DE2429729A1 - PICTURE PLAYBACK OR RECORDING MATERIAL - Google Patents

Description

The invention relates to image reproduction or recording materials respectively, -means for recording or _t, "capable of registration of images by electrical means and are thus useful for the registration or recording of different received signals such as signals from Faksimiligeräten, outputs of computers and their Output devices, data of various types of measuring devices for industry, medicine, trade and commerce and various purposes.

The recording or registration of electrical signals as image increases with the development of image radio and other Telekommunikätionsvorrichtungen from year to year to _0, the date on ausgedehntesten for such recording purposes

DeutGciio Bon! » (Munich) Account 81 / 01Θ70 Drcednor San !! (Mönsiicn) -tCto. SSSfKO Paeteshedc {Munich) Account 8? 043-iS3

The methods used are, for example, recording by means of electrical discharge, or electrolytic recording etc.

In the case of electrical discharge recording, an image is formed by applying either a white pigment layer on an electrically conductive black layer or an electrically conductive ¹ thin metal layer, for example aluminum, on the above-mentioned electrically conductive black layer and then the surface layer of white pigment or the thin metal layer is perforated by electrical discharge using a stylus (hereinafter referred to as "pen"), removing the surface layer and exposing the underlying black layer.

In the case of electrolytic recording, an image is created by first covering a sheet of paper with an electrolytic Solution impregnated and so brought into a moist state and through this an electric current means of the pen. The resulting image is formed either by a colored substance that is caused by Reaction between the ionized and pen-derived Metal and the electrolyte or a colored decomposition product that is produced by electrolysis of the

4Ö9S84 / 0988

existing electrolytes through the supplied via the pen electric current is formed.

In the electric discharge recording method, since the surface layer is perforated by heat from the electric discharge generated by the pen, there are inevitably some inconveniences such as a very irritating smell, atomized particles from the perforation of the surface layer, considerable pen wear and other disadvantages. Moreover, there is the possibility that physical effects such as wrinkle or wrinkles, applying pressure, etc., which are exposed to the coatings to expose the black layer, so that the paper easily ^M e partially colored or ¹¹ is faulty. Incidentally, do not fully covered under the surface layer is made thin to promote the discharge efficiency, lower) lying black layer so that the base color of the recording or R _e gistrierpapiers rather assumes a shade of gray than white, giving the appearance diminishes.

On the other hand is the recording paper or recording material in the wet type electrolytic recording method, of inferior storability and the quality of the image produced thereon is impaired by the electrolyte running. In addition, it suffers

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Paper deformations such as "wrinkling" on its surface as a result of drying out after taking the picture. These shortcomings are of the wet type in such a recording method fatal.

In JA patent publications 22341/1963 and 29630/1969 there is proposed a dry type electrosensitive recording material in which an image is thereby obtained becomes that an electrically reducible metal compound dispersed in an insulating resin layer is reduced by current flow to the free metal. In this electrosensitive recording material however, most metal compounds of relatively high electrical conductivity are colored, while less colored Metal compounds have a low electrical conductivity and therefore require chemical and physical treatments, so that the electric current can flow through it. However, such treatments cause coloring of the metal compounds with itself and consequently an increase in the depth of the base color of the recording material in a considerable Dimensions. In addition, difficulties in electrical conduction through the insulating resin dispersion lead to Occurrence of undesirably bad smell as a result of heating by electrical discharge during recording or Registration and - among other deficiencies - the writing

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pen considerably worn.

Furthermore, in the JA patent publications 5476/1967 and 13239/1967 described a method in which an electrically conductive thin layer on a white or transparent substance such as silica, etc. by deposition formed the vapor phase, after which the substance in the base material for the electrical conduction is dispersed. Even this procedure however, requires a considerable degree of experience and skill in the procedures for one such treatment.

It thus follows from the above that the conventional recording methods suffer from various problems associated with image generation on the recording material, as there are no effective means for electrical conduction wet-type registration or recording have been developed.

A primary object of the invention is therefore to provide image recording media or materials with a recording layer which is improved in terms of its electrical conductivity. Another one The aim is such a material on which a stable image regardless of the humidity of the surrounding atmosphere can be formed under practically dry conditions.

409184 / 0-98 *

Still another object of the invention are image recording materials and methods that are able to cope with even slight changes in the amount of electricity applied so that images of high quality can be recorded and an excellent reproduction of the image is achieved with good tone.

Still another object of the invention is an image recording material, which can correspond to high writing speeds as well as an electrical or with electrical Conductive recording method using such image recording materials.

Furthermore, according to the invention, an image recording material with a high degree of background whiteness is sought, that feels great.

Still another object of the invention are image recording materials, which can be generated by a very simple procedure. Still another object is imaging materials with high storage stability quite a long time. There is also a desire for a material that is non-toxic and safe to manufacture and use.

The characteristic features of the invention with which

400684/0088

the above objects are achieved, are that in 'the image recording materials or means with a active layer for the writing process, the at least one electrically conductive substance or such an agent imaging agent and a binder comprising electrically conductive agent composed of a porous compound, which contains a polar substance and that the desired image is recorded on the recording material, by sending an electric current into the aforementioned active writing layer.

The above objects, as well as details of construction and modes of operation of the invention, will become apparent from the following The description may be better understood by referring to the appended drawing, which shows some preferred Shows examples of practicing the invention.

, - More in detail, Figures 1 to 3 are different schematic representations showing the structure of the image-recording material and the recording process using it illustrate in different types of execution.

The image recording material according to Fig.l consists of a base layer 3 of any suitable material, a

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electrically conductive intermediate layer 2 on top of the base layer and a surface layer 1 for recording on the intermediate layer. This extensive or Web material for image recording is used to have images thereon by electrical recording methods To achieve discharge according to the invention.

The upper or writing layer 1 is made of a porous compound (A) containing a polar substance therein, a image-forming agent (B) and a binder for binding these two substances.

The image recording material according to FIG. 2 consists of the base layer 3 _{f of} the electrically conductive intermediate layer 2 on the base layer 3 and a further electrically conductive layer 5 i which corresponds to the upper writing layer 1 of FIG. 1 as described above, except that here the image-forming agent (B. ) is excluded; this layer 5 is arranged on the intermediate layer 2 and on top of the layer 5 there is arranged an image-forming layer 6 which contains therein the image-forming agent (B). In this case, the so-called writing layer, as it is used in the previous embodiment according to FIG. 1, is referred to as a combination of electrically conductive layer 5 and image-forming layer 6.

Finally, Figure 3, the image recording material according to only from the base layer 3 and the S hreibschicht _c 1, which is the same as in the image recording material according to Fig.l.

In all of these embodiments according to FIGS. 1 to 3, the reference numeral 4 denotes a source of electricity, 7 denotes a pen and 8 is a return electrode. The electrode 8 can hicht _c directly from the electrically conductive layer 2 or the writing layer 1 or the imaging S are taken. 6 The polarity of the electricity impressed on the pen 7 can either be positive (+) or negative (-χ) η, or alternating current can be used.

The porous substance (hereinafter simply referred to as Compound A) to be used as an electrically conductive agent in the present invention , which contains a polar substance, is understood to include the following physical

Has properties, namely:

l) Compound A has "pores" or "voids" within its molecular structure in which a loosely bound polar substance (which will be described in more detail later) can be held. Even in this state in which a sufficient amount of polar substance is contained in these pores or voids, the compound A does not show "stickiness ¹ ·,

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as they appear in hygroscopic and blooming phenomena in general occur with sodium chloride and similar salts but maintains an apparently dry state.

2) The compound A does not lose its crystal structure even if the polar substance contained therein is completely under the action of heat, reduced pressure or any completely removed by other means.

3) Compound A shows in consideration of the polar substance and different kinds of ions with which they coexist can, good electrical conductivity.

4) The compound A can develop its electrical conductivity by adsorbing enough water even if it is left in the natural atmosphere.

As mentioned in the previous paragraphs, compound A has very special physical properties. the The inventors have just recognized these physical properties of the compound A and after extensive and careful Investigations and experiments have found that that of a system in which the .Compound A in a binder is dispersed, image recording material produced the properties of the compound in practically the same

Can show vde it does the connection A per se.

Compounds Ä which are applicable for the purposes of the invention are as follows:
1) ion exchange resin ■

Synthetic resins composed mainly of porous high polymers containing ion-exchangeable acid groups or base groups fall under this category. Types of such ion exchange resins are cationic, anionic and aromatic ion exchange resins.

The composition of the main component of the ion exchange resin Forming high polymers may be any of the polystyrene-amine type, phenol-methylene sulfonic acid type, polystyrene sulfonic acid onic acid type, phenol-formaldehyde-polyamine type, methacrylic acid type and of vinyl resins.

The acid groups can be, for example, sulfonic acid groups, (-SOpOH), carboxyl groups (-COOH) and phenolic hydroxyl groups (-0H). The basic groups can be, for example, amino groups (-NH ₂ ), substituted amino groups (-NHR, -NRR ¹ ) and quaternary ammonium salt groups (-N ⁺ RR ¹ R ' ¹ ).

2) electron exchange resin

High polymer compounds that exhibit electron exchange fall under this category, for which polyvinyl hydro-

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quinone, hydroquinone-formaldehyde resin, dioxyphenylalanine polymers etc. can be examples.

3) Hydrophilic crosslinked copolymers

which consist of ternary components A, B and C, where component A by 60 to 90% by weight of one by N-vinyl lactam (lactum) represented heterocyclic N-vinyl monomers is formed, component B by 40 to 10 wt. a monomer selected from vinyl acetate and methyl methacrylate and component C is formed, for example, by polyethylene glycol dimethacrylate, of which 0.5 to 12 wt. to the total amount of components A and B can be added.

4) Porous polyester resin

The polyester resins are represented by those produced by the following process steps:

a) A means is provided for the formation of an internal phase, which is essentially composed of water or a Water existing liquid is formed;

b) it becomes a means of forming an external phase provided, which is formed by a polymerizable organic liquid, which is composed of the following two components consists:

Component a: is a polyester made from polycarboxylic acid and polyhydric alcohol, the molecules of which have at least one functional group represented by -CO-CH-CH-CO-;

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component b: is a low molecular weight polymerizable liquid monomeric compound which is copolymerizable with component a and is capable of containing therein a low molecular weight polymerizable non-liquid monomeric compound; '

c) Preparation of an oil-water emulsion with water as emulsifying agent in the presence of one or two or more kinds of inorganic metal compounds with less Solubility in water such as sulphides, hydroxides and oxides of mercury, lead, bismuth, copper, cadmium, antimony, Nickel, cobalt, iron, zinc, manganese, aluminum and chromium; and '

d) Block polymerization of this oil-water emulsion in the presence of a polymerization catalyst ^ and as required a polymerization accelerator for producing a porous synthetic resin, part or all of which of the internal phase forming agent of the produced synthetic resin is removed as necessary.

5) A substance with micropores inside

This substance is created by making a uniform mixed solution of - mainly - a condensed copolymer resin of dichlorodiphenyl sulfone and bis-r phenol (hereinafter referred to simply as "Polysulfone" - a branded product from OCC), chloroform as a solvent

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and an alcohol having 1 to 5 carbon atoms as a non-solvent Pour in a flat layer and then at a temperature below the softening point of the resin is subjected to evaporation and drying to form micropores in the resin layer.

6) Silicas and Silicates'

a) Porous silicas of the formula xHpO.ySiOp, known as silica gel or silica airgel;

b) Silicates of the formula xM ₂ 0.ySi0 ₂ , which occur in nature as "sticky"minerals; Examples of this are amorphous silicates such as allophane, hisingerite etc., and crystalline phyllosilicates (with leaf structure) e.g. of the montmorillonite group, pyrophyllite group, talc group, mica group, kaolin group, chlorite group, vermiculite etc.

c) Porous silica glass, which is available as an intermediate product in the production of quartz glass.

7) aluminum silicate

Different types of condensed acids can be specified here, for which natural 'zeolite is typical. This is also known as aluminum silicate and is represented by the following general formula: M ²⁺ , (M ⁺ ) ₂ 0. Al ₂ O ₃ . mSiO ₂ . nH ₂ 0 with (3 * m * 10), where: M and M ^{+ are} divalent and monovalent metal ions, of

400184/0080

most of which are usually formed by Ca ⁺ and sometimes Sr ⁺ , Ba and K ⁺ , all of which are replaceable by other cations. These zeolites have specific "voids" or "pores", in the three-dimensional skeletal structure, in which the above-mentioned replaceable cations are held together with water molecules. In addition to water, organic solvents can be absorbed in the cavities, and solvents of high polarity can be selectively absorbed. There are a wide variety of synthetic zeolites that have virtually the same three-dimensional skeletal structure as. in the case of natural zeolite and that of this with regard to the Grundsälzl. Properties are not much different.

There are also natural and synthetic compounds that have completely different chemical compositions from zeolite although they have the same basic properties, i.e. have cavities and their structures Do not change absorption and desorption of water. Such compounds are called zeolite-like compounds, which are also useful for the purposes of the invention.

Both natural ones used in the context of the invention as well as synthetic zeolites can be classified as follows will:

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(l) Analcime group: NaAlSi ₂ O ₆ . H ₂ O (x <10) Analcite (Cs, Na) AlSi 2 ° 6 * ^xH 2 ° ₂ (H ₂ 0) _{l6.0 96} Pollucite Ca ₁₀ Na ₂ Al ₁₀ 6 10 3] ₆ (H ₂ 0) ₃₂ 0 ₉₆ Viseit ^Zn 5.5 ^Ca 2.5 ^A 1 P (H)
l6 16 3] Kehoesit (2) Sodalite group: Na ₈ (Al ₆ Si ₆ O _l2 ) (0H) ₂ Hydrosodalite Na ₀₀ , Ca ,,, q (^ 1r7 *; Si-i Faujasite

Molecular sieve A ^v '

Molecular sieve Y ^vy

»SK ⁽ *) Comment: (*) Synthetic

(3) Chabazite group: Chabazite
Gmelinite

Erionite
Levynite

Molecular sieve R ^{v J}

Il nri V y

Note: (*) more synthetic

(4) Natrolite group: Natrolite

2.6
262.3H ₂ O

Na ₂ O.Al ₂ O ₃ .3 ~ 6 SiO ₂ .xH ₂ 0 practically identical to faujasite zeolite from Union Carbide Corp., USA

(Ca.Na ₂ ) Al ₂ Si ₄ O ₁₂ .6H ₂ O (Na ₂ Ca) Al ₂ Si ₄ O ₁₂ .6H ₂ O '(Ca.Mg.Na ₂ .K ₂ ) .Al ₂ Si ₄ O ₁₂ .6H ₂ O Ca (Al ₂ Si ₄ O ₁₂ ) 6H ₂ O

the same as chabazite the same as gmelinite the same as elionite Zeolite from Union Carbide Corp., U, S.A.

Na ₂ (Al ₂ Si ₃ O ₁₀ ) .2H ₂ O

-17- 2Ä29729

Mesolite Skolecite Thomsonite Edingtonite Gonnardite Rhodesite

CC O £ - \ J

Mountainit KNa ₂ Ca ₂ (HSi ₈ O ₂₀ )

(5) Harmatom group: Harmatom Phillipsite Gismondit molecular sieve B ^ '

Garronit NaCa _{2 5} (Al ₃ Si ₅ O ₁₆ J ₂ .13,5H ₂ O

Note (*) synthetic zeolite from Union Carbide Corp., U.S.A,

(6) Mordenite group:

Mordenite Na (AlSi ₅ O ₁₂ ) .3HgO

D'achiardite (Na ₂ Ca) ₂ Al ₄ Si ₂₀ O ₄₈ AaH ₂ O

Ferrierite Na ₁ , -Mg ₂ (Al ₅ c ^{S: i} -3o 5O ₇₂ ) AeH ₂ O

Zeolon 'the same as mordenite

Comment; (**) from Norton Co.

(7) Zeolites of undetermined structure: Heulandite Ca (Al ₂ Si ₇ O ₁₈ ) OH ₂ O

Clinoptilotite ^Na O, 95 ^K O, 3O ^Ca O _f 5 ^(A1 l, 35 ^Si 7 _t O5 ° 18 ⁾

5H ₂ O

Stilbit Ca (Al ₂ Si ₇ O ₁₈ ) 7H ₂ O

Epistilbit Ca!

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Brewsterite (Sr, Ba, Ca) Al ₂ Si gCL

Lauraontit ')

.Yugawaralite Ca (Al ₂ Si ₅ O ₁₄ ) .3H ₂ O

Paulingite (K, Ca, Na) ₁₂₀ [(Al, Si) _58O O _ll60 ) 690H ₂ O

Ashcroftin [KNa (Ca, Mg, Mn)] ₁₂ o ^(A1 l6O ^Si 2OO ° 72O ⁾

320H ₀ O

C-

Bikitait

The above compounds are all applicable to the present egg »- findg. useful.

(8) Zeolite-like compounds:

(8-1) Zeolite-like silicates that are not classified as zeolite but contain zeolite water.

Beryl Al ₀ Be * [si ^ O-, ο] .nH _o 0

c. j L ο Ιο ά.

Cordierite Mg ₀ Al, rAlSicO-, _Q ~ l nH _o 0

Milarite KCa ₀ AlBe ₀ LSi ₁₂ O ^ ₀ J 0.5H ₂ O

Osumilite (K, Na, Ca) (Mg ₁ Fe) ₂ (Al ₁ Fe) ₃ [(Si ,,

O ₃₀ ] H ₂ O

Hydrazine nepheline. KNa ₃ (Al ₄ Si ₄ O ₁₆ ) ^ H ₂ O Cancrinite Na ₆ Ca ₆ (Al ₆ Si ₆ O ₂₄ ) CO ₃ .3H ₂ O

Buddingtonite NH ₄ AlSi ₃ O ₈ .O, 5H _£ 0

(8-2) Other zeolite-like compounds:

(I) Germanates M ₃ [HGe ₄ (GeO ₄ ) ₃ 0 ₄ ] .4H ₂ O

where M is a metal ion

(II) phosphates, *

Arsenate, FeAsO ₄ .2H ₂ O

Scorodite

Pharmacoside K [Fe ₂ (OH) ₄ (AsO ₄ ) ₃ J .6

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(III) Hydrous metal oxides Psilomelan (Ba, H ₂ O) ₂ , Mn, -O ₁₀

(IV) three-structure complexes

: / Prussian blue M ₃ (Ve (CN) ₆ ] ₂ .12H ₂ O,

(M = Mn, Fe, "Co, Ni, Zn, Cd)

WeddeHit CaC ₉ O,. (2 + x) .H ₉ O, (x ^ 0.5)

The compounds listed above are all applicable to the invention. In particular, however, are such Compounds preferred that have a large void volume or • a high porosity and a high content of polar compound and therefore 'good electrical conductivities demonstrate.

8) Basic aluminum-magnesium carbonates

These compounds are represented by the following general formula:

(where: x, y and ζ are integers that represent the relationships

1 χ 1 2 '

- <~ <10 and - <are sufficient and a is zero or one

30 y 20 x + y ■

is an integer that satisfies the relation 0 fc - »- si.) -.

x + y

The polar substance included in Compound A detailed above as the useful active component may be included for the purposes of the invention can be demonstrated by the following examples:

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Water, alcohols, ammonia, dimethylformaldehyde, and the like polar solvents; Sodium hydroxide, potassium hydroxide, lithium chloride, magnesium chloride, sodium chloride, calcium chloride, sodium iodide, potassium iodide, sodium bromide, potassium bromide and other inorganic electrolytes. In addition to these inorganic electrolytes, there are different classes of organic electrolytes. Of these, the following are to be listed: Sulfuric acid _{derivatives such as, for example, carboxylic acid salts of compounds of the formula R (θ (CH 2} ) J _x .COOH.B, ROCO (CH ₂ ) ^ COOH. B (where B is an organic amine) etc., triethanolamine- salt of cetylsulfonic acid, diethanolamine salt of alkylsulfonic acid, naphthalene sulfonate, sodium salt of oleylbenzimidazole sulfonic acid, etc., phosphoric acid derivatives such as various kinds of salts of phosphonic acid, phosphinic acid, phosphite esters, phosphoric acid esters, etc., alkylamine salts such as 1-methyl-bigadecyl-5 Hydrochloride, dibutylphosphoric acid tetraethylene pentamine salt etc., salts of cyclic amines such as heptadecylimidazoline, dimethylamino-acetoguanamine etc., salts of amidamines of higher fatty acids and lower polyamines such as N-monoacetyl-ethylenediamine etc., -amines such as the ester-amine of stearic acid and triethanolamine or the stearic acid ester of w, w'-diaminopropyl-octadecyl-ethylene glycyl ether, etc. _f quaternary ammonium salts such as alkyldimethylbenzylammonium salt, alkyltrimethylammonium salt, etc., and salts such as guanidine salt, alkylalanine, alkylamine sulfonic acid, etc., which by conversion

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Settlement of maleic anhydride with alkylarain obtained will.

For the impregnation of the porous compound A with the polar substance, different aids such as Heating up, applying reduced pressure, etc. Depending on the Situation. However, sufficient impregnation can be achieved by making the porous connection A and simply leaves the polar substance under the natural conditions in case the latter is water. Also, if the required amount of electrical conduction for image recording by impregnation with Water alone as a polar substance cannot be reached, any of the aforementioned organic or inorganic Electrolytes for more effective image recording results be applied together with it. The impregnation ratio of the polar substance in the porous compound · A usually ranges from about 10 to 75 wt. 96 according to the invention or in particular approximately 30 to 70% by weight.

The imaging agents as used here are those capable of image formation in response to a change in energy by the application of electricity are. Any known compound can be used such as oxidation type color formers, color formers reduction type, pH indicators, heat sensitive

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Color formers and the like.

As color formers of the reduction type, leuco compounds of diphenylmethane colors such as Michler's methane bases such as bis (p-dimethylaminophenyl) methane, 9 * 9'-diethyl-6,6'-dichloro-3,3'-dicarbazoylmethane, (9- Ethyl-6-methyl-3-carbazoVl) -pdimethyl-aminophenyl-methane etc. and leuco auramines such as leuco auramine, Ν, Ν-diethyl-leuco auramine, "phenylsulfonamidbis- (p-dimethylamino-phenyl) -methane, bis- (p-dimethylaminophenyl ) -benzotriazylmethane, bis- (p-diethylaminophenyl) -morphonylmethane etc .; leuco compounds of triphenylmethane colors such as diaminotriphenylmethane like leukd malachite green, 3,3'-dicarbazoylphenyl methane etc., triaminophenylimethane like ¹ leuco -, Triethyl-3,3'3 "-tricarbazolylmethane etc. and hydroxy-triphenylmethanes such as bis- (3-methyl-4-hydroxy-5-carboxyphenyl) -2,6-dichlorophenylmethane, bis- (3-methyl-4 -hydroxy-5-carboxyphenyl) -4-diethylaminophenylmethane etc .; leuco compounds of xanthene such as 3,6-di- (dimethylamine) -xanthene; leuco compounds of acridine color such as 3,6 -Di-amino-2,7-dimethyl-9-phenylacridine, 3,6-di- (dimethylamino) acridine, etc .; Leuco compounds of azine dyes such as 2-methyl-3-amino-7-dimethyl-amino-5,10-dihydrophenazine, 3,7-diamino-5-phenyl-5,10-dihydrophenazine, etc .; Leuco compounds of oxazine dyes such as 3 »7-di- (dimethylamine) -phenoxazine, etc .; and leuco compounds of thiazines such as 3,7-di (dimethylamino) phenothiazine and the like can be mentioned.

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Furthermore, reducing bodies of indigo and indigoid colors, Leuco ferrocyanine and leuco base vat dyes of para-quinones such as benzoquinone dyes, naphthoquinone dyes, Anthraquinones, etc .; aromatic amino compounds such as p-amino-diphenylamine, diphenylbenzidine, basic oxidation substances, which form oxidation colors such as phenols such as 4-methoxy-1-naphthol, 1,5-dihydroxynaphthalene, etc .; and Sulfide dye reducing agents such as 2-mercapto-3-hydroxy-7-dimethylaminophenothiazine etc. are listed.

Tetrazolium salts can be used as the reduction type color formers such as triphenyltetrazolium chloride, ditetrazolium chloride, etc. jic-nogene salts of long-chain aliphatic acids such as Ferristearatusw .; Precious metal salts of organic acids such as silver behenate, silver stearate, etc. '; Metal oxalates such as silver oxalate, nickel oxalate etc., metal carbonates such as manganese carbonate, Cobalt carbonate, etc .; Metal chlorides such as nickel. Chloride, copper chloride, etc .; as well as heterocyclic quaternaries Ammonium salts, which can form anhydrous salts by reduction, such as l-methyl-2,2 ', V-dinitrobenzylpyridium p-toluenesulfonate, 1-methyl-A-chloroquinaldinium sulfate, etc .; and metal compounds such as molybdenum trioxide, thorium oxide, cerium oxide, phosphotungstic acid, phosphomolybdic acid, ammonium phosphomolybdate etc.

As heat-sensitive color formers, individual

Α09Θ8Α / 09 8 8

Heat sensitizers such as indole derivatives, pyrrolone derivatives and substituted aminodithioformic acid salts of heavy metals and two-component heat sensitizers such as ionogenic salts of long-chain aliphatic acids such as ferric stearate, phenols such as tannic acid, ammonium salicylate, organic heavy metal salts such as organoalcoholic salts with organic salts such as sulfonates or salts of organic metal salts such as metal alkali metal salts of organic metal salts such as metal alkali metal salts with organic metal salts such as metal alkali metal salts with organic metal salts such as metal alkali metal salts with organic salts , aromatic organic reducing bodies such as hydroquinone, protocatechuic acid, heavy metal salts of higher aliphatic acids such as ferric stearate, disubstituted dithiocarbamic acid, zinc derivatives such as zinc dibutyl thiocarbamate, and so on. In addition, there are two-component-based color-forming heat-sensitive agents such as combinations of representatives from the group of color-formable lactone compounds such as crystal violet lactone, 3-pimethyl-amino-6-methoxyfluorene; color-formable lactam compounds such as rhodamine B-lactam; Leuco compounds of dyes such as leuco crystal violet, leuco malachite green; and spiropyran compounds such as 1,3,3-trimethylindolino-8'-methoxybenzopyryl-spirane, l-amyl-3 ₁ 3-dimethylindolino-8'-ethoxybenzopyryl-spirane and a representative from "the group of acidic compounds such as bisphenol A, oc - Naphthol and palmitic acid.

So far, the incorporation of iodine compounds such as potassium iodide was known in a recording material, whereby by

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electrical stimulation, color formation occurs through iodine starch reaction, whereby a visible image can be obtained. Also been known a method in which iodine compounds and amines or their Leukoderiyate in an S _c were introduced hreibschicht reacts in the liberated iodine by electrical means with the amines or their derivatives, whereby an image is recorded on the recording material. These known methods can also be used within the scope of the invention.

Examples of iodine compounds to be used in these processes are: zinc iodide, aluminum iodide, antimony iodide, Ammonium iodide, indium iodide, uranyl iodide, cadmium iodide, Potassium iodide, calcium iodide, silver iodide, cobalt iodide, zirconium iodide, Mercury iodide, tin iodide, strontium iodide, cesium iodide, cerium iodide, tallium iodide, tungsten iodide, iron iodide, Copper iodide, thorium iodide, sodium iodide, nickel iodide, Platinum iodide, barium iodide, beryllium iodide, magnesium iodide, manganese iodide and lithium iodide. Also oxides of iodine such as iodine pentoxide, Iodetetraoxide, etc., as well as iodic acid and ammonium iodate can be used. Of these various iodine compounds those with strong ionic coupling such as iodides of alkali metals or alkaline earth metals are especially important preferred.

Compounds with the from the aforementioned iodine

The following compounds react with released iodine to produce an image: starch, starch ether, amylopectin, polyvinyl alcohol , High OH number polyvinyl formal, etc .; Except these can be piperine, cellulose treated with zinc chloride, praseodymium acetate, lanthanum propionate, nylon, etc. Also can aromatic amines such as tetramethyl-p-phenylenediamine, Ν, Ν'τ Dimethyl-p-phenylenediamine, tetramethyldiaminodiphenylmethane etc. can be used. In addition to these amines, color bases and leuco compounds such as tria- (p-dimethylaminophenyl) methane, ^, ^ - Benzo-e-dimethylaminofluorene, bis- (p-diethylaminophenyl) -phenylmethoxymethane etc. used.

There is another method of forming an image using the compounds listed below as an imaging agent, in which a writing layer containing any of these imaging elements is electrified to differentiate its properties, either hydrophilic or hydrophobic, after which it is used as a transfer element ( master plate) is used for offset printing. Examples of the above-mentioned imaging element include tetrazolium salts, Ditetrazoliumsalze, triazolium or petroleum waxes such as microcrystalline wax (with isoparaffin of 32 to 70 carbon atoms as a main component), paraffin wax having a melting point of 37.8 to 64.5 ⁰ C (with η-paraffin with 16 to 40 carbon atoms as the main component) and petroleum jelly wax with

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a melting point of 38 to 60 ⁰ C.

Apart from this, it is possible that some or all of the ions A 'such as sodium ions, potassium ions, etc. contained in the above-mentioned porous compound A are replaced by other ions B ¹ such as silver ions, gold ions, copper ions, ammonium ions , Nickel ions, cobalt ions, iodine ions, iron ions, magnesium ions, etc., which are necessary for image formation, are exchanged to form a porous compound B which is used directly as the image forming agent.

The binders used here include gelatin, natural high polymers such as starch; Cellulose derivatives such as Cellulose nitrate, carboxymethyl cellulose, etc .; semi-synthetic polymers such as natural rubber plasticizers such as chlorinated rubber, cyclized rubber, etc .; synthetic polymers of the polymerization type such as polyisobutylene, polystyrene, terpene resin, Polyacrylic acid, polyacrylate, polymethacrylate, polyacrylonitrile, polyacrylamide, polyvinyl acetate, polyvinyl alcohol, polyvinylpyrrolidone, Polyacetal polyvinyl chloride, polyvinyl pyridine, polyvinyl carbazole, polybutadiene, butadiene-styrene copolymers, Butyl rubber, polyoxymethylene, polyethyleneimine, polyethyleneimine hydrochloride, Poly (2-acryloxyethyldimethylsulfonium chloride) etc.; Condensation polymers such as phenolic resin, amino resin, toluene resin, alkyd resin, unsaturated polyester resin,

409884/09 8 8.

Allyl resin, polycarbonate, polyamide resin, polyether resin, Silicone resin, furan resin, thiokol rubber, etc .; and addition polymers such as polyurethane, polyurea, epoxy resin, etc.

The recording materials according to the invention are produced in the following manner:

The porous compound with polar substance contained therein, image-forming agent and binder (if necessary along with pigment, color control agent, and others Additives) are evenly dispersed and the dispersion liquid by layer application, dipping or other means applied to any suitable substrate to form a writing layer. The amount of porous connection with The polar substance contained therein, when used according to the invention, generally ranges from 30 to 98% by weight, based on based on the total weight of the writing layer and preferably from 50 to 95% by weight. A particularly preferred area is 70 to 90% by weight, although the invention is not limited to this particular range.

Paper, resin film, conductive material such as metal with a thin metal film can be used for the substrate or base treated conductive paper, conductive paper coated with vapor-deposited metal, coated with metal powder conductive paper, carbon treated conductive paper

409884/0988

- ²⁹ \ 2A29729

Paper, etc. can be used.

To facilitate the practice of the invention by those skilled in the art, preferred examples are set out below reproduced. Of course, these only serve to explain the invention, which is accessible to various modifications.

example 1

Sheets or web materials of conductive recording paper were made with the following composition as a writing layer:

Components parts by weight

porous connection A of a type listed in 100 Tab. 1

Rutile type titanium oxide 20

Polyvinyl butyral ".

(Degree of polymerization 1500) 30

Ethanol 200

The mixture of the above components became a full seven Milled in a ball mill for days and nights, after which 5 parts by weight of leuco malachite green as an imaging agent added to this milled mixture and further mixed sufficiently. This mixture was then added to a Using aluminum foil to form a film approximately 8µ thick

409884/0988

applied with a squeegee. The aluminum foil coated in this way was then ^{heat-treated for 5 minutes in an oven kept at 100 °} C., a writing layer being formed.

Then a tungsten pen with the positive pole and the aluminum foil with the negative pole of a DC voltage source and a voltage of approximately 150 V is applied and the pen causes the writing layer to travel at a speed of 1 m / fe. the The results obtained are shown in Table 1.

Tabel

Type of connection A

Writability

hue

"AMBERLITE IR-100 ^M (*)" AMBEkLITE IRA-401 "(*) montmorillonite kaolinite

Silica gel

Silica-Aerosil Polyviny! Hydroquinone

hydrophilic cross-linked polymer (**)

porous polyester (* ♦♦)

basic aluminum / magnesium carbonate (****)

Titanium oxide "R-5N" of rutile type (**** ♦)

O dark green green η light green. © green Δ dark green O light green Θ Δ green 0 light green U Δ Δ

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Comments: (*) strongly acidic (IR) or strongly basic

(IRA) Ion exchange resin from Röhm & Haas Co.

(**) - "from 7 parts by weight of N-vinylpyrrolidone, 3 parts by weight of methyl methacrylate. and 1 part by weight of polyethylene glycol dimethyl acrylate

from 1 part by weight of trimethylolpropane trifumarate and 1 part by weight of divinylbenzene,. MgAl ₂ (OH) ₆ CO ₃ 2H ₂ O
Titanium oxide from Sakai Kagaku KK, no

porous; used for comparison purposes only.
Explanation of the symbols for the "writability":

. ".-." "0 very good

Oh well

A writable, although not good

• X bad '

Example 2

Kaolinite, PolyV-iny! Hydroquinone, porous polyester and basic aluminum / magnesium carbonate, which show a writability "Λ" according to Example 1, were under reduced Print dried; thereafter, each of the polar substances shown in Table 2 below was tested on each of these compounds A

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adsorbed.

Afterwards, writing layers in exactly the same way were made with each of these compounds with the respective polar substances in the same manner as mentioned in Example 1, and the writing layer produced in the same manner as in Example 1 "described". The following descriptions of the Writing layers with each of the polar substances noted:

Table 2

Polar substance enhancement of descriptive

availability

Glycerin O Polyethylene glycol Δ Lithium chloride © Sodium chloride O Monoethanolamine butyrate A. Sodium N-steroid sarcosinate O Alkyl trimethyl ammonium salt Θ

Note: The symbols for improving the writability have the following meanings:

0 very notable improvement over example 1
O ·· .. ».. remarkable improvement over

example 1
^ \ .... ·. · Slight improvement compared to example 1

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From Table 2 it follows that the presence of polar substances unlike water in particular, different types of electrolytes improve the writability serves.

Example 3

To a mixture of 2 g of ditetrazolium chloride, 10 g Polyvinyl butyral (degree of polymerization of 1,500), 5 g of rutile type titanium oxide and 150 g of ethanol became 30 g of different Types of porous compounds as shown in Table 3 below, added and the batches two full days and Nights kneaded or ground.

The compounds of the G _r oup A indicated in the table were such porous compounds containing only the zeolitic water primarily contained in the compounds, whereas the compounds of group B of the Table are those compounds, the sodium chloride (NaCl) in the so-called. " Voids "or" pores "that they have contained.

After grinding, the. i liquid dispersion coated on an aluminum coated paper in a film thickness of about 10 ^ by means of a Rackels and then dried 5 minutes at a temperature of 100 ⁰ C long. After drying, the writing paper thus produced was subjected to electrical conduction recording with a tungsten pen

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connected to the negative pole and the aluminum-coated paper to the positive pole of a DC voltage source and a voltage of approximately 150 volts was applied and the pen was caused to scan the paper at a speed of 70 cm / s. The results of this recording are shown in Table 3 below.

Table 3

links Writability B. Molecular sieve * SK-40 A. ζο \ Molecular Sieve * 13X Γο \ Molecular Sieve * 5A Θ Θ Weddellite O Θ Gismondite o ■ O Chabazit Δ O Scorodit Δ O Clinoptilotite Δ O Mordenite A. O Sodalite • Δ O Analcite Δ Δ Psilomelan Δ Λ Concrinit Δ Δ Δ

Note (*) from Union Carbide Corp.

Meaning of the symbols for the writability © very good
Oh well

writable, although not good.

409814/0988

It follows from the above that the writability improves in the presence of the electrolytes in the porous compound.

Example 4

Using Group A molecular sieve SK-40 and B. of Example 3, writing layers were produced and the writing speeds of the pen were changed tested. The composition of the recording material or recording paper and the working conditions for the recording were exactly the same as in Example 3. The results of the tests are shown in Table 4.

Table 4

"Scan speed of the 0.7 Be honored i bbarke it link • Θ Pen (πι / β) ι, ο link CB) Θ - 2.0. ". ■■ · ■■■: ■ (A) ■ Θ 3.0 O O 4.0 O Λ Δ Δ

The symbols shown in the table have the same Meaning as in Example 3. It follows from the above experiments that, thanks to the presence of electrolytes, high writing speeds possible are.

409884/0908

Example 5

In this example, recording materials or recording papers were made using an electrically conductive one Prepared by means of adsorption of 10% aqueous solutions of different electrolysis, as shown in Table 5 indicated on the porous connections.

The writing layers were then subjected to electroconductive recording and the results compared with each other; the comparison results are given in Table 5.

Molecular sieve 13X (from Union Carbide Corporation, U.S.A.) impregnated with 10 # aqueous electrolyte solution of the type shown in Table 5, the electrolyte at the connection in sufficient Amount were adsorbed.

Polyvinyl butyral in a weight ratio of 5 to 1 was used as the binder. Likewise, as that imaging agents triphenyltetrazolium chloride in a weight ratio of 1/20 with respect to the total weight of the porous connection used.

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Table 5

Electrolyte Improvement of writability

Sodium chloride 0

Lithium chloride φ

Sodium iodide ©

Triethanolamine cetyl sulfonate ^

Dimethylaminoacetoguanamine &

sulfate

Potassium Oleate Q

Alkyl benzene calcium sulfonate O

Laurylamine hydrochloride ^

Sodium stearyl aminopropionate O

Note: The symbols for improving the writability have the following meaning:

0 ..... very remarkably improved beach friction

availability

Q · .. · · remarkably improved writability Δ · ■ ···· slightly improved writability

Example 6

The scanning of the writing layer by the pen at a rate of 0.7 ω / s as in Example 4 was made under the following conditions of relative humidity and tested the writability of the layer. The co-

409884/09

The setting of the writing layer and other conditions were those same as in Example 4; the results are given in Table 6:

Table 6

relative humidity (%) Writability Connection B 60
40
20th
10
5 Connection A Θ
Co)
Θ
O
O Θ
. Θ
O
O
Δ

Note: The symbols for the writability have the same meaning as in example 4

From the above results, it follows that there is improved writability when recording under low humidity
thanks to the presence of the electrolyte could be achieved.

Example 7

Different types of recording materials or recording papers were produced in the same way as described in Example 1, except that different image-forming agents were used instead of leuco-malachite green. The chart papers were written on using electricity, with the results shown in Table 7
were received,

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Tabel

imaging agent,

Writability Registration color Polarity of the pen ¹

O
CO
GO
OO

O
CO
OO
OD

Leucoauramine O

3,6-di (dimethylamino) xanthene 0

3,7-diamino-5 * 10-dihydrophenazine 0

3,7-Di- (dimethylamino) -phe.nothiazine · 0

4-methoxy-1-naphthol q

Bis (p-dimethylaminophenyl) methane 'O *

Leuco crystal violet ©

Bis- (3-methyl-4-hydroxy-5-carboxy-0 phenyl-2,6-dichlorophenyl) methane 3,6-diamino-2,7-dimethyl-9-phenylacridan · O

3,7-Di- (diethylamino) -phenoxazine Θ Indigo white ■ 0

P-aminodiphenylamine ©

1-methyl-2,2 · ^ '- dinitrobenzyl per- ^) idinium-p-toluenesulfonate

yellow + Red ■. + Red : blue blue blue + purple-blue ⁺ purple + Red + blue dark blue + dark blue purple-blue

imaging agent

Dibromophenolsulfophthalein Phenolphthalein triphenyl tetrazolium chloride Ditetrazolium chloride nickel oxalate cobalt carbonate Silver behenate phosphotungstic acid Nickel hypophosphite zinc oxide writability registration color polarity of

Pen

ic) Red O Red Θ Red Θ dark blue O gray-brown O gray-brown O gray-brown Θ grey black O gray-brown Θ gray blackζ

Example 8

Instead of applying direct current of positive or negative polarity to the pen as in the example above 7, an alternating current of approximately 150 V was used of the record "in the same way as above Example imprinted. As a result, the images and records were good Preserved with no change in shade.

Example 9

A mixture of the following ingredients was made for two milled full days and nights in a ball mill for manufacture a dispersion liquid.

component Part by weight of 500) 10.0 Moritol Morillenite 3.0 Polyvinyl butyral 8th) (Degree of polymerisation 1.0 Sodium iodide 1.0 Addition (see table 30.0 Ethanol

The dispersion liquid thus prepared was coated on an aluminum-coated paper in a thickness of approximately 8 iu applied and dried to obtain a recording paper or recording material.

This recording paper was created under the same conditions

409884 / 098.8-

Conditions as in Example 1 with the pen for image recording traversed, the results shown in Table 8 were obtained.

Table 8

Registration color additive Red Glutin rice starch purple Amylopectin dark brown Lanthanum propionate dark brown Piperine dark brown Cellulose with zinc chloride treated blue Tetramethyl paraphenylenediamine blue N, N ^t -dimethyl-paraphenylenediamine blue Tetramethyl-diaminodiphenylmethane Tris- (p-dimethylaminophenyl) -

methane

3,4-benzo-6-dimethylaminofluoran

Bis (p-diethylaminophenyl) phenylmethoxymethane

without additive

purple red blue

very light yellow

Example 10

A mixture of the following ingredients was milled in a ball mill for a full two days and nights for the preparation of a dispersion liquid.

409884/0988

Component parts by weight of montmorillonite 10.0

Polyvinyl butyral

(Pg 1500) "" 3.0

Sodium j ο di d 1.0

Ethanol 30.0

The dispersion liquid prepared in this way was applied to an aluminum-coated paper in a thickness of approximately 8 μ and dried to obtain the recording paper I.

On the other hand, another dispersion liquid was made from a mixture of the following ingredients and then applied to impregnation paper, which is dried and made into recording paper-II became.

Component parts by weight

Polyvinyl alcohol (degree of polymerization of 1.0 * 1000)

Addition (see table 9) 0.2 water 10.0

When the above recording paper I is electrically conductive registration under the same conditions as in Example 1 was subjected, showed on the image

409884/098 8

drawing paper a light yellow section. Afterward Papers I and II were placed on top of one another and passed through a pair of heated rollers set at 140.degree. C. for 5 seconds were held, whereupon an image having a color shown in Table 9 was attached to the image recording paper II pale yellow sections on the recording paper I corresponding locations was obtained.

Table 9

Additional registration color

Glutin rice starch red

Amylopectin purple

Lanthanum propionate dark brown

Piperine dark brown

Tetramethyl-paraphenylenediamine blue

N, N ^f -dimethyl-paraphenylenediamine blue

Tetramethyl-diaminodiphenylmethane blue

Tris (p-dimethylaminophenyl) methane purple

Light yellow without additive

Example 11

10 g of microcrystalline wax were added to a mixture of 30 g of "Amberlite IRA-401 ¹ · (ion exchange resin from Rohm & Haas Co.), 10 g of rutile type titanium oxide, 10 g of polyvinyl butyral (degree of polymerization of 1500) and 150 g of ethanol was added

40 9-8 84/0988

and the entire batch in for a full two days and nights ground in a ball mill to produce a dispersion liquid.

The dispersion liquid produced in this way was applied to an aluminum plate about 50 η thick by means of a doctor knife in a layer thickness of about 10 η and dried under natural conditions to obtain a writing plate. This was then subjected to an electrically conductive recording in which a tungsten pen connected to the negative pole and the aluminum plate to the positive pole and a. Voltage of about 150 V was applied while the pen drove along the writing plate. As the current flowed, the sections became transparent and at the same time water-repellent. -

The writing surface on which such an image was recorded was then used for offset printing by means of a The offset printing device was used, whereby a good print of an image could be obtained which the electrically conductive image recording. The duration of use this writing plate for offset printing was approximately 4000 to 10000 sheets.

Instead of the above-mentioned microcrystalline wax, paraffin wax was used for the production of the dispersion

409884/0988

liquid is used in the same way as mentioned above. The application of the dispersion liquid to the writing plate, the electrically conductive recording on the coated writing plate and the subsequent offset printing were carried out in exactly the same way as above. the results obtained were practically the same as above.

Example 12

A mixture of the following ingredients was made in a ball mill for a full two days and nights ground a dispersion liquid.

Component quantity .

5-phenyl-2,3-bis- (p-di- 6g ' phenyl) tetrazolium chloride

faujasite-like synthetic zeolite (molecular sieve 1-3X from ^{30 ß} Union Carbide Co.)

Rutile type titanium oxide 10 g

Polyvinyl butyral (degree of polymerization 1500) 10 g

Ethanol 150 g

The resulting dispersion liquid was applied onto an aluminum plate of about 50 n. Thickness using a Rackels to a film thickness of about 10 / a, and dried under natural conditions. Thereafter, the writing plate was subjected to electroconductive recording by

400884/0988

a tungsten pen with the negative pole and the aluminum plate with the positive pole of a power source connected and a current of about 150 V was impressed, while the pen on the writing plate with a "Scan speed of 50 cm / s along. As a result of the electrical current flow, the claimed Parted a reddish-purple color and became at the same time water repellent.

The writing plate with the image recorded in this way was then subjected to offset printing using an offset printing apparatus, whereby a good print of an image corresponding to the electrical image recording could be obtained. The useful life of this described plate for offset printing was approximately 3000 to 5000 impressions.

Instead of the above-mentioned 5-phenyl-2,3-bis (p-diphenyl) tetrazolium chloride different imaging agents as shown in 'Table 10' were used for the Preparation of the dispersion liquid used in the same manner as mentioned above. The application of the dispensing liquid on the writing plate, the electrically conductive recording on the coated writing plate and the subsequent one Offset Dr.uck were made in exactly the same way as stated above. The results obtained are shown in Table 10.

. 409884/0988

Table 10

imaging agent printability

2,5-diphenyl-3- (4-styryl-phenyl) -tetrazolium chloride

3.3 ^l - (4,4'-biphenylene) -bis- (2,5-diphenyltetrazolium chloride) 3,3'-dianisole-bis (4,4'- (3,5-diphenyl) -tetrazolium chloride1 O Θ

CH

Il

-N

(1)

of

= N-I

(13)

NO ₀

2,2 ', 5,5'-Tetra-p-nitrophenyl-3,3' - (3,3'-dimethoxy-4,4'-biphenylene) -ditetrazolium chloride

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imaging agent

Printability

3,3 '-Dime thoxy-4, A'-diphenylene-O ¹ , 3 "■ bis- F2-pheriy1-5- (2-hydroxyphenyl) -tetrazoliumacetic acid salt ^)

2,5-diphenyl-3- (4-nitr.ophenyl) tetrazolium fluoroborate

Comment:

Θ O

very good good

Example 13 .

As the porous compound A, molecular sieve 13X from Union Carbide Corporation, USA), "Amberlite IR-120" (Rohm & Haas Co., USA) and bentonite (clay mineral of the montmo.rillonite group) were selected, and each of these substances underwent an exchange reaction in an aqueous solution to a sufficient degree with each of the different. Cations B ¹ that contribute to image formation, such as silver ions, copper ions, nickel ions, cobalt ions and zinc ions, are subjected to B to produce various compounds.

. ' After drying the compounds B in vacuo were 50 g of each to a mixture of 15 g of polyvinyl butyral (degree of copolymerization of 1500), 10 g of titanium oxide and 100 g Ethanol was added and the entire batch was ball milled in a ball mill for a full two days and nights to prepare

40988A / 0988

a dispersion liquid.

The dispersion liquid thus obtained was then applied to an electrically conductive carbon paper with a doctor blade in a coating thickness of 10 yes and dried for 2 minutes at a temperature of 100 ^° C., whereby conductive recording paper or recording material was obtained.

Thereafter, the recording paper was subjected to electrically conductive recording by using a tungsten pen connected to the negative pole and the conductive carbon paper to the positive pole of a power source and A direct current of about 200 V was applied while the pen touched the recording paper at one speed of 50 cm / s. The results are shown in Table 11.

Table 11

Exchangeable cation B ¹ Porous connection Descriptive color

availability

silver

Copper nickel cobalt zinc

4Q9S84 / 0988

Molecular sieve N Θ greyish 13X Il black M. Θ Brown N Θ M. O Il O H

Exchangeable cation B 'Porous connection Descriptive shade

availability

silver

Copper nickel cobalt zinc

Silver copper nickel cobalt zinc

Amberlite U greyish IR-120 black N O Brown H O M ' R. O H N Δ M. Bentonite O Il N Δ M. Ν Δ H H Δ N M. Λ H

Note: The symbols for the writability mean: 0 very good

■ "■" o- ^{···· ßut}

Δ. ··. ···· - ··. ·· acceptable ^

Example 14

In the dispersion liquid of Example 13, 2 g of each of the electrolytic shown in Table 12 was added Color former "was uniformly dispersed and image recording was carried out in the same manner as in Example 1. As a result were made by reversing the polarity of the pen

09884/0988

get two color images from positive to negative and vice versa. As a porous compound B was with silver ions exchanged molecular sieve 13X used. The results are shown in Table 12.

Table 12

electrolytic color registration ink registration ink
builder (with positive Po- (with negative Po

larity of the pen) larity of the pen)

Leucoauramine yellow greyish black

3,6-Di- (dimethylamine) - red greyish black

xanthene

3,7-diamino-5-phenyl-red greyish black

5,10-dihydrophenazine

Leuco malachite green green. greyish black

4-methoxy-l-naphthol blue grayish black

409884/0988

Claims (9)

Claims ⁽ , 1. Image recording material, characterized by a recording or writing layer with at least one electrically conductive agent, which is formed by at least one representative of the group of porous compounds with a polar substance contained therein .. 2. Recording material according to claim 1, characterized in that that the registration or writing layer also contains an image-forming agent and / or a binder contains. 3 »Recording material according to claim 1 _%, characterized in that the recording or writing layer is a single layer which has at least one representative from the group of porous compounds with a polar substance contained therein and an image-forming agent, 4. Recording material according to claim 1, characterized in that that the registering or writing layer comprises a conductive layer which has at least one representative from the group of porous compounds with polar substance contained therein and an image-forming substance Layer containing at least one image-forming agent, wherein the image-forming layer on the conductive Layer is piled up. 409884/0988 5. Recording material according to claim 1, characterized in that the porous substance containing a polar substance Compound at least one representative from the group of ion exchange resins, electron exchange resins, hydrophilic crosslinked polymers, porous polyester resins and microporous bodies of copolycondensed resins of dichlorodiphenylsulfone and bisphenol is each at least one member from the group of polar solvents, inorganic Contain electrolytes and organic electrolytes, 6. Recording material according to claim 1, characterized in that the polar substance absorbing or containing porous compound at least one representative from the group of silicas, silicates, aluminum silicates and basic aluminum / magnesium carbonates, each of which has at least one representative from the group of polar solvents, contain inorganic electrolytes and organic electrolytes. 7. Recording material according to claim 1, characterized in that the A _n part of the polar substance ent-. holding porous compound in the recording or writing layer of 30 to 98 wt.% And in particular 70 to 90 Gew.5ό, based on the total weight of the writing layer, ranges. 409884/0988 8. Procedure for registration or image recording by electrical current flow, characterized in that an electrical current is passed through a writing layer that sends at least one image-generating agent in it and contains at least one member from the group of porous compounds with polar substance contained therein and registered an image. 9. The method according to claim 8, characterized in that the absorbing or containing a polar substance porous compound at least "one representative from the group of ion exchange resins, electron exchange resins, hydrophilic crosslinked polymers, porous polyester resins and microporous bodies of copolycondensed resins of Dichlorodiphenylsulfone and bisphenol 'is, each of which contains at least one representative from the group of polar solvents, inorganic electrolytes and organic electrolytes Iyte included. 10, method according to claim 8, characterized in, that the porous compound containing a polar substance has at least one representative from the group of silicic acid ^ Silicates, aluminum silicates and basic aluminum / magnesium carbonates is, each at least one representative from the group of polar solvents, inorganic electrolytes and organisehen, contain electrolytes. 409884/0988 Il. Method according to claim 8, characterized in that that the current flow is brought about by a stylus or a pen. 84/0988