JPS5913122B2 - semiconductor elements - Google Patents

Description

[Detailed description of the invention] The present invention relates to electronic conductor compositions.

The utility of organic electronic conductor compositions is based on the following: (1) desirable electronic properties (e.g., low resistivity), (2) chemical stability, and (3) physical properties that enable the production of useful industrial products.
It is highly related to the combination of various properties such as chemical properties.

A number of inorganic materials well known in the art,
For example, metals (eg, silver, copper) or electronic conductors (eg, germanium, silicon) share the first two of the above properties. However, the greater chemical flexibility of organic molecules provides organic electronic conductors with advantages over inorganic materials. It is therefore possible to introduce or modify physical and chemical properties such as solubility, melting point, etc. by relatively small changes in the chemical structure of organic molecules. In other words, organic electronic conductors open up the possibility of customizing conductive materials with properties not found in inorganic materials. The production of organic materials that exhibit appreciable electrical conductivity has been reported in a few publications and journals [e.g.
．． OkamOtO and W. Brenner, “Organic Semiconductors”, Lehnhold Publishing, New York (1964)
:F-Gutamann and L. F. LyOn8 [Organic Semiconductor], John Willi and Sons, New York, (1967): and J. E. KatOn's "organic semiconductor polymer" is produced by Marcel Detska (Mi
rcelDekker, lnc. Enter New York (1
968)] was the subject of his paper.

These are broadly classified into the following four groups: 1) Non-complex organic electronic conductors consisting of one type of monomer. (The term "electronic conductor" as used herein refers to electrically conductive materials having a resistivity in the range of 10-3 to 109 ohm-m. These materials are often referred to as "semiconductors"
It is called. )2) Generally, at least two types of monomers (
A complex salt organic electronic conductor consisting of an electron donor portion and an electron acceptor portion, respectively. 3) Non-complex polymeric organic electronic conductors.

4) Complex salt organic electronic conductors in which at least one electron donor moiety or electron acceptor moiety is attached to a polymer chain or to a portion of a polymer chain.

Most of the known organic electronic conductors exhibit resistivity values lower than 104 ohms and belong to the second and fourth categories; Things are unstable under ambient conditions.

Therefore, the usefulness of these organic electronic conductors is rather small. Furthermore, these organic electronic conductors of reasonable stability are usually available in insoluble, unmeltable powder form, which is unsuitable for the fabrication of useful industrial products. . Recent publications [e.g. Y. Matunagaf) J
．． ChemPhy8.42, 2248 (1965) and Y. Ok5OtO,S. Shah and Y. Mats
unagaf) J. Chem. Phy8. ,43'19
03 (1965)] describes new organic electronic conductors with low resistivity.According to this document, the sulfur-containing polycyclic hydrocarbon (tetrathiotetracene) of these organic electronic conductors has three Organic acceptor: Coordination charge transfer complex (Dativ
e′″Type chargetransfercOmp
lexes) acts as an electron donor.

(Term “coordination type charge transfer complex (Dative-Type)
A charge transfer complex refers to a complex in which charge is transferred between an electron donor and an electron acceptor, and each component within the complex exists in an ionized form in the ground state of the complex. Such complexes are also referred to by the term "ion-radical salts", where the electron donor becomes the cation-radical and the acceptor becomes the anion-radical. ) However, the above complexes are not soluble in organic solvents or water. Similarly, tetrathiotetracene itself is reported to be one of the uncomplexed organic electronic conductors exhibiting low resistivity (resistivity of compacted powder is 104 Ω-
(of the order of m). However, it is only slightly soluble in a few very strong organic solvents at room temperature. None of the above-mentioned organic electronic conductors have sufficient solubility to readily make footwear, films, fibers, etc. using such materials. It is therefore an object of the present invention to provide a new class of electronic conductor compositions which have good electrical conductivity virtually independent of humidity.

This object is achieved by compositions comprising, in a binder, amine salts prepared by the interaction of certain organic amines with suitable inorganic or organic acids.

The starting material amine is (5) an organic amine compound (free amine) selected from the group consisting of the following members: (1) N-(p-anilinophenyl)-1,4-benzoquinone imine, (2) N-
[p-(4-anilino)anilinophenyl]-1,4-
Benzoquinoneimine, (3) N-(p-anilinophenyl)-N''-(p-aminophenyl)-1,4-benzoquinonediimine, (4) N-[p-(1,4-benzoquinonediimino)phenyl]- N'-phenyl 1,
4-benzoquinone diimine, (5) N-[p-(4-aminoanilino)phenyl] to N'-(p-aminophenyl)-1,4-benzoquinone diimine, (6) N-(p
-[4-(p-anilino)anilino]anilinophenyl}-N″-{p-[N-(p-aminophenyl)-1,
4-benzoquinone diimine]-phenyl}-1,4-benzoquinone diimine, (7) N-(p-dimethylamino)7enyl-1,4 benzoquinone diimine, (8)
N-[p-(1,4-benzoquinonediimino)7enyl]-1,4-benzoquinonediimine, (9) N,N'
-diphenyl-1,4-benzoquinone diimine, σIN
-[p-(4-aminoanilino)7enyl]-1,4-
Benzoquinoneimine, (auto)N-[p-(4-hydroxyanilino)phenyl]-1,4-benzoquinoneimine, ([2) N-{p-[4-(1,4-benzoquinoneimino)anilino] 7enyl}-1,4-benzoquinoneimine, 03)N-[p-(4-dimethylaminoanilide phenyl]-1,4-benzoquinoneimine, 04)N
-[P-(4-anilino)anilinophenyl]-N'-
Acetyl-1,4-benzoquinone diimine, 05) N
-{p-[4-(p-methoxyanilino)anilino]phenyl}-1,4-benzoquinoneimine, A6)N-(
P-anilinophenyl)-N′-[p-(4-aminoanilino)phenyl]-1,4-benzoquinone diimine,
and A7) N-(p-anilinophenyl)-N5-
[p-(1,4-benzoquinoneimino)7enyl]-1
, 4-benzoquinone diimine, (branch) emeraldine, i.e.,
,5-cyclohexadiene-1-ylideneamino)phenylimino]-2,5-cyclohexadiene-1-ylidene}-p-phenylenediamine, and ([9) N
-(p-anilinophenyl)-ma-p-aminophenyl-1,4-benzoquinone diimine 0 and (b) an acid selected from the group consisting of the following members: (1)
Malenic acid, (2) dichloroacetic acid, (3) trifluoroacetic acid, (4) phthalic acid, (5) hydrobromic acid, (6) sulfuric acid, (7) hydrochloric acid, (8) hydrofluoric acid, and (9) nitric acid.

For convenience, the compounds used in the compositions of the invention are referred to as amine salts.

However, the conduction mechanism is electronic. Charge carriers are therefore electrons and/or holes.

This is in contrast to pure ionic conduction as seen in ordinary salts, where the charge carrier is migrating and ionized. The compounds of the present invention also include Mat
It is different from ion radical salts such as sunaga.
This is because the compound of the present invention is a conductive salt, so it is a coordination type charge transfer complex (Dative-Type charge transfer complex).
It is believed that the presence of ion-radicals as part of the etransfer complex is not required. The amine salt of the present invention contains a neutral amine moiety,
Moreover, this amine moiety has only neutral acidic molecules. Another amine salt of the present invention is one that contains a positively charged amine moiety and has therewith a negatively charged acidic molecule. Since the conduction of the compounds of the present invention is electronic, the conduction is substantially independent of moisture and is observed even in high vacuum. Owing to their substantially moisture-independent character, the compounds of the invention are well suited for use under varying moisture conditions. - Generally, the compounds used in the compositions of the invention are formed by interaction of amines selected from the table above with acids selected from the table above.

The original amine compound is suitably oxidized to a leuco or higher oxidation state than the lowest oxidation state.

The oxidized amine is then dissolved in a solvent such as an ether (e.g., tetrahydroethyl ether, isopropyl ether, etc.), a ketone (e.g., acetone, etc.), an alcohol (e.g., methanol, ethanol, n-probanol, isopropanol, etc.), - interaction with acidic compounds in aromatic solvents (eg benzene, toluene, etc.) or water or mixtures of these or other solvents; If the resulting amine salt is substantially soluble in the solvent or mixed solvent used, separation of the solid is carried out at a concentration that exceeds the solubility limit of the amine salt in the selected solvent or mixed solvent. The precipitate is then passed through the mouth and washed. This method is used, for example, by A. G. Gree
J.N. et al. Chcm. SOc,. 97,2392 (19
10), R. Chem. Willstatter et al. B
er. , 4O, 2677 (1907). The electronic conductor composition is prepared by adding a binder to a solution of the electronic conductor, and then applying the mixture onto a suitable substrate, impregnating it into a substrate, or forming a self-supporting layer. It can be made by

Evaporation of the solution yields a coating in which the conductive material is dispersed in a polymeric binder. It is also possible to re-create the former by coating a soluble derivative of an insoluble electronic conductor material and heating or chemically treating this coating. Layers containing an amine component and an acidic component may be applied in succession to create a conductive coating of an amine salt electronic conductor.X. ) In this case, the conductive material is formed near the boundary. This result is similarly achieved if one component of the salt is applied and then exposed to the vapors of another component. The polymeric acidic material may be coated from a solvent with or without a polymeric binder, followed by further coating with a soluble derivative of the amine-like moiety. In this case, a salt of a conductive polymer is obtained. Binders used in making electronic conductor compositions are generally film-forming materials.

This type of substance is both natural and synthetic. Typical examples of this substance are: 1. Natural resin, however,
Gelatin, cellulose ester derivatives such as carboxylates, alkyl esters of cellulose, hydroxy
Ethyl cellulose, carboxy methyl cellulose,
Contains carboxy methyl hydroxy ethyl cellulose, etc.

．． Vinyl resins: However, the following also contain 0 TlOa) polyvinyl esters, such as vinyl acetate resins, copolymers of vinyl acetate and crotonic acid, vinyl acetate, vinyl alcohol and higher aliphatic carboxylic acids (e.g. lauric acid or stearic acid). copolymers with esters of, poly(vinylhaloarylates) (e.g. poly(vinyl-m-bromobenzoate)), terpolymers of vinyl butyral, vinyl alcohol and vinyl acetate, vinyl formal, terpolymers of vinyl alcohol and vinyl acetate, etc. :b) Polymers of vinyl chloride and vinylidene chloride, such as poly(vinyl chloride), copolymers of vinyl chloride and vinyl isobutyl ether, copolymers of vinylidene chloride and acrylonitrile, vinyl chloride,
Terpolymers of vinyl acetate and vinyl alcohol, poly(vinylidene chloride), vinyl chloride, terpolymers of vinyl acetate and maleic anhydride, copolymers of vinyl chloride and vinyl acetate, etc.: c) Styrene polymers, e.g. polystyrene, nitrated polystyrene, styrene d) Polymers of methacrylic esters, e.g. methacrylate) etc.: e) Polyolea J
C, such as chlorinated polyethylene, chlorinated polypropylene, etc.: f) poly(vinyl acetal),
For example, poly(vinyl butyral), etc.: and g) poly(vinyl alcohol): . Polycondensates containing a) polyesters of 1,3-disulfobenzene and 2,2-bis(4-human-komaxyphenyl)propane; b) diphenyl-P,p'-disulfonic acid and 2, 2-bis (4
- polyester of hydroxyphenyl)propane; c)
4,4'-dicarpoxyphenyl ether and 2,2-
Polyester of bis(4-hydroxyphenyl)propane d) Polyester of 2,2-bis(4-hydroxyphenyl)propane and fumaric acid e) Pentaerythritol
Phthalates: f) resin-like terpene polybasic acids; g) polyesters of phosphoric acid and hydroquinone; h) polyphosphites; 1) polyesters of inopentyl glycol and isophthalic acid; j) polycarbonates, including polythiocarbonates, e.g. 2,2-bis(4-hydroxyphenyl)proban polycarbonate k) isophthalic acid, 2,
Polyester of 2-bis-4-(β-hydroxyethoxy)7enylpropane and ethylene glycol 1) Polyester of terephthalic acid, 2,2-bis-4-(β-hydroxyethoxy)7enylethylene glycol m) Ethylene glycol Polyesters of neopentyl glycol, terephthalic acid and isojalic acid; n) polyamides; 0) ketone resins; and p) phenol formaldehyde resins; Silicone resin: and. Alkyd resins, including styrene-alkyd resins, silicone-alkyd resins, and Sawyer alkyd shugetsumai.

Solvents for preparing the composition of the present invention include various solvents.

For example, various alcohols such as aliphatic alcohols with 1 to 8 carbon atoms such as methanol, ethanol, propanol, and isopropanol, aromatic alcohols, polyhydric alcohols, substituted alcohols (including 2-methoxyethanol), and aliphatic ketones. (e.g. acetone, 2-butanone, or methyl isobutyl ketone), aromatic ketones (
(including cyclohexanone), chlorinated solvents such as aliphatic chlorinated solvents (e.g. methylene chloride, ethylene chloride, or propylene chloride), organic carboxylic acids having 1 to 10 carbon atoms (e.g. formic acid, acetic acid, or propionic acid), substituted carboxylic acids such as esters derived from organic carboxylic acids having 1 to 10 carbon atoms (e.g. methyl acetate or ethyl acetate), lower dialkyl sulfoxides (e.g. dimethyl sulfoxide), dimethylformamide, Acetonitrile and water. It may also be a mixture of the above solvents or a mixture with another organic solvent. In preparing the composition, the electronic conductor is present in at least about 1 part of the composition.
Useful results are obtained when present in equal weight percentages.

The upper limit for the amount of electronic conductor present is 99% by weight of the amount of coating. The preferred weight range of the electronic conductor is 10% to 60% by weight. The thickness of the coating of the electronic conductor composition on the support can vary widely.

Typically, useful thicknesses are about 0.001 inch (0.0025
4 mm) to approximately 0.01 inch (0.254 m). The thickness of the coating before drying ranges from about 0.0002 inch (0.00508 inch) to about 0.0008 inch (0.005 inch).
．． 02032wt). However, useful results can be obtained outside this range. Suitable media for applying the electronic conductor composition are any of a wide variety of supports, such as fiber, film, glass, paper, or metal. Due to its chemical and physical properties, the organic electronic conductor of the present invention can be easily added to a thin film having a surface resistivity of less than 10 11 Ω/hole. Surface resistivity is measured under ambient room temperature.
Its unit Ω/mouth is 0bm/Sq. (Om Pai Square). As is well known to those skilled in the art, surface resistivity is defined as 2 for a given length.
This value is determined by placing book electrodes in parallel on the surface to be measured, separated by a distance equal to the length of the electrodes, and measuring the resistance between these electrodes along the surface to be measured. As the length of the electrodes increases, the resistance between the two electrodes is supposed to decrease, but since the distance between the electrodes increases accordingly, the resistance increases to offset this. Therefore, a surface resistance value that is not affected by the length of the electrode can be obtained. Therefore, the surface resistivity, expressed in ohms, squares, is a measure of the resistance measured under the special conditions that the electrode length and electrode spacing are the same and therefore cancel each other out. It can be said that it is a value. This resistivity is virtually independent of relative humidity and remains within this range even in vacuum. As a result of the aforementioned good electrical properties, such films are useful in the manufacture of numerous industrial products.
For example, one is an inert film support (which may have a subbing layer to improve adhesion);
Used in antistatic photographic film elements comprising a conductive layer comprising one of the organic electronic conductors of the present invention and a silver halide emulsion layer sensitive to electromagnetic radiation. These layers are provided with a conductive layer and an emulsion layer on both sides of the support. It is also possible to have both layers on the same side and one layer on top of the other. In some cases, it is preferred to provide an insulating polymer layer that can be added to the element, either below, above, or between any of the layers described above. Another example is use in antistatic magnetic tape.

This tape consists of the same arrangement of layers as the photographic film element described above, except that the appropriate layer of magnetic material is replaced with a photographic emulsion. Further examples include an inert insulating film support (which may have a subbing layer to improve adhesion), an electrically conductive layer containing one of the organic electronic conductors of the invention; and in direct electrorecording film elements consisting of silver halide emulsion layers sensitive to electron beams. In this case, on one side of the support, both layers are
One layer is placed on top of the other. Also, as in the previous element, thin layers of insulating polymers may be provided above, below, and in between the conductive and photoconductive layers. Another example is the use in the manufacture of optically transparent conductive elements.

In such elements, a conductive layer containing an organic electronic conductor of the invention is applied to an insulating inert support. The thickness of the conductive layer is such that the optical density in the 400 to 800 nm spectral range is not greater than about 0.5. Such elements are used in the production of antistatic windows for electronic instruments, antistatic lenses for cameras and other optical devices, transparent heating panels, photographic products, etc. It is also possible to incorporate the organic electronic conductor of the present invention in a supportless non-conductive film together with a polymeric binder. The organic electronic conductor of the present invention can be incorporated into static free textile articles.

Fibers containing this organic electronic conductor can be added to the textile article as a single component or mixed with non-conductive fibers. Such fibers may also consist of an electrically conductive core containing an organic electronic conductor with or without a polymeric binder surrounded by a polymeric coating free of electronic conductors. Good too. In electronic components, this organic electronic conductor is coated on an insulating support and shaped in any manner to form passive electronic components such as resistors or capacitors.
electrOnicOmpOnents).

In addition, this organic electronic conductor can be used as an active element such as a rectifier or a transistor.
ts). The shaped conductor can contain the organic electronic conductor of the present invention together with a polymeric binder. Next, reference examples and examples of the present invention will be shown.

Reference Example 1 The above-mentioned free amine 3 was converted into A. G. It was prepared by the method of Green et al. (supra).

A solution of 0.5f of this amine in 250m ether was added to a stirred solution of 1.2t maleic acid in 100m ether. A blue-green precipitate formed, which was separated by filtration, washed with 50 d of ether and dried at room temperature. The volume resistivity of this material, measured as a compacted powder, was 140 Ω-m. Elemental analysis showed that the product was essentially the maleate salt of the free amine. Reference Example 2 A solution containing 200me of ether and 0.3f of the free amine of Reference Example 1 was prepared.

This solution was added to ether 50me with 2.51 g of dichloroacetic acid.
! 11 was added to the solution. A blue-green precipitate was formed, which was separated by filtration and diluted with ether 80d.
3ml of dichloroacetic acid! and dried at room temperature. The volume resistivity of this amine dichloroacetate as a compressed powder was 8500 Ω-m. Reference example
3 A solution containing 0.05f of the free amine of Reference Example 1 and 50d of ether was prepared.

Add this solution to ether 5017! 1 to a solution containing an excess of trifluoroacetic acid (X.'o as long as the acid-amine ratio is substantially greater than about 3.1). An orange-green precipitate formed. This was separated by filtration, then washed with ether 70d and dried at room temperature. The volume resistivity of the trifluoroacetate of this amine measured as a compressed powder was 7800Ω.
one? It was hot. Reference Example 4 A solution containing 0.05f of the free amine of Reference Example 1 and 50d of ether was prepared.

This solution was added to a second volume containing 0.03f of phthalic acid and 50d of ether. A dark green precipitate was formed. This was separated by filtration, then washed with 70me ether and dried at room temperature. The volume resistivity of this amine phthalate salt measured as a compressed powder was 3.5×10 4 Ω-m. Example 1 A solution containing 0.05 t of the maleic acid amine salt of Reference Example 1, 10 d of a 2% methanol solution of poly(vinyl acetate), and 40 d of methanol was stirred for 5 minutes.

This solution was passed through the mouth, applied to a polyethylene terephthalate film support, and dried at room temperature. The surface resistivity of this coated product was measured by using a graphite electrode coated on the surface of this film and measuring the resistivity with an electrometer. The term surface or "thin film" resistivity refers to the electrical resistance of a square thin film of material, measured in the plane of the material between the two sides. For films that follow Ohm's law, this is an inherent property of the film. If the resistivity is measured in ohms, the resistivity or surface resistivity of the thin film is expressed as Ω/mouth. (R.E. Aitchi
sOn. Aust. J-Appl.Sci. ,5,lO
(1954)). The resistivity of the coated material is 4.1×107
Ω/It was hot with my mouth. And this value is a high degree of vacuum (1×10
There was no substantial change even when the temperature was set at a weir at a pressure of -5wnHf or less. Example 2 The dihydropromide salt of amine 4 described above was prepared using the method of Willstatter et al. (cited above, p. 2682).

However, hydrobromic acid was used instead of hydrochloric acid, and acetone was used instead of the mixture of ethanol and chloroform. A solution containing 0.05 f1 of this salt and 2 (F6 methanol solution and 257 nt of methanol) of poly(vinyl acetate) as a binder was stirred for 5 minutes. This solution was passed through the mouth and applied to a polyethylene terephthalate film support. This coating was dried at room temperature and cured at 100°C for 3 minutes, and the surface resistivity of this coating was measured and found to be 2.2 x 10 8 Ω/mouth.Example 3 Hydrobromic acid and Amine salt 0.08f1 poly(vinyl acetate) 2 made by reaction with the free amine 3 mentioned above.
A solution containing 5 d of methanol solution and 15 d of methanol was prepared by stirring for 5 minutes.

The filter solution was applied to a poly(ethylene terelyte) film support and dried at room temperature. The surface resistivity of this coating was found to be 6.3×10 9 Ω/mouth. Example 4 A solution containing 0.057 amine salt produced by the reaction of sulfuric acid with the free amine 2 described above, a 2% methanol solution of poly(vinyl acetate) and 30 rnt of methanol was prepared by stirring for 5 minutes and then evaporated through the mouth. did.

This mouthwash was applied to a poly(ethylene terephthalate) film support, dried at room temperature, and cured at 120° C. for 3 minutes. The surface resistivity of this coated product was measured as in Example 5 and was found to be 2.4 x 10<7>Ω/mouth. Example 5 A solution was prepared by stirring 0.05 fl of an amine salt produced by the reaction of hydrochloric acid with the above-mentioned free amine 5 and 9.5 fl of methanol for 10 minutes.

Then, 0.5 i of a solution of poly(vinyl acetate) in 296 acetone was added with stirring, and then passed through the mouth. This filtration solution was applied to a poly(ethylene terephthalate) film support and dried at room temperature. The surface resistivity of this coating was 4.3×10 7 Ω/mouth. The resistivity measured in a high vacuum after being exposed to a high vacuum overnight is 1.
．． It was 1 x 107Ω/mouth. Example 6 Emeraldine was produced and purified, and R. It was isolated as the hydrochloride salt using the method generally described by Willstatter (supra).

Emeraldine hydrochloride 0.05f to 20f! 11 in methanol and stirred for 10 minutes, then alcohol-soluble cellulose acetate butyrate polymer [47
．． 2% butyl, 1.6% acetyl, 4.5% hydroxyl, each containing 6.5% n-propanol29
A coating solution was prepared by adding 1.0111 t of 1.11 methanol solution as a binder. 1 Emeraldine, Chemical Abstracts, Vol. 69, p. 502G (1968
(July-December 2016 Index Guide).

The chemical name of emeraldine is N-{p-[p-(p-aminoanilino)anilino]phenyl}-N″-{4-[p-
(4-phenylimino-2,5-cyclohexadiene-1-ylideneamino)phenylimino]-2,5-cyclohexadiene-1-ylidene}-p-phenylenediamine, and its structural formula is as follows. The above solution was passed through the mouth, a small amount of which was applied onto a polyester film support, and dried at room temperature.

When this coated product was measured in the same manner as in the previous example, it had a surface resistivity of 8.3×10 8 Ω/hole. After overnight exposure in high vacuum, the resistivity of this coating was L9XlO9Ω/mouth. Example 7 A coating consisting of an amine salt produced by the reaction of hydrobromic acid with the free amine 5 described above and a binder [the binder is poly(pinylacetate)] was supported on the same poly(ethylene terephthalate) film as in Example 5. It was made by applying it on the body.

When the surface resistivity was measured in the same manner as in Example 1, it was found to be 1.5×10 7 Ω/mouth at room temperature. When measured in a high vacuum, the surface resistance was 1.7×10 7 Ω/hole. The surface of the coating layer of the strip coated with the coating layer of amine salt was coated with Kl. Apply graphite on two opposing sides of the square with a 9cm x 1.9cm square part in between to create two parallel graphite electrodes, and pass through these graphite electrodes to remove the graphite left in the square. A DC voltage of 47 volts was applied to the uncoated portion of the amine salt coating layer.

Direct current was applied continuously for 7 days while maintaining a high vacuum (pressure <1 x 10''5 trmHf). At the end of this time the resistivity of the coating was 2.0 x 10 7 Ω/port.
Due to the geometry and physical properties of this coating, the total amount of charge (1.53 coulombs) passed through this coating is equal to the total charge carried by all ions under one electrode. It was calculated to be 320 times larger than the amount. Therefore, due to electrophoresis and/or holes, and not due to iontophoresis, this conductivity is at least 99.7 If
It is clear that it is 6. This behavior of typical coatings containing organic electronic conductors of the type described in this invention is such that conduction (if any) occurs through the movement of ions in the presence of absorbed moisture. This is in marked contrast to that of conventional amine salts or quaternary ammonium salts.

) In such cases, conductivity decreases substantially as the moisture content decreases (by reducing the relative humidity in the air).

Also, at low relative humidity or in a high vacuum, such materials do not have effective electrical conductivity and are classified as insulators. Example 5 The following compounds were prepared by the method previously described, and their volume resistivities were measured in the same manner as in Reference Example 1.

The results are shown below. Example 8 A solution containing 0.5f of the above-mentioned amine 3 in 50d of acetone was added to a mixed solvent containing 30d of acetone and 20d of methanol, and 0.5f of a 1:1 copolymer of ethylene and maleic acid was added to a mixed solvent containing 30d of acetone and 20d of methanol.
5t was added to the dissolved binder solution while stirring.

Add 300 d of ethyl ether to the resulting dark green solution.
was added to precipitate the amine salt of the polymer.

The solid salt was removed from the solution by filtration and dried in vacuo. The volume resistivity of this material measured as a compressed powder was 2 x 106 Ω-d. EXAMPLE 9 The reaction mixture of Example 9 in which a polymeric electronically conductive amine salt was dissolved was coated onto a poly(ethylene tererate) film support without separation of the solid electronic conductor.

This coating was then dried. When this coated product was measured by the method of Example 1, it had a surface resistivity of 1.8×10 10 Ω/hole. After overnight exposure in a high vacuum, this coating was measured in a high vacuum to give a rating of 1.9X1.
It had a resistivity of 0.010 Ω/mouth. Example 10 Mixture of 2-methoxyethanol and ethanol 10
N-(p-[4-anilino]anilinophenyl) at 0i
-1,4-benzoquinone imine hydrobromide 0.22
A solution of f and poly(vinyl formal) 0.16f in propylene chloride, 1,1,2-trichloroethane [22% propylene chloride, 13% 1
, 1,2-trichloroethane, 10% 2-methoxyethanol, and 55 (!I ethanol (each % by volume)
A mixture of the following was used as a solvent for dissolving poly(vinyl formal)] was applied to a subbed polyester film support by conventional coating methods.

The solution was evaporated, leaving a thin conductive layer on the support. A 2.5 percent solution of a terpolymer of methyl acrylate, vinylidene chloride, and itaconic acid (34 parts by weight of methyl acrylate, 64 parts by weight of vinylidene chloride, 2 parts by weight of itaconic acid) in methyl isobutyl ketone was then applied to this conductive layer, and This solution was evaporated.
The surface electrical resistance of this element made in this way is approximately 2
It was hot at ×108Ω/mouth. A silver halide gelatin emulsion sensitive to radiation was coated on top of the previous coat and dried to create a static-free photographic element. It is sometimes advantageous to use a separate, thin, underlayer between the terpolymer layer and the radiation-sensitive layer as this improves the adhesion of both layers. In order to investigate the usefulness of this static-free photographic element, the sensitometric properties were compared with those of a control element without a conductive layer.

As a result, it was found that the presence of a conductive layer prevents harmful sensitometric effects from entering. Normal handling of the control element resulted in electrostatic marks on the control element. However, the photographic element with the conductive layer was free of static marks. Example 11 A photographic element was made and investigated in a manner similar to that of Example 11.

However, one side of the primed film support was coated with a conductive layer and a layer of terpolymer, and the opposite side of the primed film support was coated with a layer of radiation-sensitive silver halide gelatin. As is well known in the art, subbing layers are often desirable to improve emulsion adhesion;
A polymer of methyl acrylate, vinylidene chloride and itaconic acid may be used followed by a thin layer of gelatin.

When I investigated the photographic elements created using this method, I found the following.

That is, the presence of a conductive backing layer did not change the sensitometric properties of the layer sensitive to radiation and also served as an antistatic agent. Example 12 To 100 d of a mixture of methanol and 2-methoxyethanol [a mixture of 96 vol.% methanol and 4 vol.% 2-methoxyethanol], N-(p-[4-aniline]anilino-1)-1 , 0.75 f hydrobromide of 4-benzoquinone imine and a copolymer of methyl methacrylate and methacrylic acid [54.4% methyl acrylate and 45.6 (f) methacrylic acid (each wt%
)] A solution containing 0.62 t was applied to a primed polyester J C column support by conventional coating methods.

Claims (1)

[Claims] 1 (a) An organic amine compound selected from the group consisting of the following members: (1) N-(p-anilinophenyl)-1
, 4-benzoquinone imine, (2) N-[p-(4-anilino)anilinophenyl]-1,4-benzoquinone imine, (3) N-(p-anilinophenyl)-N'-(
p-aminophenyl)-1,4-benzoquinone diimine, (4)N-[p-(1,4-benzoquinone diimino)
Phenyl]-N'-phenyl-1,4-benzoquinone diimine, (5) N-[p-(4-aminoanilino)phenyl]-N'-(p-aminophenyl)-1,4-benzoquinone diimine, (6) N-{p-[4-(p-aniline)anilino]anilinophenyl}-N'-{p-[
N-(p-aminophenyl)-1,4-benzoquinonediimino]-phenyl}-1,4-benzoquinonediimine, (7) N-(p-dimethylamino)phenyl-1,4
-benzoquinone diimine, (8)N-[p-(1,4-
benzoquinonediimino)phenyl]-1,4-benzoquinonediimine, (9) N,N'-diphenyl-1,4-
Benzoquinonedidiimine, (10) N-[p-(4-aminoanilino)phenyl]-1,4-benzoquinoneimine, (11) N-[p-(4-hydroxyanilino)phenyl]-1,4-benzoquinone imine, (12)N-
{p-[4-(1,4-benzoquinoneimino)anilino]phenyl}-1,4-benzoquinoneimine, (13)
N-[p-(4-dimethylaminoanilino)phenyl]
-1,4-benzoquinoneimine, (14)N-[p-(
4-anilino)anilinophenyl]-N'-acetyl-
1,4-benzoquinone diimine, (15) N-{p-[
4-(p-methoxyanilino)anilino]phenyl}-
1,4-benzoquinoneimine, (16)N-(p-anilinophenyl)-N'-[p-(4-aminoanilino)
phenyl]-1,4-benzoquinone diimine, (17)
N-(p-anilinophenyl)-N'-[p-(1,4
-benzoquinoneimino)phenyl]-1,4-benzoquinonediimine, and (18) emeraldine, i.e., N-{p-[p-(p-aminoanilino)anilino]phenyl}-N'-{4-[p-( 4-Phenylimino-
2,5-cyclohexadien-1-ylideneamino)phenylimino]-2,5-cyclohexadien-1-ylidene}-p-phenylenediamine, and (b) an acid selected from the group consisting of the following members: (1 )
Malenic acid, (2) dichloroacetic acid, (3) trifluoroacetic acid, (4) phthalic acid, (5) hydrobromic acid, (6) sulfuric acid, (7) hydrochloric acid, (8) hydrofluoric acid, and (9) nitric acid; and an electronic conductor composition comprising a binder.