DE2262743C3 - Organic semiconductor material - Google Patents

Description

a, m, ii, ρ, χ and y are whole numbers within the framework of the following combinations:

u = 0, m = 1, je = I, y = 0 ρ = 0 η = 0.

p = l π = 0, ρ = 2 π = 0,

ρ = 1 η = 0,

ρ = 2 η = 0,

ρ = 3 π = 0

α = 1, m = 0, χ = 0, y = \ ρ = 0 π = 0,

ρ = 1 π = 0,

ρ = 2 η = 0,

, 2. 3, 4,, 2,3

2, 3, 4, 5,

, 2,3,4, 2

, 2, 3, 4,, 2,3

Ri and R «each represent a hydrogen or halogen atom, a hydroxy radical, an alkyl or alkoxy radical each having 1 to 8 carbon atoms, an optionally substituted amino radical, an optionally substituted aryl radical, a Acyl, carboxylate, thio, nitrate, sulfonate or cyano radical, where Ri and R4 are the same or different;

R2 and Ri each (I) an oxo, optionally

alkyl-substituted (with 1 to 8 carbon atoms) or aryl-substituted or acyl-substituted imino or thioxo radical or (2) an alkoxonium, optionally alkyl or dialkyl substituted (with t to 8 Carbon atoms) iminium or sulfonium radical; A is a monomeric or polymeric acid molecule or the metal salt of an acid, when R2 and Ri are neutral radicals, or a monomeric or polymeric acid anion if R2 and / or Ri are charged Leftovers are and

q is a whole or fractional number from> 0 to 9,

as semiconductor material.

2. Use according to claim 1, characterized

marked that

a = 0, m = I, χ = |, v = Op = 0 »ι = 0, 1, 2, 3 - I, m = 0. χ - \, y --- {) ρ = 0 11 = 0 , I, 2

ρ = I / 1 = 0, I

«= 1,1» = 0, χ = 0, ν = I ρ = 0 η = 0, I, 2

P-IB = O

i. Use of the amine salts of hydrobromic acid, nitric acid or p-toluenesulfonic acid and N-fp ^ -anilinoJ-anilinophenylJ-l ^ -benzoquinoneimine according to claim 1.

4. Use of the amine salts from sulfuric acid, hydrobromic acid or fluoroboric acid and N- {p- [4- (p-Methoxyanilino) anilino] -phenyl (-1,4-benzoquinone imine according to claim I.

5. Use of the amine salts from perchloric acid, fluoroboric acid or hydrogen bromide and N- {p- [4-

(p-Hydroxyanilino) anilino] -phenyl} -l, 4-benzoquinoneimine according to claim I.

6. Use of the amine salts from hydrobromic acid c. Nitric acid or p-toluenesulfonic acid and N- (p-anilinophenyl) -N '- (p-aminophenyl) -1,4-benzoquinonediimine according to claim 1.

7. Use of the amine salt of polyacrylic acid and N- (p-anilinophenyl) -N '- (p-aminophenyl) -1,4-benzoquinone according to claim 1.

8. Use of the amine salt of polyethylene maleic acid and N- (p-anilinophenyl) -N '- (p-aminophenyl) -l, 4-benzoquinone according to claim 1.

9. Use of the amine salts according to Claims 1 to 8 in the form of layers.

As is known, the usability of semiconducting organic compounds as semiconductor materials depends largely on the combination of their properties, such as e.g. B. (I) their electronic properties (e.g. a low electrical resistivity), (2) their chemical stability and (3) their physical and chemical properties. The first two properties mentioned have a large number of known inorganic substances, e.g. B. the metals, such as silver and copper and the semiconductors, such as germanium with silicon. The extraordinarily great chemical versatility of organic molecules, however, gives organic semiconductors a clear advantage over inorganic substances, since it is possible with them through

proportionality minor changes in their chemical structure, certain physical and to change chemical properties, e.g. B. the solubility or the melting point Organic compounds open up the possibility of tailor-made To produce semiconductor materials with properties that are not found in inorganic substances.

The usability of organic compounds as semiconductor materials is known from, for example the books by Y. Okamoto and W. Brenner, "Organic Semiconductors", Reinhold Publishing Corp, New York (1964); F. Gutmann and L F. Lyons, "Organic Semiconductors", John Wiley and Sons, Inc, New York (1967) and J. E. K a to η, "Organic Semiconducting Polymers", Marcel Dekker, Inc New York (1968). They can be divided into four broad groups, namely:

1. Non-complex organic semiconductors, which consist of individual monomers (the term "semiconductors" refers to electrically conductive substances with a specific resistance of 10 " ³ to 10 ^s ohm · cm); 2. Complex organic semiconductors, which are generally made up of there are at least two types of monomers (with an electron donor group and an electron acreptor group, respectively) which are associated with one another to a certain extent by charge transfer;

3. non-complex polymeric organic semiconductors and

4. Complex organic semiconductors in which at least one of the electron donor residues or the Electron acceptor residues is bound to a polymer chain or a part thereof.

Most of the known organic semiconductors which have resistivity ^{values below 10 4} OlIm · cm belong to the second and fourth groups, but many of them are unstable under normal temperature conditions, which considerably limits their usefulness. In addition, the semiconductors, which have sufficient stability, were usually obtained in the form of insoluble, infusible powders which are generally not suitable for further processing, for. B. for the production of coatings. This applies e.g. B. also for those from the book by JE K at ο η, “Organic Semiconducting PoIy mers «, pages 160/161 known salts of leuco bases.

From the reference »J. Chem. Phys. ", 42, 2248

(1965) and »J. Chem. Phys. «, 43, 1904 (1965) are des another organic semiconductors with a low specific resistance known in which a sulfur containing polycyclic hydrocarbon (Tetra thiotetracene) in charge transfer complexes from

Dative type with one of the three organic acceptors

o-chloranil, o-bromanil or tetracyanoethylene as

ίο Electron donor functions (the expression »charge transfer complex of the dative type« denotes a charge transfer complex between an electron donor and an electron acceptor which the constituents in the ground state of the complex

is in an ionized form; these complexes can also be referred to as »ion radical salts«, with the electron donor forming the »cation part« and the electron acceptor forming the »anion part«). The known complexes are, however neither soluble in organic solvents nor in water. Even tetrathiotetracene itself is only a few, very strong organic ones at room temperature Solvents very slightly soluble, although there is a specific electrical resistance in the lower Be rich in the specific electrical resistance values of the known non-complex organic semiconductors (the specific resistance of the pressed powder is of the order of 10 ⁴ ohm · cm). None of these known organic semiconductors has itself has sufficient solubility that it can be used for the production of coatings, Foils, fibers, etc. allows.

The object of the invention is to provide new organic semiconductor materials which are free from the The disadvantages described above are, dissolve in common solvents and have specific resistance ^{values between 10 -3} and 10 ohm · cm.

It has been found that certain organic

Amine salts of the composition given below can be used excellently as semiconductor materials.

The invention relates to the use of organic amine salts of the general formula:

O> -

in which:

ti, m, η, ρ, χ and y are each whole numbers within the following combinations:

(i = 0, m = Ι, .ν = l, v = 0 / '= 0/1 = 0, 1, 2, 3, 4, 5

/ 5 = 1 11 - 0, 1, 2, 3 P = In = 0, I

(I = I, »1 0, .v = 1, V = 0 ρ = 0 η - = 0, 1. 2, 3, 4, 5,

l> = 2 11th 0, 1.2

/) 3/1 - 0

I, / 11 - 0, ν 0. r

P = 0 / ι 0, I, 2. 3, 4. 5 / ι Ι / ι - 0. I. 2. 3 ο = 2 / ι - 0. I.

Ri and R ₄ each represent a hydrogen or halogen atom, a hydroxy radical, an alkyl or alkoxy radical each having 1 to 8 carbon atoms, an optionally substituted amino radical, an optionally substituted aryl radical, an acyl, carboxylate, thio, nitrate, sulfonate - Or cyano radical, where Ri and R4 are identical or different, R ² and R ³ each (1) an oxo, optionally alkyl-substituted (having 1 to 8 carbon atoms) or aryl-substituted or acyi-substituted imino or thioxo radical or (2) a Alkoxonium, optionally alkyl or dialkyl-substituted (with 1 to 8 carbon atoms) iminium or sulfonium radical; A is a monomeric or polymeric acid molecule or the metal salt of an acid if R ₂ and R _{3 are} neutral radicals, or a monomeric or polymeric acid anion if R ₂ and / or R _{3 are} charged radicals and q is an integer or fractional number> 0

till 9, as semiconductor material.

R ₁ and R ₄ can thus represent, for example, a methyl, ethyl, isopropyl, butyl or methoxy, ethoxy, propoxy or butoxy radical or an alkyl or dialkylamino radical with 1 to 8 carbon atoms in each alkyl group or an acylamino radical , e.g. B. an acetylamino, benzoylamino, naphthoylamino radical or a phenyl, naphthyl or tolyl radical or an acetyl, benzoyl or naphthoyl radical.

R2 and R ₃ can e.g. B. consist of phenylimino and naphthylimino residues and acetylimino and benzoylimino residues.

The alkoxonium radicals represented by R ₂ and R ₃ correspond to the formula

= OR

in which R is an alkyl radical having 1 to 8 carbon atoms. The iminium radicals for which R ₂ and R _{3 can} stand can be given by the formula

= NH,

reproduce in which one or both hydrogen atoms can be substituted by alkyl radicals having 1 to 8 carbon atoms.

The use of compounds of the formula given has proven to be particularly advantageous, in the

a = 0, m = 1, χ = 1, y = 0 ρ = 0 η = 0, 1, 2, 3 «= 1, m = 0, X = Uy = Op = On = O, 1,2

p = l η = 0.1

a = 1, m = 0, χ = 0, y = 1 ρ = 0 η = 0, 1, 2

ρ = 1 «= 0

It should be noted that the two terminal radicals in the right-hand part of the formula given are divalent Represent remnants of which only one is present at a time. For simplicity, the bindings are this divalent radicals in the formula represented by a solid or a dashed line.

The organic compounds used as semiconductor materials according to the invention can be passed through Produce reaction of corresponding organic amines with inorganic or organic acids.

The amines used as starting compounds are insulators or, at best, semiconductors with a low electrical conductivity, whereas the amine salts derived therefrom are highly electrically conductive semiconductor materials. The specific resistance of the semiconductor compounds used according to the invention is practically independent of moisture and is from ³ to 10 ^q ohm-cm. Most of the salts obtained by reacting an organic amine with an acid are not semiconductors. So show z. B. amine salts ^ such as rosaniline hydrochloride, malachite green, pararosaniline hydrochloride, auramine O and methylene violet specific resistance values of 10 ohm · cm when they are jet-tested in a vacuum and in the absence of moisture. From "Compt Rend.", 260, 5026 (! 965) it is known that emeraldine sulfate has a high electrical conductivity if it contains excess sulfuric acid and / or water. However, the material described is an in suitable solvents insoluble microcrystalline Powder which is therefore unsuitable for the production of electrically conductive coatings.

The type of acid molecule A, which can be inorganic or organic in nature, is obviously just playing around plays a subordinate role, while the amine is obviously decisive for the electrical properties of the amine acid. Regarding the choice of There is therefore a wide scope for the acids that can be used, since changes in the radical A are only moderate

Changes in the electrical conductivity of the amine salt lead. By choosing the remainder A. however, the solubility of the salt in common solvents can be significantly influenced, by most Acids that are used for the production of the invention Salts used can be used is not known to be useful as components for the manufacture of organic semiconductors. It was therefore Surprisingly to find that a wide variety of inorganic and organic acids, as well as polymers Acids, used in the manufacture of semiconductor materials.

Examples of suitable inorganic acids which can form the radical A are halogen acids, e.g. B. Hydrogen chloride, hydrogen bromide, hydrogen fluoride, Hydriodic and fluoroboric acids; also sulfuric acids, e.g. B. sulphurous acid, sulphurous, thiosulphurous, Thiocyanic and p-toluenesulfonic acid; Phosphoric acids, z. B. phosphorous acid and phosphoric acid, and nitric acids, e.g. B. nitrous acid and nitric acid re. Examples of suitable organic acids are mono-, di- and polyfunctional organic acids, e.g. B. saturated and unsaturated aliphatic acids with 1 to 8 carbon atoms, e.g. B. ant, vinegar, propionic, maleic, fumaric, butynedic, oxalic, amber, adipic and Acetylenedicarboxylic acid; also aromatic acids, e.g. B. phthalic, terephthalic, benzoic, toluic and naphthoic acid and barbituric acid and 2-thiobarbitic acid. Except The listed monomeric inorganic and organic acids can contain a wide variety of poly mer acids can be used. All of them can be used Polymers with an acidic function, for example a carboxy or sulfo radical, or a sufficient one acidic hydrogen atom, as in certain polyhydro

xy substituents. Examples of suitable polymers are vinyl polymers, for example

(a) acid polymers, e.g. B. polyacrylic acid, polymethacrylic acid;

(B) copolymers of esters and acids, e.g. B. poly (methyl methacrylate / methacrylic acid), poly (butyl methacryl la t / methacrylic acid), poly (vinyl acetate / maleic acid);

(C) copolymers of an ether and an acid or an acid anhydride, e.g. B. polyvinyl methyl ether / maleic anhydride);

(D) copolymers of an olefin and an acid, e.g. B. Poly (ethylene / ma! One acid);

(E) other copolymers, terpolymers and quaternary polymers, which include the acidic Have residues;

(f) polymers which contain sulfo groups ,? .. B. sulfonated polystyrene and

(g) copolymers, terpolymers and quaternary polymers, which contain a sulfo group.

In addition to the vinyl polymers, other classes of polymers, e.g. B. natural resins, cellulose, Polycondensates, silicones, alkyd resins and polyamides can be used, provided that they are due to the Exercise an acid function in the presence of carboxy or sulfo groups or of acidic hydrogen atoms. Particularly suitable polymers are polyacrylic acid and poly (ethyene / maleic acid).

The radical A can, however, also partially or completely consist of a metal salt derived from an acid, e.g. B. zinc chloride exist. For example, a semiconductive amine salt can be prepared in which the radical A, as can be shown by elemental analysis, / is composed of '2 moles of zinc chloride and 3V ₂ mol hydrochloric acid. The electrical conductivity of this connection is practically independent of the relative humidity. The salt is also electrically conductive in a high vacuum.

The amine radical of the salts used according to the invention cannot be in completely reduced or leuco form, but must contain at least one quinoid ring. However, the number of quinoid rings cannot be more than half the total number of rings +1 present. The presence of quinoid rings creates a conjugation between certain rings within the structure. The given general formula thus represents an expedient representation of the compounds used according to the invention. However, it is not intended to indicate which rings are aromatic and which are quinoid, ie have a quinone structure. Although certain rings are not necessarily always aromatic or quinoid, there is always a p-bond of all anilino, substituted anilino, quinoid, and substituted quinoid radicals.

The rings of the amine moiety bonded to one another in the para position can be substituted in the ortho or meta positions. Examples of suitable substituents are hydroxy radicals, optionally substituted Alkyl radicals with 1 to 6 carbon atoms, ζ. Β. Methyl, ethyl, isopropyl and tert-butyl radicals, if appropriate substituted alkoxy radicals having 1 to 6 carbon atoms in the alkyl group, optionally substituted acrylic radicals, optionally substituted aryl radicals, e.g. B. the Phenyl, tolyl and naphthyl radicals and other radicals, z. B. aroxyl, sulfo, carboxyl, amino, alkylamino, Arylamino, nitro and cyano radicals and halogen atoms.

5 °

55 examples of free amines which are suitable for the preparation of the compound which can be used according to the invention are;

Table I.

1 N- (p-anilinophenyl) -1, 4-benzoquinoneimine

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-Benzoquinonediimino) phenyl] -N'-phenyl-1,4-benzoquinonediimine

5 N- [p- (4-AminoaniIino) phenyl] -

N '- (p-aminophenyl) -1, 4-benzoquinonediimine

6 N- (p- [4-anilino) anilino] anilinophenyl | -
N '- (p- [N- (p-aminophenyl) -1, 4-benzoquinonediimino] -phenyl) -1,4-benzoquinonediimine

7 N- (p-Dimethylamino) phenyl-1,4-benzoquinonediimine

8 N- [p - (!, 4-Benzoquinonediimino) phenyl] -1,4-benzoquinonediimine

9 N, N-diphenyl-1,4-benzoquinonediimine

10 N- [p- (4-aminoanilino) phenyl] -1,4-benzoquinone imine

11 N- [p- (4-Hydroxyanilino) phenyl] -1,4-benzoquinone imine

12 N- | p- [4- (1,4-Benzoquinonimino) anilino] -phenylj-1,4-benzoquinoneimine

13 N- (p- (4-Dimethylaminoanilinojphenyl] -1,4-benzoquinone imine

14 N- [p- (4-anilino) anilinophenyl] -N'-acetyl-1,4-benzoquinonediimine

15 N- {p- [4- (p-Methoxyanilino) anilino] phenyl (-1,4-benzoquinone imine

16 N- (p-anilinophenyl) -N '- [p- (4-aminoanilino) phenyl] -1,4-benzoquinonediimine and

17 N- (p-anilinophenyl) -N '- [p- (1,4-benzoquinonimino) -phenyl] -1, 4-benzoquinonediimine

Although the compounds used according to the invention are referred to as amine salts, they have an electronic conduction mechanism. The charge carriers are therefore electrons and / or "positive holes", in contrast to purely ionic conduction, as is typical for common salts, in which migrating ionized residues act as charge carriers. The compounds used according to the invention also differ from ion radical salts (cf. »J. Chem. Phys. 42 [1965], 2248) in that the presence of an ionic radical as part of the charge transfer complex of the dative type does not affect the electrical conductivity of the salts is required. The amine salts used according to the invention can consist of an amine radical which is neutral and contains only one or more associated neutral acid molecules A. Other amine salts used according to the invention can have an amine radical which is a positively charged radical which is associated with one or more negatively charged acid molecules.

Since the electrical conduction of the connections used according to the invention is electronic, it is of practically independent of humidity. For this reason, the semiconductor materials can be used with advantage Use wherever there are variable humidity conditions.

Compounds used according to the invention can, as already stated, by reacting a prepare the corresponding amine with a monomeric or polymeric acid. That as the starting compound Amine used is expediently in a higher oxidation state than the leuco or lowest oxidation state oxidized. The oxidized amine is then combined with the acidic component in one Solvent, for example an ether, e.g. B. tetrahydrofuran, ethyl or isopropyl ether, a ketone, ζ B. acetone, an alcohol, e.g. B. methanol, ethanol, n-propanol or isopropanol or an aromatic Solvents, e.g. B. benzene or toluene, or water or in a mixture of these or other solvents implemented. Has the resulting amine salt in the solvent or solvents used If the solvent mixture has considerable solubility, the salt is separated off in such a way that one used concentrations that the solubility limit of the amine salt produced in the chosen Solvent or the selected solvent mixture exceed. The precipitate will then filtered off and washed. Processes of this type are, for example, from »J. Chem. Soc ", 97, p. 2392 (1910) and from "Chem.Ber.", 40, 2677 (1907) known.

Semiconductor elements can be produced from the semiconductor compounds used according to the invention, by adding a solution of the compound, optionally after mixing with a binder, on Applying substrate or soaking a substrate with the solution or producing a self-supporting layer. To the evaporation of the solvent results in a layer in which the electrically conductive components in the polymeric binders are present in dispersed form. It is also possible to use a soluble derivative of an insoluble semiconductor material to use and to produce the latter by heating or by chemical treatment of the layer produced. Electrically conductive Layers and coatings of the semiconductor materials can also be produced by on a substrate successively applies layers that contain amine components and acidic components, wherein the electrically conductive material is formed at the interface. This can also be done through this achieve that one applies a component of the salt to the substrate and then the vapor of the lets other components act. For example, a polymeric acid can be obtained from a solvent apply with or without additional polymeric binder to a substrate, whereupon a layer of a so soluble derivative of the amine moiety is applied, creating an electrically conductive polymeric salt is obtained.

The binders preferably used for the production of semiconductor elements are in general to film-forming binders, natural as well as synthetic origin. examples for such binders are:

I. Natural resins, e.g. B. gelatin, cellulose ester derivatives, for example alkyl esters of carboxylated cellulose, hydroxyethyl cellulose, carboxymethyl cellulose and carboxymethyl hydroxyethyl cellulose;
II. Vinyl resins, e.g. B.

(a) polyvinyl ester, e.g. B. vinyl acetate resins, vinyl acetate / crotonic acid copolymers, Copolymers of vinyl acetate and an ester of vinyl alcohol with a higher one aliphatic carboxylic acid, e.g. B. lauric or stearic acid, polyvinyl stearate, vinyl acetate / maleic acid copolymers, Poly (vinyl haloarylates) e.g. B.

Poly (vinyl m-bromobenzoate), vinyl butyral / vinyl alcohol / vinyl acetate terpolymers such as

Vinyl formal / vinyl alcohol / vinyl acetate polymers;

(b) vinyl chloride and
Vinylidene chloride polymers, e.g. B. poly (vinyl chloride),

Vinyl chloride / vinyl isobutyl ether copolymers,

Vinylidene chloride / acrylonitrile copolymers,

Vinyl chloride / vinyl acetate / vinyl alcohol terpolymers, polyvinylidene chloride, vinyl chloride / vinyl acetate / maleic anhydride terpolymers and
Vinyl chloride / vinyl acetate copolymers;

(c) styrene polymers, e.g. B. polystyrene, nitrated polystyrene,

Styrene / monoisobutyl maleate copolymers, styrene / methacrylic acid copolymers, Styrene / butadiene copolymers, dimethyl itaconate / styrene copolymers and polymethylstyrene;

(d) methacrylic acid ester polymers, e.g. B. poly (alkyl methacrylates;

(e) polyolefins, e.g. B. chlorinated polyethylene and chlorinated polypropylene;

(f) polyvinyl acetate, e.g. B. polyvinyl butyral as well

(g) polyvinyl alcohol;

III. Polycondensates, ζ. B.

(a) Polyester from 1,3-disulfobenzene and 2,2-bis (4-hydroxyphenyl) propane;

(b) polyesters made from diphenyl-p, p'-disulfonic acid and 2,2-bis- (4-hydroxyphenyl) propane;

(c) polyester made from 4,4-dicarboxyphenyl ether and 2,2-bis- (4-hydroxyphenyl) propane;

(d) polyester

2,2-bis- (4-hydroxyphenyl) propane and fumaric acid;

(e) pentaerythritol phthalate;

(f) resinous polybasic terpenic acids;

(g) polyester made from phosphoric acid and hydroquinone;

(h) polyphosphates;
(i) polyester made from neopentyl glycol and

Isophthalic acid;
(j) Polycarbonates, including the polythiocarbonates, e.g. B. polycarbonates from

2,2-bis (4-hydroxyphenyl) propane; (k) polyester from isophthalic acid, 2,2'-bis-4 - (/ hydroxyethoxy) phenylpropane

and ethylene glycol;
(1) Polyester from terephthalic acid, 2,2-bis-4 - (/ Miydroxyäthoxy) -phenylpropane

and ethylene glycol;
(m) Polyester made from ethylene glycol, neopentyl glycol.

Terephthalic acid and isophthalic acid; (n) polyamides;
(o) ketone resins and
(p) phenol formaldehyde resins;

IV. Silicone resins and

V. alkyl resins, including styrene-alkyd resins, the silicone alkyd resins and the soybean oil alkyd resins.

A wide variety of solvents are suitable for producing the coating compositions, e.g. B. alcohols, for example the aliphatic alcohols with preferably 1 to 8 carbon atoms, such as methanol, Ethanol, propanol, isopropanol, aromatic alcohols, polyhydroxy alcohols, substituted alcohols, / .. B. 2-methoxyethanol, ketones, e.g. B. aliphalic ketones, for example acetone, 2-butanone and methyl isobutyl ketone, aromatic ketones such as cyclohexanone, chlorinated Solvents, e.g. B. aliphatic chlorinated solvents, e.g. B. methylene chloride, ethylene chloride and propylene chloride, organic carboxylic acids having 1 to 10 carbon atoms, e.g. B. formic, acetic and propionic acid, substituted carboxylic acids, including those of organic carboxylic acids of 1 to 10 Esters derived from carbon atoms, e.g. B. methyl acetate and ethyl acetate, short-chain dialkyl sulfoxides, e.g. B. Dimethyl sulfoxide, dimethylformamide, acetonitrile and water. Mixtures of these solvents can also be used with each other or with other organic solvents.

The concentration of the semiconductor materials in the layers should be at least 1% by weight. The upper concentration limit can be very different. In those cases where a binder is used the semiconductor material must be present in a concentration of 1 to 99% by weight of the layer. A preferred concentration range for the semiconductor material in the layer is 10 to 60% by weight.

The thickness of the layer applied to a layer support can also be very different. In the As a rule, layers with a layer thickness of 0.00254 to 0.254 mm, measured before drying, are proved suitable. The layer thickness is preferably 0.0051 to 0.0203 mm, measured before drying. Suitable carriers to which the coating compositions can be applied are films, glass and paper and metals and fibers.

Because of their chemical and physical properties, those used according to the invention can Semiconductor materials easily become thin films with a surface resistivity of less processed as 10 "ohms / surface unit. The specific resistance is from the relative Moisture practically independent and remains constant even in a vacuum. Because of the good electrical Properties make these films suitable for the production of a wide variety of objects. Suitable for example semiconductor materials for the production of antistatic photographic recording materials from an inert layer support, which may be used to improve the layers to be applied may have an adhesive layer, an electrically conductive layer which is one of the invention contains organic semiconductor compounds used and one against electromagnetic radiation sensitive silver halide emulsion layer. The layers can be arranged so that the electrically conductive layer and the emulsion layer are on different sides of the support condition. However, both layers can also be arranged one above the other on the same side of the layer support being. It may be useful to have additional layers of an insulating polymer to use which are arranged either below, between or above each of the mentioned layers could be.

The amine salts used according to the invention can also be used to produce antistatic Use magnetic tapes having the same layer arrangement as the recording material described above have, however, the photographic emulsion layer by a magnetic Layer is replaced.

The amine salts described can also be used for the production of electron recording materials use made of an inert, insulating

κι layer support, an electrically conductive layer, the contains one of the organic amine salts described, and one sensitive to electron beams Silver halide emulsion layer exist. In this case both layers are on the same side of the Layer carrier arranged one above the other. If necessary, to improve the I laftung on the Carrier coated layers to eliminate undesirable changes in electron sensitivity Additional layers of an insulating polymer may also be present in the emulsion layer.

The amine salts can also be used for the production of electrophotographic recording materials use that contain an electrically conductive layer with one of the amine salts. The electrically conductive

The 2s layer is placed on an inert support applied and coated with a second layer containing a photoconductor. As in the case of the Recording materials already described can in this case also contain additional thin layers made of insulating polymers below, between or on top of the electrically conductive and photoconductive ones Layers are arranged.

The amine salts used as semiconductor materials are also suitable for the production of optical transparent, electrically conductive elements with an electrically conductive one containing an amine salt Layer applied to an inert, insulating support. The strength of the electrically conductive The layer is such that the resulting optical density in the spectral range from 400 to 800 nm is not is greater than about 0.5. Such an element is suitable for the production of so-called. Antistatic windows for electronic instruments, from antistatic lenses for cameras and other optical devices as well as for transparent heating plates and photographic products.

Furthermore, the amine salts can also be used in conjunction with a polymeric binder for production self-supporting electrically conductive films can be used. If the remainder A of the amine salt consists of one If the residue is polymeric, the use of an additional polymeric binder is not required, though a binder can also be used in this case.

The amine salts can also be used to make static-free fabrics will. Fibers that contain the semiconductor materials can also be incorporated into tissue. Such fibers can also be made from a semiconductor material and optionally containing a polymeric binder Electrically conductive cores consist of a polymer shell containing no semiconductor material are surrounded.

Finally, in electronic components, the amine salts can be applied to an insulating carrier and for the production of passive electronic components, e.g. B. of resistors or capacitors, can be brought into any desired shape. the

Amine salts can also be used as part of the active components, for example in rectifiers or transistors, be incorporated. Shaped, electrically conductive objects can also use the semiconducting material or contain no polymeric binder. s

The following examples are intended to illustrate the invention in more detail.

example 1

The free amine No. 3 in Table I was determined according to the m from »J. Chem. Soc ", 97, 2392 (1910) Process made. A solution containing 0.5 g of this amine in 250 ml of ether was filtered into a Stir a solution of 1.2 g of maleic acid in 100 ml of ether. This resulted in a blue-green precipitate, ι see which was filtered off, washed with 50 ml of ether and dried at room temperature. The one on one The specific volume resistivity of the material measured on the pressed powder was 140 ohm · cm. the Elemental analysis indicated that the product was the dimaleate salt of the free amine.

Example 2

A solution was prepared which contained 0.3 g of the free amine of Example 1 and 200 ml of ether. the Solution was filtered into a solution of 2.5 ml of dichloroacetic acid in 50 ml of ether. It was imagining again blue-green precipitate which is filtered off with a solution containing 3 ml of dichloroacetic acid in 80 ml of ether washed and dried at room temperature. The specific measured on a pressed powder Volume resistivity of the dichloroacetate salt of the amine was 8500 ohm · cm.

Example 3

IS

A solution was prepared which contained 0.05 g of the free amine of Example 1 in 50 ml of ether. the Solution was filtered into a solution containing, based on the amine, an excess of trifluoroacetic acid in Contained 50 ml of ether. An olive-green precipitate formed, which was filtered off and washed with 70 ml of ether and dried at room temperature. Volume resistivity measured on a pressed powder of the trifluoroacetate salt of the amine was 7800 ohm · cm.

Example 4

A solution was prepared which contained 0.05 g of the free amine of Example 1 and 50 ml of ether. the Solution was filtered into a second solution of 0.03 g of phthalic acid in 50 ml of ether. It imagined dark green precipitate, which is filtered off, washed with 70 ml of ether and dried at room temperature would. The volume resistivity of the phthalate salt of the measured on a pressed powder Amine was 3.5 · WOhm · cm.

Example 5

A solution containing 0.05 g of the amine salt of Example 1 and 1.0 ml of a 2% solution of polyvinyl acetate in 40 ml of methanol. The solution was after Filtration in the form of a layer on a polyethylene terephthalate support applied and dried at room temperature. The surface resistivity the layer produced was in air by placing graphite electrodes on the surface of the layer and measuring the resistance by means of an electrometer.

As used herein, "surface resistivity" or "film resistivity" indicates the electrical resistance of a unit area of a thin film, measured in the plane of the material between the opposing sides. In films that obey Ohm's law, this is a property inherent in the film. If the resistance is measured in ohms, the specific resistance of the thin film or the surface is expressed by the dimension ohms per unit area (cf. R. L · A itchis ο η, "Aust. J. Appl. Sei.", 5, 10 [1954]). The specific resistance of the layer in the present special case was 4.1 χ 10 ⁷ ohms / unit area. The value remained practically unchanged when measured in a high vacuum.

Example 6

The dihydrobromide salt of amine no. 4 in Table 1 was determined according to the method from »Chem. Ber. ”, 40, 2677 (1907), but this time using hydrobromic acid instead of hydrochloric acid and acetone instead of a mixture of ethanol and chloroform. After stirring for 5 minutes, a solution was prepared containing 0.05 g of this salt, 1.0 ml of a 2% solution of polyvinyl acetate in methanol, and 25 ml of methanol. The solution was filtered and then applied in the form of a layer to a polyethylene terephthalate support. The layer produced was dried at room temperature and ^{cured at 100 °} C. for 3 minutes. Then the surface resistivity was measured. It was 2.2 · 10 ⁸ ohms / unit area.

Example 7

Stirring for 5 minutes produced a solution containing 0.08 g of the Hydrobromic acid with the free amine No. 3 of Table I amine salt obtained, 5 ml of a 2% strength Solution of polyvinyl acetate in methanol and 15 ml of methanol contained. The filtered solution was shaped one layer applied to a poly (ethylene terephthalate) support and at room temperature dried. Then the surface resistivity of the layer was measured. It was included

6.3 · 10 ⁹ ohms / unit area.

Example 8

A solution was prepared by stirring for 5 minutes and then filtering, which contained 0.05 g of the amine salt prepared by reacting sulfuric acid with the free amine No. 2 in Table 1, 1.0 ml of a 2% strength solution of polyvinyl acetate in methanol and Contained 30 ml of methanol. The filtered solution was in the form of a layer on a poly (ethylene terephthalate) -Schichtträger applied, dried and cured for 3 minutes at room temperature at 120 ⁰ C The as determined in Example 5, the surface resistivity of the layer was

2.4 · 10 ⁷ ohms / unit area

Example 9

Stirring for 10 minutes became a solution prepared containing 0.05 g of the by reaction of hydrochloric acid with the free amine No. 5 of the Table I formed amine salt and 9.5 ml of methanol

Then 0.5 ml of a 2% solution of polyvinyl acetate in acetone were added with stirring. The filtered solution was then applied in the form of a layer to a Pclyiäthyleri.erephthalaO support and dried at room temperature. The specific surface resistance of the layer is 4.3-10 ⁷ ohm / unit area. After the layer had been exposed to a high vacuum overnight, the specific resistance was measured again. He was in a high vacuum at I. ' - 10 ⁷ ohms / unit area.

Example 10

After the in »Chem. Ber. ”, 40, 2677 (1907) known method, emeraldine was produced, purified and isolated in the form of the hydrochloride. By stirring 0.05 g of emeraldine hydrochloride in 20 ml of methanol for 10 minutes and then adding 1.0 ml of a 2% strength solution of an alcohol-soluble cellulose acetate butyrate polymer in methanol containing 6.5% n-propanol, a coating mass was produced which filtered, applied to a polyester film support and dried at room temperature. The layer obtained had a surface resistivity of 8.3 · 10 ⁸ ohms / unit area. After the layer overnight, the effect of a high vacuum had been exposed to the measured under high vacuum resistivity was 1.9 × 10 ^q ohms / square.

Example 11

A layer of an amine salt which had been prepared by reacting hydrobromic acid with the free amine no. The specific surface resistance determined as in Example 5 was 1.5 · 10 ⁷ ohms / surface unit at room temperature. When measured in a high vacuum, the specific surface resistance was 1.7 · 10 ⁷ ohms / surface unit.

Table II

Structure and specific resistance of typical amine salts used according to the invention

No. Aminsal /

A DC voltage of 47 volts was applied to a strip of the layer, the contact being established by graphite electrodes painted on the surface. In this case, an area of about 1.9 cm χ 13 cm remained between the electrodes unbeschichteL is then allowed to continuously for 7 days by flowing a direct current, during which time a high vacuum (of 1 x 10- ⁵ mm Hg) was maintained. After that, the specific resistance was

o the layer 2.0 · 10 ohm / area unit.

From the geometry and the physical properties of the layer it was calculated that the total electric charge (1.53 coulombs) that had passed the layer was 320 times greater than that

is electrical charge carried by all ions underneath an electrode could have been transported. This is conclusive evidence that the electrical Conductivity to at least 99.7% on the migration of electrons and / or "positive voids" and is not based on an ionic migration.

This behavior of a typical layer with an organic amine salt used according to the invention stands in clear contrast to the behavior of the usual amine salts or the quaternary ammonium

2s salts in which the electrical conduction, if any occurs at all, is based on ion migration in the presence of absorbed moisture. In these Cases leads to a decrease in the moisture content (by reducing the relative humidity of the Air), leads to a considerable decrease in electrical conductivity. Such materials have a low relative humidity or in a high vacuum does not have suitable electrical conductivity.

35

O -N <O> -N \ / OIH ₂ SO ₄

O ■ N ·. O V N <
ι O N O O I. ₂ SO ₄ > - NH ₂ HF - O H I.
H <' O - N
I. - / ο V- N ' N- <°> > —NH ₂ HNC ]
H ( ο "; ν-. _Ν -N-- < \ °} ~ N- <°> -NH 2HBr ί
H N ■■ ' 'O V-NH ₂ ; < ο '
χ / λ-N ο N- ■ -N- O NH ₂ - O N '. O - ■ N - ~> N ' H N ■ N
I 1 <O. · N
1 ι - ο O ' - N "'' ' ο

Example 12

The following compounds were prepared in the manner indicated, their volume resistivity as described in Example 1, was determined. The results are shown in Table II below compiled.

Specific resistance in Ohm ■ cm

320

420

260

3600

2, KHCI

> N \ O> NH ₂

HC!

29 (1 (1

709 686/262

Example 13

A solution of 0.5 g of Amine No. 3 of Table I in 50 ml of acetone was stirred into a solution of 0.5 g of an ethylene / maleic acid (1/1) copolymer, dissolved in a solvent mixture of 30 ml of acetone and 20 ml of methanol was added. To the one The dark green solution obtained was added to 300 ml of ethyl ether in order to precipitate the polymeric amine salt. The solid salt was removed from the solution by filtration and dried in vacuo. the specific volume resistivity of the material, measured on a pressed powder, was included 2 x 10 "ohms cm.

Example 14

The reaction mixture of Example 13 containing the dissolved polymeric amine salt was applied to a poly (ethylene terephthalate) substrate without isolating the solid semiconductor material, and the applied layer was then dried. The coating obtained in this way had a specific surface resistance of 1.8 · 10 ¹⁰ ohms / unit area. After the layer had been exposed to a high vacuum overnight, it had a specific resistance, measured in a high vacuum, of 1.9 · 10 ¹⁰ ohms / unit area.

The following examples explain the use of the amine salts as semiconductor materials in image recording materials, which contain a semiconductor layer and a photosensitive layer.

The following Example 15 describes a photographic recording material in which the electrically conductive layer and the barrier layer underneath the radiation-sensitive layer, however are arranged on the same side of the substrate. In the following Example 16, a photographic Recording material described in the; the electrically conductive layer and the barrier layer on top of the The back of the support are arranged, while the radiation-sensitive layer is on the front of the layer support is located. Example 17 describes an electrophotographic recording material in which the electrically conductive layer serves as an electrically conductive electrode for the The functioning of the electrophotographic process is essential when an insulating substrate (e.g. a Layer support) is used.

Example 15

A solution of 0.22 g of the hydrobromide salt of N- (p- [4 anilino] anilinophenyl) -1, 4-benzoquinone imine
and 0.16 g of poly (vinyl formal) in 100 ml of a mixture of propylene chloride, 1,1,2-trichloroethane, 2-methoxyethanol and ethanol was applied to a conventional, adhesive-coated polyester base. After the solvents had evaporated, a thin, electrically conductive layer remained on the substrate. A 2.5% strength solution of a methyl acrylate / vinylidene chloride / itaconic acid terpolymer in methyl isobutyl ketone was then applied to this layer, whereupon the solvent was evaporated. The specific electrical surface resistance

The density of the recording material obtained in this way was about 2 × 10 7 "ohms / area thereafter a radiation-sensitive, aqueous gelatin-silver halide emulsion was applied to the previously applied Layers applied, and after drying a static-free photographic Recording material was obtained.

It can optionally be advantageous to improve the adhesion of the layers to one another

ίο an additional thin layer of adhesive between the Terpolymer layer and the radiation-sensitive layer to be arranged.

The beneficial properties of this from einfx Electrostatic charge-free photographic recording material result from a Comparison of its sensitometric properties with those of a reference material which is not electrically conductive layer contained. It was found that the presence of the electrically conductive layer did not lead to any adverse sensitometric effects. When handling the comparison material emerged electrostatic markings, while such markings in which the electrically conductive Layer-containing recording material did not occur.

Example 16

Following the procedure described in Example 15

- ¹⁰ a photographic recording material was produced and tested, but this time the electrically conductive layer and the terpolymer layer were applied to one side of the substrate provided with an adhesive layer, while

rend the radiation-sensitive gelatin-silver halide emulsion layer on the opposite side of the substrate provided with an adhesive layer was applied.

The adhesive layer consisted of a terpolymer

• * ^c from methyl acrylate, vinylidene chloride and i taconic acid.

When examining the recording material produced in the manner described, it was found that that the presence of the electrically conductive backing layer does not result in any changes

¹ ^ the sensitometric properties of the radiation-sensitive layer and that an advantageous protection against electrostatic charges was achieved through the presence of the electrically conductive layer.

Example 17

A 0.75 g of the hydrobromide salt of ss N- (p- [4-anilino] -anilinophenyl) -1, 4-benzoquinone imine
and 0.62 g of a methyl methacrylate / methacrylic acid copolymer in 100 ml of a solution containing a mixture of methanol and 2-methoxyethanol, applied to a polyester support provided with an adhesive layer. After the solvents had evaporated, a thin electrically conductive layer remained on the substrate. This layer was then coated with a 0.5 μm thick barrier layer by applying a 2.5% strength solution of an acrylonitrile / vinylidene chloride / acrylic acid Terpohs lymerisats in methyl isobutyl ketone and subsequent evaporation of the solvent. A third layer was then made from a methylene chloride solution,

consisting of an organic photoconductor and a soluble polyester binder, applied. The electrophotographic recording material obtained in this way had a specific resistance of about J.5 · 10 ⁷ ohms / unit area. After the electrostatic

see charging, imagewise exposure with a Tungsten light source and development with a solid commercial electrophotographic toner this recording material provided electrographic Good quality images.

Claims (1)

Patent claims: 1. Use of organic amine salts of the general formula: CRmJU NHV-f / oV-N = <(^ y = N (Rj), in which: