JPH0388887A - Electrical resistance film - Google Patents

Abstract

PURPOSE:To obtain an electrical resistance film, composed of an organic polymer having quinone diimine structure units and phenylenediamine structural units as principal recurring units and specific physical properties with resistivity always within a prescribed range without depending on ambient environmental conditions. CONSTITUTION:The objective electrical resistance film composed of an organic polymer which is a polymer, having quinone diimine structural units expressed by the formula (m and n are as follows; 0<m<1; 0<n<1; m+n=1) and phenylenediamine structural units as principal recurring units and soluble in organic solvent in a dedoped state with >=0.40dl/g intrinsic viscosity [eta] measured in N-methylpyrrolidone at 30 deg.C and >=1.0 ratio (Ia/Ib) of the intensity (Ia) for Raman lines of skeletal stretching vibration appearing at a higher wave number than 1600cm<-1> to the aforementioned intensity (Ib) appearing at a lower wave number than 1600cm-1 in skeletal vibration of a p-substituted benzene in a laser.Raman spectrum obtained by excitation at 457.9nm wavelength.

Description

[Detailed Description of the Invention] The present invention relates to an electrically resistive film, and more specifically, it has a volume resistivity that stably ranges from lOs to 10 Ω・marks regardless of the surrounding environmental conditions. Regarding electrical resistance films.

For example, the developing resistance roller for an electronic copying machine has the role of uniformly charging its surface and transporting toner by uniformly adhering the toner to the surface. Usually, its volume resistivity is , 10'-10'' spanning from the semiconductor region to the dielectric region
It is said that it is desirable that it be in the range of Ω·cm.

Such resistance rollers are usually formed by providing a conductive polymer layer on the circumferential surface of a metal shaft. Dispersion is used. However, in such a resistance roller, the resistance value is an apparent resistance value due to the contact resistance of the conductive filler, and it is difficult to obtain uniform contact between the conductive fillers. It is not easy to stably obtain resistance values within this range, and the resistance values vary widely.

The amount that B should be An object of the present invention is to provide an electrically resistive film having a volume resistivity of .

The electrically resistive film according to the present invention for i ° Own<1, m+n=1) A polymer having a quinonediimine structural unit and a phenylenediamine structural unit as main repeating units, which are soluble in an organic solvent in a dedoped state, and N-methyl The intrinsic viscosity [η] measured at 30°C in pyrrolidone is 0.40 dl/g or more, and
Among the skeletal vibrations of rose-substituted benzene in the laser Raman spectrum obtained by excitation with light with a wavelength of 457.9 nm, the Raman line intensities 1a and 1600 cm- of skeletal stretching vibrations that occur at higher wave numbers than 1600 cs+-'
It is characterized by being made of an organic polymer in which the ratio I a / I b of the Raman line intensity 1b of the skeleton stretching vibration occurring at a wave number lower than ' is 1.0 or more.

A polymer having a quinonediimine structural unit and a phenylenediamine structural unit represented by the above general formula as main repeating units used in the present invention, which is soluble in an organic solvent in a dedoped state, and has a predetermined intrinsic viscosity and laser/Raman spectrum. Polyaniline having the above characteristics (hereinafter referred to as dedoped polyaniline) is prepared by adding aniline to aniline in a solvent in the presence of a protonic acid having an acid dissociation constant pKa value of 3.0 or less at a temperature of 5°C or less, preferably 0. While maintaining the temperature below °C, an aqueous solution of an oxidizing agent having a standard electrode potential of 0.6 V or more, which is defined as the electromotive force in a reduction half-cell reaction based on a standard hydrogen electrode, is added to the oxidizing agent per mole of aniline. 2 equivalents or more, preferably 2 to 2.5 equivalents, defined as the amount obtained by dividing 1 mole of Oxidized polymer of aniline doped with polyaniline (hereinafter referred to as doped polyaniline)
and then dedoping this doped polyaniline with a basic substance.

First, the production of the above doped polyaniline by oxidation of aniline in the presence of a protic acid will be described.

As the oxidizing agent, manganese dioxide, ammonium peroxodisulfate, hydrogen peroxide, ferric salt, iodate, etc. are particularly preferably used. Among these, for example, ammonium peroxodisulfate and hydrogen peroxide each involve two electrons per molecule in their oxidation reaction, so they usually contain 1 to 1.25 moles per mole of aniline. A range of quantities is used.

The protonic acid used in the oxidative polymerization of aniline is
There are no particular limitations as long as the acid dissociation constant pKa value is 3.0 or less, and examples include hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, fluoroboric acid, phosphohydrofluoric acid, hydrofluoric acid, Si acids such as hydroiodic acid, benzenesulfonic acid,
Aromatic sulfonic acids such as pt-toluenesulfonic acid, alkanesulfonic acids such as methanesulfonic acid and ethanesulfonic acid, phenols such as picric acid, aromatic carboxylic acids such as m-nitrobenzoic acid, dichloroacetic acid, Examples include aliphatic carboxylic acids such as malonic acid. Polymeric acids can also be used. Examples of such polymer acids include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallylsulfonic acid, polyvinyl sulfuric acid, and the like.

The amount of protic acid used depends on the reaction mode of the oxidizing agent used. For example, in the case of manganese dioxide, the oxidation reaction is expressed as MnO,+4H''+2e-4Mn''+2HtO, so it is necessary to use a protic acid that can supply at least four times the molar amount of protons as the manganese dioxide used. Also, in the case of hydrogen peroxide, the oxidation reaction is expressed as HtOt+2H"+2e-→2HzO, so it is necessary to use a protic acid that can supply at least twice the molar amount of protons as the hydrogen peroxide used. On the other hand, For ammonium belloxonisulfate,
The oxidation reaction is expressed as 5zOs"-+2e-→2SO,"-, so there is no need to use a protic acid. However, even when ammonium beroxonisulfate is used as the oxidizing agent, the Preference is given to using molar amounts of protic acids.

As a solvent for oxidative polymerization of aniline, aniline,
A substance that dissolves the protonic acid and the oxidizing agent and is not oxidized by the oxidizing agent is used.

Water is most preferably used, but if necessary, alcohols such as methanol and ethanol, nitriles such as acetonitrile, N-methyl-2-pyrrolidone,
Polar solvents such as dimethyl sulfoxide, ethers such as tetrahydrofuran, and organic acids such as acetic acid can also be used. Moreover, a mixed solvent of these organic solvents and water can also be used.

During the above oxidative polymerization reaction of aniline, in particular, while adding the oxidizing agent solution to the aniline solution, the temperature of the reaction mixture was always kept at 5.
It is important to keep the temperature below ℃. Therefore, the oxidizing agent solution is added gradually to the aniline until the temperature of the reaction mixture reaches 5.
It is necessary to ensure that the temperature does not exceed °C. When adding an oxidizing agent rapidly, external cooling may raise the temperature of the reaction mixture and produce a low molecular weight polymer, or even after dedoping as described below, a solvent-insoluble oxidized polymer may be produced. do.

In particular, it is preferable to maintain the reaction temperature at 0°C or lower, so that after dedoping, the intrinsic viscosity (hereinafter the same) measured in N-methyl-2-pyrrolidone at 30°C [
η] of 1.0 dl/g or more, a high molecular weight, solvent-soluble polyaniline can be obtained.

The protonic acid-doped polyaniline obtained in this way is generally compatible with most organic Not soluble in solvents.

However, polyaniline doped with such a protic acid becomes soluble in organic solvents by dedoping. Since such dedoping of doped polyaniline is a kind of neutralization reaction, the basic substance that can be used for dedoping is particularly limited as long as it is a basic substance that can neutralize the protonic acid as a dopant. Preferably, aqueous ammonia, sodium hydroxide,
Metal hydroxides such as potassium hydroxide, lithium hydroxide, magnesium hydroxide, and calcium hydroxide are used. Dedoping may be carried out by directly adding a basic substance to the reaction mixture after the above-mentioned oxidative polymerization of aniline, or by once isolating the polymer and then allowing a basic substance to act on it.

Doped polyaniline obtained by oxidative polymerization of aniline usually has a conductivity of 10-''S/cn+ or higher and has a black edge color, but after dedoping, it has a purple or purplish copper color. This discoloration is due to the conversion of the amine nitrogen in the salt structure in the polymer to a free amine.The electrical conductivity is usually on the order of 10-''S/C111. Therefore,
The volume resistivity is on the order of 10 9 Ω·cm. However, as described below, by adjusting the ratio of the quinonediimine structural unit and phenylenediamine structural unit in the polymer,
The value of volume resistivity can be varied.

The dedoped polyaniline thus obtained has a high molecular weight and is soluble in various organic solvents. Examples of such organic solvents include N-methyl-2-pyrrolidone, N,N-dimethylacedeamide, N,N-dimethylformamide, dimethyl sulfoxide, 1,3-dimethyl-2-silidinone, and sulfolane. I can do it. The solubility varies from 0.5 to 100% of the polymer, depending on the average molecular weight of dedoped polyaniline and the solvent.
can be dissolved to obtain a 1-30% by weight solution.

In particular, dedoped polyaniline is N-methyl-2
- High solubility in pyrrolidone, typically 20% of the polymer
~100% dissolves and 3-30ft 1% solution can be obtained. However, it does not dissolve in tetrahydrofuran, 80% aqueous acetic acid, 60% aqueous formic acid, acetonitrile, etc.

According to the present invention, the resistive film according to the present invention can be obtained by dissolving the solvent-soluble dedoped polyaniline in an organic solvent, coating it on a suitable base material, and drying and volatilizing the solvent. Therefore, by forming a thin film of dedoped polyaniline on a metal shaft with a smooth surface, a resistance roller having a volume resistivity of 105 to 1Q13 Ω·0 can be obtained.

Particularly, when the drying condition of the solvent is set to 130° C. or higher, the obtained thin film has excellent flexibility and is very strong, and does not crack even when bent.

Moreover, the thin film obtained in this way is N-methyl-2
- Does not dissolve in pyrrolidone and furthermore does not dissolve in concentrated sulfuric acid.

Such undoped polyaniline used in the present invention is determined by elemental analysis, infrared absorption Svec)/L/, ES
From the R spectrum, laser/Raman spectrum, thermogravimetric analysis, solubility in solvents, and visible to near-infrared absorption spectra, it was determined that (0<m<1, Own<1, m+n=1.) It is a polymer having a quinonediimine structural unit and a phenylenediamine structural unit as main repeating units.

The polyaniline constituting the thin film made insolubilized in the solvent by drying the solvent at a temperature of 130°C or higher also exhibits essentially the same infrared absorption spectrum as the solvent-soluble polyaniline, and also shows elemental analysis, infrared absorption spectrum, and ESR spectrum. , laser Raman spectra, thermogravimetric analysis,
Based on its solubility in solvents, visible to near-infrared absorption spectra, etc., it appears to be composed of substantially the same repeating units, although it has a crosslinked structure. However, the volume resistivity is approximately one digit higher when formed into a film.

In the solvent-soluble polymer represented by the above general formula, m
The values of and n can be prepared by oxidizing or reducing the polymer. That is, by reducing
m can be decreased and n can be increased. Conversely, oxidation can increase m and decrease n. When the quinone diimine structural units in the polymer are reduced by reduction of the polymer, the solubility of the polymer in a solvent is increased. Furthermore, the viscosity of the solution decreases compared to before reduction.

Furthermore, the volume resistivity decreases to 105Ω.

For the reduction of such solvent-soluble polymers, hydrazines such as hydrazine hydrate and phenylhydrazine, metal hydrides such as lithium aluminum hydride and lithium borohydride, hydrogen, and the like are preferably used. Phenylhydrazine is most preferably used because it is soluble in organic solvents, particularly N-methyl-2-pyrrolidone, but does not reduce N-methyl-2-pyrrolidone. On the other hand, the oxidizing agent used for oxidizing the solvent-soluble polymer may be any oxidizing agent as long as it can oxidize the phenylenediamine structural unit in the general formula. An oxidizing agent having a standard electrode potential defined as electric power of 0.3 V or more is particularly preferably used. For example, silver oxide, which is a mild oxidizing agent, is preferably used. Oxygen blowing is also useful. As a strong oxidizing agent, for example, potassium permanganate or potassium dichromate can be used, but when using them, it is necessary to take care not to cause deterioration of the polymer.

By such oxidation treatment, m in the above general formula can be increased, and the volume resistivity increases to 1013Ω·0. By oxidizing or reducing the solvent-soluble polymer thus obtained, it is possible to adjust its volume resistivity.

Here, the characteristics of dedoped polyaniline obtained from laser Raman spectra will be explained in comparison with conventionally known so-called polyaniline.

Generally, there is vibrational spectroscopy as a means of obtaining information regarding vibrations between atoms constituting a substance, and this includes infrared spectroscopy and Raman spectroscopy. Infrared spectroscopy is active on vibrational modes that result in a change in dipole moment, and Raman spectroscopy is active on vibrational modes that result in a change in polarizability. Therefore,
The two have a complementary relationship; generally, vibrational modes that are strong in infrared spectroscopy are weak in Raman spectroscopy.
On the other hand, vibrational modes that appear strongly in Raman spectroscopy are weak in infrared spectroscopy.

Infrared absorption spectra are obtained by detecting energy absorption between vibrational levels, and Raman spectra are
Scattered light (Raman scattering) that occurs when molecules fall to a higher vibrational level of the ground state after being excited by light irradiation.
obtained by detecting. At this time, the vibrational energy level can be determined from the energy difference between the scattered light and the irradiated light.

Usually, a Raman spectrum is obtained by visible light excitation from an argon laser or the like. It is known that when a sample has an absorption band in the visible region, a very strong Raman line can be obtained when the wavelength of the irradiated laser beam and the absorption band are matched.

This phenomenon is called the resonance Raman effect, and according to this, a Raman line that is 104 to 105 times more intense than a normal Raman line can be obtained. According to such a resonance Raman effect, information about the chemical structure portion excited by the wavelength of the irradiated laser light can be obtained in a more emphasized manner. Therefore, by measuring the Raman spectrum while changing the wavelength of the irradiated laser light, the chemical structure of the sample can be analyzed more accurately. Such features are features of Raman spectroscopy that are not found in infrared spectroscopy.

Figure 1 shows N-methyl-2, which is soluble in organic solvents.
- Intrinsic viscosity [η] measured at 30°C in pyrrolidone is 1
．． A laser beam obtained by irradiating a disk-shaped sample of dedoped polyaniline powder used in the present invention with an excitation wavelength of 2 dl/g with an excitation wavelength of 457.9 nm.
This is a Raman spectrum.

Attribution of Raman lines is as follows. 1622 and 1
591 cm-' is the skeletal stretching vibration of para-substituted benzene,
1489 and 1479 cm-' are C=C and C=N stretching vibrations of the quinone diimine structure, and 1220 cm-' is C
- Mixture of N stretching vibration and c-c stretching vibration, 1185 and 1
165CO1-' is the in-plane bending vibration of C-H.

Figure 2 is from Y. Furukawa et-al.
5ynth, Net,.

16, 189 (1986), obtained by irradiating polyaniline in a dedoped state with an excitation wavelength of 457.9 nm. This polyaniline was obtained by electrolytic oxidative polymerization of aniline on a platinum electrode.

As shown in Figure 1, in the solvent-soluble dedoped polyaniline used in the present invention, among the skeletal vibrations of rose-substituted benzene, the Raman line intensity of the skeletal stretching vibration that occurs at a wave number higher than 1600 cts-' 1a and 1600
Raman line intensity 1b that occurs at a lower wave number than cn+-'
The ratio I a / I b is 1.0 or more. On the other hand, all conventionally known polyanilines including the polyaniline shown in FIG. 2, including those produced by chemical oxidative polymerization, have the ratio 1a/Ib smaller than 1.0.

The Raman lines at 1622 and 1591 cm-' are both based on skeletal stretching vibrations of para-substituted benzene. Polyaniline in a reduced state does not have a quinone diimine structure and therefore produces a Raman line only at 1621 cm-', but undoped polyaniline, which has a quinone diimine structure, produces Raman lines at 1622 and 159 cm-', as described above.
A Raman line is detected at 1 cm-'. These Raman lines exhibit excitation wavelength dependence as shown in FIG.

As the excitation wavelength is changed from 488.0 nm to 476.5 nm to 457.9 nm,
Ia/Ib changes. That is, 488.0 n
When m, Ia/Ib is smaller than 1.0, but 457
At ゜9 nm, it is 1.0 or more, 488.0
Compared to the case of nm, the I a / I b intensity is reversed. This reversal phenomenon may be explained as follows.

Figure 4 shows the electronic spectrum of dedoped polyaniline.* The peak at 647 nm disappears when polyaniline is reduced, so it appears to be derived from the quinone diimine structure, and the peak at 334 nm, on the other hand, is due to reduction of polyaniline. This increases the strength by
It seems to originate from the π-π0 transition of para-substituted benzene. FIG. 4 shows the Raman excitation wavelengths described above. Here, for the para-substituted benzene skeleton stretching vibration band, the excitation wavelength is set to 488. When changing the wavelength from Onm to 457.9 nm, the resonance condition of the resonance Raman effect of the 1622 cm-' band becomes more favorable than that of the 1591 cm-' band, and the relative intensity as described above becomes more favorable. It is thought that changes will occur.

Next, in the spectra shown in Figures 1 and 2, 15
The fact that the relative intensities of the Raman lines 91c1' and 1622 cm-' are different despite having the same excitation wavelength (457,9 nm) may be explained as follows:
N as a model compound of phenylenediamine structure,
N'-diphenyl-p-phenylenediamine is 1611
Only cta-' has a Raman line, and N,N'-diphenyl-p-benzoquinone ξine, which is a model compound with a quinone diimine structure, has Raman lines at 1568 cm-' and 1621c.
Since it has a Raman line at m-', as shown in (a) below, the para-substituted benzene ring that is non-conjugated with the quinone diimine structure has a 1 622c whose intensity increases upon excitation with short wavelength light.
As shown in (b) below, the para-substituted benzene ring conjugated with the quinone diimine structure is estimated to have Raman lines of 1591 cm-' and 1622 cm-'.

■N,N'-diphenyl--phenylenediaminequinonediimine structure (a) (b) 1622cm-591cm 1622cm-' From the results of elemental analysis, the number of quinonediimines and phenylene diimine in dedoped polyaniline Since the number of amines appears to be approximately equal, the structural chain of such undoped polyaniline is an alternating combination of quinone diimine structures and phenylene diamine structures, as shown in (C), from the connection mode of quinone diimine structures and phenylene diamine structures. They are classified into two types: polymer chains and block copolymer chains with a quinone diimine structure and a phenylene structure as shown in (a). In the figure, the para-substituted benzene ring indicated by an arrow indicates a benzene ring non-conjugated with quinone diimine, and in the above alternating copolymer chain, for example,
2 per octameric chain unit, and in block copolymer chains, e.g. 3 per octameric chain unit.
It is one. When the chain unit is long, the difference in the number of quinone diimine and non-conjugated benzene rings in both becomes even larger. This difference is 1591cm-' and 1622cm
This can be said to be caused by the difference in the relative intensity of the Raman line -'.

In dedoped polyaniline, the I a / I b ratio in the laser Raman spectrum is 1.0.
From the above, it seems that the quinone diimine structure and a large amount of non-conjugated benzene rings are contained, and thus it has the above-mentioned block copolymer-like chain.

The organic solvent solubility of dedoped polyaniline is rationally explained by having such block copolymer-like chains. Generally, the imine nitrogen (-N-) in the quinone diimine structure is replaced by the nearby secondary amine nitrogen (-
Although it is known to form hydrogen bonds with (NH-),
Macromolecules, 21.1297 (
198B)), the hydrogen bonds between the secondary amino group nitrogens are not strong.

Therefore, when polyaniline has the above-mentioned alternating copolymer chains, it forms a strong network of hydrogen bonds as shown in (f). The reason why conventionally known polyaniline is insoluble in many organic solvents even in an undoped state is thought to be due to the formation of such a strong network of hydrogen bonds.

On the other hand, when the polymer chain is a block copolymer chain as in the solvent-soluble dedoped polyaniline used in the present invention, the block chains usually have different lengths, so that As seen in (e), even if the phenylenediamine structural part and the quinonediimine structural part are adjacent to each other, many hydrogen bonds cannot be formed, and the solvent enters between the polymer chains. It forms hydrogen bonds and dissolves in organic solvents. If all parts of a block chain had exactly the same length, it would form a network of hydrogen bonds as described above, but the probability of having such a structure is extremely small, so it is usually ignored. obtain.

/ \ Furthermore, such interchain interactions can also be explained from the C-H in-plane bending vibration of the laser Raman spectrum.

The C- of polyaniline in the dedoped state shown in FIG.
The Raman line at 1 162 cm-', which is attributed to H in-plane bending vibration, becomes 1181 cm-' when polyaniline is reduced and all imine nitrogens are converted to secondary amino nitrogens.
Shift to a higher wavenumber.

As mentioned above, dedoped polyaniline is C-
As a Raman line attributed to H-plane bending vibration, 1165
and 1185cm+-'.

This Raman line of 1185cs+-' is not observed in conventionally known undoped polyaniline, and is attributed to C-)1 in-plane bending vibration in the reduced state.1181ci+-' It shows a value close to .

From these points, it is thought that the solvent-soluble dedoped polyaniline used in the present invention has a block copolymer-like chain and has an atmosphere of a reduced structure. From this, the dedoped polyaniline used in the present invention is likely to have high solubility in organic solvents despite its high molecular weight. It is a new polymer with a different structural chain from polyaniline.

The electrically resistive film according to the present invention is made of the new undoped polyaniline as described above, and since the electrical conductivity of this polyaniline is based on electron conduction, it is not affected by moisture and is not affected by environmental conditions. It has a stable resistance value. Moreover, since its volume resistivity is in the range of 10 5 to 1Q13 Ω·cm spanning the semiconductor region and the insulator region, it can be suitably used as a resistive film for a resistive roller for a copying machine, for example. Furthermore, the thin film of dedoped polyaniline according to the invention is
It also has excellent chemical resistance and mechanical strength.

EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples in any way.

Reference Example 1 (Production of doped conductive organic polymer by oxidative polymerization of aniline) 6000 g of distilled water, 360 ml of 36% hydrochloric acid, and 400 g of aniline ( 4,295 moles)
were added in this order to dissolve the aniline. Separately,
1493g of distilled water in a beaker while cooling with ice water
434 g (4,295 mol) of 97% concentrated sulfuric acid was added and mixed to prepare a sulfuric acid aqueous solution. This sulfuric acid aqueous solution was added to the above-mentioned rubber rub flask, and the entire flask was cooled to -4°C in a low temperature constant temperature bath.

Next, add 2293 gls of distilled water in a beaker.
980 g (4,295 mol) of Lt ammonium oxonisulfate was added and dissolved to prepare an oxidizing agent aqueous solution.

The entire flask was cooled in a low-temperature thermostat, and while the temperature of the reaction mixture was maintained at -3°C or lower, the above aqueous solution of ammonium beroxon disulfate was added to the acidic aqueous solution of aniline salt from a straight tube adapter using a tubing pump while stirring. 1
It was gradually added dropwise at a rate of ml/min or less. Initially, the colorless and transparent solution turned from greenish-blue to a black-rimmed color as the polymerization progressed, and then a black-rimmed powder was precipitated.

An increase in temperature is observed in the reaction mixture during this powder precipitation, but in this case as well, in order to obtain a high molecular weight polymer according to the present invention, the temperature in the reaction system must be kept below 0°C, preferably below -3°C. It is important to keep it to a minimum. After the powder is precipitated, the dropping rate of the aqueous solution of beroxonisulfate may be slightly faster, for example, about 8 ml/min. but,
In this case as well, it is necessary to monitor the temperature of the reaction mixture and adjust the rate of addition so as to maintain the temperature below -3°C. Thus, after completing the dropwise addition of the aqueous solution of ammonium beroxonisulfate, which took 7 hours,
Stirring was continued for an additional hour at a temperature below -3°C.

The obtained polymer powder was filtered, washed with water and acetone,
It was vacuum dried at room temperature to obtain 430 g of a black-rimmed polymer powder. This was pressure-molded into a disk with a diameter of 13++s and a thickness of 700 μm, and its electrical conductivity was measured by the van der Boe method and found to be 14S/cm.

(Dedoping of conductive organic polymer with ammonia) 350 g of the doped conductive organic polymer powder was added to 2N ammonia water 42, and stirred for 5 hours at 500 rpm using an autohomogen mixer. The mixture changed from a black border color to a blue-purple color.

The powder was filtered out using a Buchner funnel, washed repeatedly with distilled water while stirring in a beaker until the filtrate became colorless, and then washed with acetone until the filtrate became neutral. Thereafter, the powder was vacuum dried at room temperature for 10 hours to obtain 280 g of a dark brown undoped polymer powder.

This polymer is soluble in N-methyl-2-pyrrolidone, and the solubility is 8 g (7.4%) per 100 g of the same solvent.
)Met. Further, the intrinsic viscosity [η] measured at 30° C. using this as a solvent was 1.23.

This polymer had a solubility of less than 1% in dimethyl sulfoxide and dimethyl formamide.

Tetrahydrofuran, pyridine, 80% acetic acid aqueous solution, 6
It was not substantially dissolved in 0% formic acid aqueous solution and acetonitrile.

FIG. 1 shows a laser Raman spectrum obtained by irradiating a disk-shaped bottom sample of this dedoped polyaniline powder with an excitation wavelength of 457.degree. 9 nm.

For comparison, Y. Furukawa et al.
5ynth, Met,, 16.189 (198
Regarding the undoped polyaniline shown in 6),
This polyaniline, whose laser Raman spectrum obtained by irradiation with an excitation wavelength of 457.9 nm is shown in FIG. 2, was obtained by electrolytic oxidative polymerization of aniline on a platinum electrode.

In addition, by changing the wavelength of the laser excitation light,
FIG. 3 shows the results of measuring the ramance vector in the range of 1700c+a-'. Set the excitation wavelength to 488.0
As the wavelength changes from nm to 457°9 nm through 476.5 nm, Ia/Ib changes,
At 457.9 nm, it is 1.0 or more, and 488
．． It is shown that the Ia/Ib intensity is reversed compared to when it was 0 nm.

Further, FIG. 4 shows the electronic spectrum.

Next, regarding the organic solvent soluble polyaniline, N-
Using a GPC column for methyl-2-pyrrolidone, G
PC measurement was performed. Three types of columns for N-methyl-2-pyrrolidone were used in combination. Further, as an eluent, a solution of lithium bromide in N-methyl-2-pyrrolidone with a concentration of 0.01 mol/l was used. FIG. 5 shows the results of GPC measurement.

From this result, the organic solvent-soluble polyaniline has a number average molecular weight of 23,000 and a weight average molecular weight of 160,000.
(All values are based on polystyrene standards).

Similarly, by varying the reaction conditions, organic solvent-soluble polyanilines having different intrinsic viscosities [η] measured in N-methyl-2-pyrrolidone at 30°C were obtained. Table 1 shows the intrinsic viscosity [η], number average molecular weight, and weight average molecular weight determined by GPC for these.

Table 1 Reference Example 2 (Preparation of self-supporting film using dedoped polyaniline) 75 g of the dedoped polyaniline obtained in Reference Example 1 was
It was added little by little to 95 g of -methyl-2-pyrrolidone and dissolved at room temperature to obtain a black-blue solution. Add this solution to 03
When vacuum filtration was performed using a glass filter, extremely small amounts of insoluble matter remained on the filter. After washing this filter with acetone and drying the remaining insoluble matter,
When the weight was measured, it was 75 cm. Therefore, 98.5% of the polymer was dissolved, and the insoluble matter was 1.5%.

The polymer solution thus obtained was cast on a glass plate and squeezed with a glass plate, and then N-methyl-2-pyrrolidone was evaporated and diffused in a hot air circulating dryer.

After this, by immersing the glass plate in cold water, the polymer film will peel off naturally from the glass plate, thus
A polymer film with a thickness of 40 Ijm was obtained.

After washing this film with acetone, it was air-dried at room temperature to obtain a film with copper-colored metallic luster.

Films differ in strength and solubility depending on their drying temperature. When the drying temperature is below 100°C, the resulting film dissolves in a small amount in N-methyl-2-pyrrolidone and has relatively low strength; however, the film obtained by heating at a temperature of 130°C or above has It is very tough and does not dissolve in N-methyl-2-pyrrolidone or other organic solvents. It also does not dissolve in concentrated sulfuric acid. Thus, it appears that when heated at high temperatures, the polymer molecules crosslink with each other in the process and become insoluble.

The volume resistivity of the undoped polyaniline films thus obtained was 10''Ω·0.

Furthermore, the film did not crack even after being bent 10,000 times, and its tensile strength was 850 kg/cd.

Reference Example 3 (Preparation of solvent-soluble and solvent-insoluble films made of dedoped polyaniline, chemical structure of dedoped polyaniline) Powder of dedoped polyaniline obtained in Reference Example 1 and powder of dedoped polyaniline obtained in Reference Example 2 The FT-IR spectra of the solvent-insoluble film obtained by the KBrBr method are shown in Figures 6 and 7, respectively.
As shown in the figure. In the spectrum of the insoluble polymer film obtained in Reference Example 2, some absorption at 1660 cm-' due to residual N-methyl-2-pyrrolidone is observed;
Since the two spectra are almost the same, it can be seen that although the polymer becomes insolubilized in the solvent by crosslinking when the dedoped polyaniline is heated and dried in the solvent after casting, there is no major change in the chemical structure.

The results of thermogravimetric analysis of the solvent-soluble dedoped polyaniline powder and the solvent-insoluble film are shown in FIG. 8, and both have high heat resistance. Considering the insolubility in concentrated sulfuric acid, the polymer molecules in the solvent-insoluble film are shown to be cross-linked since the solvent-insoluble film does not decompose up to higher temperatures.

In addition, the ESR spectrum is shown in Figure 9. The spin concentration is 1.2 x 10" spins/g for the soluble polymer, and as the heating temperature increases, the spin concentration increases, indicating that radicals are generated by heating. This radical coupling appears to cause the polymer to crosslink, making the heated film insoluble.

Next, the results of elemental analysis of solvent-soluble dedoped polyaniline and solvent-insolubilized polyaniline are shown below.

No-buttarebo! Anin C,77,19; H,4,76i N, 14.86
(Total: 96.81) Polyanine film C, 78,34; H, 4,99; N, 15.16
(Total 98.49) Based on this elemental analysis, C
I2. The m weight of solvent soluble dedoped polyaniline normalized to OO is cog. . Ha,. N1.91
The compositional formula of solvent-insolubilized polyaniline is CI
2. . . H9, □N1.99. On the other hand, similarly, C
I 2. The quinone diamine structural unit and the phenylenediamine structural unit normalized to OO are as follows.

Therefore, both the solvent-soluble dedoped polyaniline and the solvent-insolubilized polyaniline contain mainly repeating quinone diamine structural units and phenylene diamine structural units, as described above. It is a polymer having as a unit.

Example 1 The dedoped polyaniline obtained in Reference Example 1 was dissolved in N-methyl-2-pyrrolidone to prepare a 10% by weight solution, which was applied onto a metal roller and heated at 150°C for 2 hours. and a thickness of 2 consisting of dedoped polyaniline.
A 0 μm resistive film was formed to obtain a resistive roller.

The volume resistivity of the resistance film in these resistance rollers is 7.
The resistance value in the thickness direction (electrode area 1 cIi) was 1.5×10 5 Ω.

Even after this resistance roller was left in a humidity of 80% for 100 hours, and even after it was left in a constant temperature oven at 100° C. for 100 hours, no change was observed in the resistance value in the thickness direction.

Similarly, resistance rollers having resistance films of various thicknesses were manufactured, and the relationship between the film thickness, the resistance value in the thickness direction (electrode area 1ed), and the electrical conductivity was investigated. The results are shown in FIGS. 10 and 11, respectively. According to the present invention, it is shown that the variation in resistance value is small.

[Brief explanation of drawings]

Figure 1 shows the laser Raman spectrum of the organic solvent-soluble aniline oxidized polymer in a dedoped state according to the present invention when excited with light at a wavelength of 457.9 nm, and Figure 2 shows the conventionally known 457.9n of polyaniline
Figure 3 shows the laser Raman spectrum when the same aniline oxidized polymer as in Figure 1 is excited with light of a wavelength of m. , an organic solvent soluble aniline oxidized polymer in a dedoped state according to the present invention, N-methyl-2
-Electronic spectrum of pyrrolidone solution. FIG. 5 shows the GP of solvent-soluble polyaniline according to the present invention.
FIG. 6 is a graph showing the molecular weight distribution according to C.
FT-IR spectrum obtained by the r-tablet method; FIG. 7 shows the FT-IR spectrum obtained by the KBr tablet method of a solvent-insoluble film obtained by casting the above-mentioned solvent-soluble polymer; FIG. and thermogravimetric analysis of the insoluble polymer film. FIG. 9 is a diagram showing changes in the ESR spectrum when the above-mentioned soluble polymer is heated. Figure 1O is a graph showing the relationship between the thickness of the resistive film and the resistance value in the thickness direction (polarity area ICTII) of the resistive film according to the present invention, and Figure 11 is a graph showing the relationship between the thickness of the resistive film and the electrical conductivity. This is a graph showing.

Claims (3)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. < n < 1, m + n = 1) A polymer having a quinone diimine structural unit and a phenylene diamine structural unit as main repeating units, which are soluble in an organic solvent in a dedoped state, and N- The intrinsic viscosity [η] measured at 30°C in methylpyrrolidone is 0.40 dl/g or more, and
Among the skeletal vibrations of para-substituted benzene in the laser Raman spectrum obtained by excitation with light with a wavelength of 457.9 nm, the intensity Ia of the Raman line of the skeletal stretching vibration that appears at a higher wave number than 1600 cm^-^1 and 1600 cm
An electrically resistive film comprising an organic polymer having a Raman line intensity Ib ratio of skeletal stretching vibration appearing at a wave number lower than ^-^1, Ia/Ib, of 1.0 or more. (2) A resistance roller comprising the electrically resistive film according to claim 1. (3) The volume resistivity of the electrically resistive film is 10^5 to 10^1^
3. The resistance roller according to claim 2, wherein the resistance roller is in the range of 3 Ω·cm.