on the outer peripheral surface was produced.

[Comparative Example 4]
(Preparation of base layer material)
Silicone rubber (manufactured by Shin-Etsu Chemical Co., Ltd., KE1350AB) in which carbon black was dispersed was prepared.

(Preparation of surface layer material)
A conductive composition was produced in the same manner as the surface layer material of Example 4 .

(Preparation of charging roll)
A charging roll having a two-layer structure in which a base layer (thickness 3 mm) is formed on the outer peripheral surface of a shaft body and a surface layer (thickness 50 μm) is formed on the outer peripheral surface using the base layer material and the surface layer material. Produced.

[Comparative Example 5]
(Preparation of intermediate layer material)
98 parts of non-conjugated polymer TPU (manufactured by Nippon Milactolan, E980) was dissolved in 300 parts of THF, 150 parts of MEK and 100 parts of toluene, and then tetrabutylammonium bromide (TBAB) [Lion Corporation] 2 parts was added and kneaded using three rolls to prepare a conductive composition (coating liquid).

(Preparation of surface layer material)
A conductive composition was produced in the same manner as the surface layer material of Example 4 .

(Preparation of charging roll)
A base layer (thickness 3 mm) is formed on the outer peripheral surface of the shaft body, and an intermediate layer (thickness 35 μm) is formed on the outer peripheral surface in the same manner as in Reference Example 9 except that the intermediate layer material and the surface layer material are used. Further, a charging roll having a three-layer structure in which a surface layer (thickness: 15 μm) was formed on the outer peripheral surface was produced.

  Using the charging rolls of Examples and Comparative 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 = 15 ° C. × 10% RH) at the low temperature and low humidity (15 ° 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 dependency of the electrical resistance was displayed by the number of fluctuation digits by Log (Rv = 15 ° 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. We evaluated the fluctuations. 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 sample was left for 100 days in an environment of 50 ° C. × 95% RH, and the electric resistance before and after was applied with 10 V in an environment of 25 ° C. × 50% RH, and measured according to SRIS 2304. Then, the number of digits of electrical resistance fluctuation due to the environment was determined by Log (Rv = 100 days / Rv = 0 day).

  From the above results, the product according to the example was superior in charging roll characteristics as compared with the product according to the comparative example.

  Next, using the conductive composition, a transfer roll was produced as follows.

[Example 5 ]
(Preparation of base layer material)
Silicone rubber (manufactured by Shin-Etsu Chemical Co., Ltd., KE1350AB) in which carbon black was dispersed was prepared.

(Preparation of surface layer material)
A conductive composition was prepared in the same manner as in Example 3 .

(Preparation of transfer roll)
A two-layer structure in which a base layer (thickness: 6 mm) is formed on the outer peripheral surface of the shaft body and a surface layer (thickness: 50 μm) is formed on the outer peripheral surface in accordance with Reference Example 9 except that the material for forming each of the above layers is used. A transfer roll having a structure was prepared.

[Comparative Example 6]
(Preparation of base layer material)
Silicone rubber (manufactured by Shin-Etsu Chemical Co., Ltd., KE1350AB) in which carbon black was dispersed was prepared.

(Preparation of surface layer material)
98 parts of TPU which is a non-conjugated polymer (manufactured by Nippon Milactolan, E980) is dissolved in 300 parts of THF, 150 parts of MEK and 100 parts of toluene, and then tetrabutylammonium bromide (TBAB) which is an ionic conductive agent [Lion Corporation 2 parts was added and kneaded using three rolls to prepare a conductive composition (coating liquid).

(Preparation of transfer roll)
A transfer roll having a two-layer structure in which a base layer (thickness 6 mm) is formed on the outer peripheral surface of the shaft body and a surface layer (thickness 50 μm) is formed on the outer peripheral surface using the base layer material and the surface layer material. Produced.

  Using the transfer rolls of Examples and Comparative Examples thus obtained, each characteristic was evaluated according to the evaluation criteria for the charging roll. These results are also shown in Table 7 below.

  From the above results, the example product was superior in the transfer roll characteristics as compared to the comparative example product.

  Next, using the conductive composition, a transfer belt was produced as follows.

[Example 6 ]
(Preparation of base layer material)
A base layer material was prepared by blending 15 parts of acetylene black (Denka Black HS100, manufactured by Denki Kagaku Kogyo Co., Ltd.) with 100 parts of amidoimide (Toyobo Co., Ltd., Bilomax HR16NN) and dispersing with a bead mill.

(Preparation of surface layer material)
A conductive composition was prepared in the same manner as in Example 3 .

(Preparation of transfer belt)
A transfer belt (endless belt) having a two-layer structure in which a surface layer (thickness: 50 μm) was formed on the outer peripheral surface of the base layer (thickness: 0.3 mm) was produced using the material for each layer.

[Comparative Example 7]
(Preparation of surface layer material)
A conductive composition was produced in the same manner as the surface layer material of Comparative Example 6.

(Preparation of transfer belt)
A transfer belt (endless belt) having a two-layer structure in which a surface layer (thickness 50 μm) is formed on the outer peripheral surface of a base layer (thickness 0.3 mm) in the same manner as in Example 6 except that the surface layer material is used. ) Was produced.

  Using the transfer belts of Examples and Comparative Examples thus obtained, each characteristic was evaluated according to the evaluation criteria of the charging roll. These results are also shown in Table 8 below. Note that the electrical resistance of the transfer belt is measured by measuring the electrical resistance between the portion contacting the SUS rod and the SUS plate in accordance with SRIS 2304 by placing a 10 mm diameter and 1 kg weight SUS rod inside the transfer belt. did.

  From the above results, the example product was superior in transfer belt characteristics as compared with the comparative example product.

  Next, using the conductive composition, a developing roll was produced as follows.

[Example 7 ]
(Preparation of base layer material)
Silicone rubber (manufactured by Shin-Etsu Chemical Co., Ltd., KE1350AB) in which carbon black was dispersed was prepared.

(Preparation of intermediate layer material)
A conductive composition was produced in the same manner as the surface layer material of Example 4 .

(Preparation of surface layer material)
A conductive composition was prepared in the same manner as in Example 2 .

(Preparation of developing roll)
A base layer (thickness of 4 mm) is formed on the outer peripheral surface of the shaft body, an intermediate layer (thickness of 5 μm) is formed on the outer peripheral surface, and the outer periphery thereof, in accordance with Reference Example 9 , except that the forming material for each of the above layers is used. A developing roll having a surface layer (thickness: 45 μm) formed on the surface was prepared.

[ Reference Example 11 ]
(Preparation of base layer material)
Silicone rubber (manufactured by Shin-Etsu Chemical Co., Ltd., KE1350AB) in which carbon black was dispersed was prepared.

(Preparation of intermediate layer material)
A conductive composition was produced in the same manner as the surface layer material of Example 4 .

(Preparation of surface layer material)
A conductive composition was prepared in the same manner as in Reference Example 7 .

(Preparation of developing roll)
A base layer (thickness of 4 mm) is formed on the outer peripheral surface of the shaft body, an intermediate layer (thickness of 5 μm) is formed on the outer peripheral surface, and the outer periphery thereof, in accordance with Reference Example 9 , except that the forming material for each of the above layers is used. A developing roll having a surface layer (thickness: 45 μm) formed on the surface was prepared.

[Comparative Example 8]
(Preparation of surface layer material)
A conductive composition was prepared in the same manner as in Comparative Example 1.

(Preparation of developing roll)
A base layer (thickness 4 mm) is formed on the outer peripheral surface of the shaft body, an intermediate layer (thickness 5 μm) is formed on the outer peripheral surface, and the outer periphery thereof is the same as in Example 7 except that the surface layer material is used. A developing roll having a surface layer (thickness: 45 μm) formed on the surface was prepared.

  Using the developing rolls of Examples and Comparative Examples thus obtained, each characteristic was evaluated according to the evaluation criteria for the charging roll. These results are also shown in Table 9 below.

  From the above results, the example product had a smaller number of digits of variation in electrical resistance due to the environment than the comparative example product.

Semi-conductive member for electronic photographic apparatus of the present invention can be suitably used in an electrophotographic apparatus member, such as a charging roller.

Claims (2)

A semiconductive member for an electrophotographic apparatus having the following (A) and (B) as essential components, and measured by thermogravimetric analysis when the weight of the above (A) is 100% (A) A semiconductive member for electrophotographic equipment, characterized in that the amount of free dopant therein is less than 30% by weight, and the electrical resistance of (A) is 100 Ω · cm or more.
(A) A solvent-soluble conductive polymer obtained by conducting a π-electron conjugated polymer with a dopant, and the monomer constituting the π-electron conjugated polymer is aniline, thiophene, pyrrole, o-toluidine, at least one selected from the group consisting of o-anisidine, 2-ethylaniline, 2-propylaniline, 2-sec-butylaniline and derivatives thereof, and the dopant has two or more alkyl substituents. And an alkylbenzene sulfonic acid having a total of 10 to 37 carbon atoms in the alkyl substituent or a salt thereof.
(B) A non-conjugated polymer having a structure of a sulfonic acid group or a salt thereof, which is at least one selected from the group consisting of acrylic resins, urethane resins, and thermoplastic elastomers . The semiconductive member for electrophotographic equipment according to claim 1, wherein the alkylbenzenesulfonic acid or a salt thereof has at least one alkyl substituent having 4 to 18 carbon atoms.