DE2303814B2 - Electrically sensitive recording material - Google Patents

Description

3 4

An electrically sensitive recording material that uses an electrically reducible metal compound

Contains CuJ, but can be electrically conductive. However, CuJ can be up to 30 parts by weight each

capable carrier. Part by weight of metal compound can be used.

As noted above, it has been found that, by adding copper iodide to a layer of copper iodide, it is illustrated by the drawings in which FIG - obtained recording material according to the invention using tric conductivity and is an intensive one of paper as a non-conductive carrier,
High density patterns on the electrically sensitive- F i g. 2 a cross-section of an embodiment of the borrowed registration layer can be formed, xo registration material according to the invention using

The electrically reducible metal compounds, using a metal-coated paper as an elec-

which is responsible for the formation of the electrically sensitive registration troconductive carrier,

layer can be used are as follows: Fig. 3 shows the method of registration

Zinc Oxide (ZnO), Cadmium Oxide (CdO), Blarium- the electrically sensitive registration layer that

oxide (BaO), tin oxide (SnO ₂ ), lead oxide (PbO, 15 was produced according to the invention.

Pb, O _a , PbO ₂ ), titanium oxide (TiO.,), Zirconium oxide (ZrO,), The figures show the strength of the paper and the

Antimony oxide (Sb ₂ O ₃ , Sb ₂ O ₄ , Pb ₂ O ₅ ), bismuth oxide coated layer on it enlarged for reasons

(Bi ₂ O; ,, Bi ₂ O ₄ , Bi ₂ O ₅ ), vanadium oxide (V ₂ O ₅ ), molyb- the better illustration.

denoxide (MoO ₃ ), tungsten oxide (WO-), cerium oxide A binder, the ~ us of the above

(CeOj), molybdic acid (H ₂ MoOA tungstic acid 20 group of orsanischer BindenJttel is selected,

(H ₂ WO ₄ ), molybdates (Na ₂ MoO ₄ , K ₂ MoO ₄ , CaMoO ₄ , is dissolved in a solvent and this solution

PbMoO ₄ , (NHJ ₂ MoO ₄ , (NHJ ₆ Mo ₇ O ₂₄ ■ 4H "0, at least one of the electrically reducible metal

Na ₂ Mo ₈ O ₂₅ -HH ₂ O, (NHJ ₈ [CrMo ₁₂ O ₄₂ ] ^ HAMo compounds and CuI in the above-mentioned

lybdosilicic acid (H ₄ [SiO ₄ MOi ₂ O ₃₆ ]), molybdophos ratio added. The mixture obtained is

phosphoric acid (H ₃ [PO ₁ Mo ₁₂ O ₃₈ ]), tungsten phosphorus 25 parts or suspended in a ball mill to obtain a

acid (H ₃ [PO ₄ W ₁₂ O ₃₈ ]), cobalt oxides (Co ₂ O ₃ , homoeene distribution of the metal compound and CuJ

Co ₃ O ₄ ), mercury oxide (HgO), chromium oxide (Cr ₂ O ₃ ), to be obtained in a solution of the binding agent. Which he-

Niobium oxide (Nb ₂ O ₅ ), tantalum oxide (Ta ₂ O ₅ ), manganese-containing dispersion is applied to a paper surface 1

oxide (MnO ₂ ), antimonic acid (HSbO ₃ , IL ₁ SbO ₄ ), with the help of a wire hanger, for example.

Stannic acid (SnO ₂ -XH ₂ O), titanic acid (H ₄ TiO ₄ , 30 and then brought at a temperature of about

H ₂ TiO ₃ ), vanadium _{acid (HVO 3} ), selenic acid (H ₂ SeO ₄ ), 10O ⁰ C with the formation of an electrically sensitive

Bismuthate (NaBiO ₃ ), zinc sulfide (ZnS) and antimony registration layer 2 on the surface of the paper 1

sulfide (Sb ₂ S ₅ ). dried. The preferred strength of the registration

Among the metal compounds mentioned, the layer can be about 5 to 100 a.

ZnO, TiO ₂ , V ₂ O ₅ , H ₂ MoO ₄ , H ₂ WO ₄ and 35 As in Fig. 2 is shown alternatively, a

(NH ₄ ) Mo O -4HO electrically sensitive registration plates; ht two on each other

^{7 24 2 of} a metal coating 3 of a metal-coated

are most preferably used. Paper 1.

The following organic compounds can according to FIG. 3, the thus obtained can be electrically preferred 40 sensitive recording material aJ uses a flat plate 4 as a non-conductive binding agent are: polyvinyl alcohol, polyvinyl acetate, polyvinyl are brought, and a constant or alternating chloride, Ethyl cellulose, gelatin, butadiene-styrene voltage of 50 to 2 (K) volts is connected to a uadei-like Copolymer, Vinyhcctat-Crotonsäure-Misch- electrode 5 and a lead wire 6 applied, and the polymer, polymethyl methacrylate, Polyäthylmeth- needle-like electrode is at a speed acrylate and the like. Preferred solvents for dissolving 45 from 25 to 400 m / min, in light contact with the of the binder are as follows: Registration layer 2 is drawn through.

Water, aqueous ammonia, toluene, xylene, ethyl- A current of 5 to 20OmA flows between the methyl ketone, methyl isobutyl ketone, cyclohexane, Al needle-like electrode 5 and the registration layer 2, Alcohols such as methyl alcohol and ethyl alcohol, aliphatic and the continuity of the current cause the metal tables Hydrocarbons, like Petroleumlösui.gs- so bond, to a dark compound that leads to the medium and isoparaffinic solvents. surrounding non-reduced parts of the electrically

The carrier of the registration-sensitive registration layer according to the invention in the color contrast material can preferably be a non-conductive carrier to be reduced. An intense black paper or plastic film can be used. A pattern is formed corresponding to the path of the needle-electrically conductive carrier, for example a 55-like electrode. The following examples of metal-coated film, such as with aluminum, illustrate the invention,
layered paper or foil and metal foil, such as

Aluminum foil, however, can also be used. Example X
the.

The electrically sensitive Re-60 A dispersion was used to produce a

The registration material consists of 1 part by weight of binding agent. Use electrically sensitive registration material.

and 5 to 10 parts by weight of a mixture of det, made up of the following ingredients

Copper iodide and at least one of the above:

given electrically reducible metal compounds. - _M _ ._

The mixture is distributed in the binder. 65 HgMoO ₄ to g

The electrically reducible metal compound and ~ ^uJ ·. · ■ · · -; ; ■ · · :. ' · ■ ¹ V; ^G

Copper iodide is preferably used in a ratio of butadiene-styrene mixed polymer ... 15g

^{1 to 10 parts by} weight of copper iodide per part by weight of ^{toluene 10L ml}

The butadiene-styrene copolymer was dissolved in toluene, and H ₂ MoO ₄ and CuI were added to this solution. This mixture was homogenized in the ball mill for 24 hours. The homogeneous dispersion produced in this way was applied to a paper surface with the aid of a wire hanger and then dried at a temperature of about 100 ° C. in order to obtain an electrically sensitive recording material according to the invention in which a pale yellowish recording layer with a thickness of 10 μ formed on the paper The resistance of this recording layer was 10 ³ Ω / ηι ^2. In the electrically sensitive recording material thus produced, a pattern of the type shown in FIG Volt (the needle-like electrode is the positive electrode) and a moving speed of the needle-like electrode of 100 m / min. An intense black pattern with a density of 1.3 was obtained on the recording layer, and the density was determined by a densitometer. For comparison, an electrically sensitive The recording material was prepared in the same way as mentioned above, except that 120 g of H ₂ MoO _{4 were used} in place of 20 g of H ₂ MoO ₄ and 100 g of CuI. The resistance of the registration layer obtained in this way was approximately ΙΟβΩ / m ² .

For the comparative registration material, the same procedure mentioned above was followed for the purpose of FIG Formation of a pattern is repeated except that a DC voltage of 200 volts instead of 100 volts was applied. However, the pattern could not be obtained. An electrically sensitive one Registration material, which through education eirtör electrically sensitive registration layer was produced, which does not contain any CuJ on a non-conductive substrate, there can be no pattern on the registration layer as shown in FIG. 3 result. Another electric Comparative sensitive registration material containing CuI was tested on the same as mentioned above Wise made except that aluminum coated paper is used as a support instead of paper

ίο was used. The registration material produced in this way could give a blackish pattern with a density of 1.0 by repeating the same procedure mentioned above except that a DC voltage of 80 volts and an electrode speed of 160 m / min. An electrically sensitive material with a registration layer containing CuJ on an electrically conductive substrate can even be an intensive one Patterns result when a relatively high speed of movement of the electrode is used. It an increase in the registration speed can be achieved in this way.

Examples 2 to 10

Other electrically sensitive recording materials 2 to 10 were made by using the same The procedure as that of Example 1 was repeated except that metal compounds, binders and solvents as indicated in the table below were used. In these examples paper was used as a support.

A sample was produced for each of the recording materials 2 to 10 analogously to Example 1 and that samples obtained in this way are assessed. The results obtained are summarized in the table below.

at
game metal
link CuJ binder solvent Created
DC voltage template colour density (G) (G) (G) (ml) (V) greenish black 1.2 2 H ₂ MoO ₄
20th 60 Ethyl cellulose
10 Ethyl alcohol
70 100 black i, c 3 H ₂ MoO.,
20th 20th Vinyl acetate
Crotonic acid
Mixed poly
merisat
5 methyl
alcohol
50 100 green Brown 0.8 4th KiMoO ₄
20th 100 Butadiene styrene
Mixed poly
merisat
15th toluene
100 200 black 1.0 5 H ₈ WO ₄
20th 20th Vinyl acetate
Crotonic acid
Mixed poly
merisat
5 methyl
alcohol
50 100 black 1.0 6th (NH ₄ V
Mon ₇ O ₂₄ ·
4H ₂ O
20th 20th Vinyl acetate
Crotonic acid--
Mixed poly
merisat
5 methyl
alcohol
50 100 sehwäfz I ^ 7th VA
20th 30th Polyvinyl
alcohol water
50 LöO *

metal
link ZnO 10 TiO ₂ 10 7th 2 303 814 binder solvent b 8th template colour density (G) H ₂ MoO ₄ (ΝΗ ₄ ) _β CuJ (il) (ml) Brown 0.8 At-
game 10 Mon ₇ O ₂₄ · (G) Vinyl acetate methyl Created
DC voltage black 4H ₂ O 40 Crotonic acid alcohol (V) 8th 10 Mixed poly 70 100 ZnO merisat 10 black 1.0 Butadiene styrene toluene 40 Mixed poly 70 9 merisat 100 10 blue black 0.7 Butadiene styrene toluene 40 Mixed poly 70 10 merisat 100 1.0

As can be seen from the data given above, it is preferable to use electrically sensitive recording materials can be obtained by using an electrically sensitive recording layer, the CuJ in an amount of 1 to 10 parts by weight per part by weight of an electrically reducible metal compound contains on a non-conductive carrier, forms. If the electrically sensitive registration layer, which contains CuJ, on an electrically conductive one Support such as aluminum foil or aluminum coated paper is formed, so can be a good one High density patterns with relatively low voltage and high electrode movement speed can be obtained.

1 sheet of drawings

409.527 / 31

Claims (2)

which are described in U.S. Patent Claims: 3,138,547 and 3,516,911. The electrically sensitive registration material consists of the 1. Electrically sensitive recording material, essentially consisting of a recording layer formed on an electrically conductive one consisting of a carrier and a recording layer formed on the carrier. The electrically sensitive register layer located on the registration carrier consists of a powder mixture of an electrically reducible metal compound, such as ZnO, and the electrically sensitive registration layer SnO ₂ , TiO ₈ , Bi ₂ O ₃ , V ₂ O ₅ , Sb ₂ S ₅ or H ₂ MoO ₄ and a binding agent and an electrically reducing synthetic rubber or ethyl cellulose distributed in the binding agent such as a synthetic resin. metal compound and copper iodide (CuJ) The electrically kitable carrier is for example consists. a metal foil or an electrically conductive plastic 2. Electrically sensitive recording material, film. The electrically sensitive registration according to Claim 1, characterized in that the material can be used for the same purposes Mixture of one part by weight of the electrical 15 den as the dry registration material. A blackness reducible Metal connection and 1 to 10 matched pattern is formed on the registration thread, important copper iodide. by drawing the needle-like electrode through it. 3. Electrically sensitive registration material! The object of the invention is now to provide a according to claim 1, characterized in that improved electrically sensitive recording material to provide the electrically reducible metal compound ZnO 20. and / or TiO ₂ and / or V ₂ O ₅ and / or H ₂ MoO _{4 The} subject of the invention is thus an electrical and / or H ₂ WO ₄ and / or (NH ₄ ) _e · Mo ₇ O ₂₄ · 4H ₂ O sensitive recording material that consists of a carrier is. and one on the carrier electrically sensitive registration layer and that 25 is characterized in that the electrically sensitive Borrowed registration layer made of a binder and a in the binder distributed mixture of an electrically reducible metal compound and copper There is already known a dry recording material consisting of iodide (CuJ). which consists of the components indicated below 30 According to a preferred embodiment of the and produced as follows: electrically sensitive regions according to the invention The dry registration material is produced, the mixture consists of a mixture of an electrically destructible substance on a weight part of the electrically reducible metal electrically conductive carrier is applied, the bond and 1 to 10 parts by weight of copper iodide, an electrically conductive layer, for example carbon. The electrically reducible metal is preferred. lenstoffschicht, has on a carrier surface. compound ZnO and / or TiO- ₂ and / or V ₂ O ₅ and The electrically destructible substance is, for example, H ₂ MoO ₄ and / or H ₂ WO ₄ and / or (NH ₄ ) ₆ Mo ₇ O ₂₄ · a synthetic resin. 4H ₂ O. In the dry recording material, the electrical resistance of the recording electrically conductive layer according to the invention as the one electrode material is low. It can therefore turn a non-conductive one, and the other electrode is a metallic, carrier can be used and consequently cheap needle-like electrode, which can be obtained with the layer of recording material. Further, an electrically destructible substance may find an intense black pattern of high density in contact. The registration layer can be obtained by applying a constant or alternating layer.
Voltage, for example from 100 to 150 volts, between 45 CuJ is one of the two which increases the electrical conductivity due to the destructible substance. If the electrodes are not separated, an electrical current flows. The metal compound and CuJ are in the binding current (10 to 20 mA), and as a result of this, the medium is evenly distributed. The electrically sensitive one Layer is destroyed and the soot layer occurs. The recording material is electrically sensitive. jo borrowed registration layer, which has a high electrical The needle-like electrode is with simultaneous conductivity. The electrically sensitive one in touch with the layer. The carbon black pattern recording material of this invention has the advantages Is on the carrier by controlled through-on that • stretching of the electrode formed. _{1 A non-conductive door should} be left The dry registration material is on the fac- 55 _{can (the} use of an electrically conductive Original prayer applied. _t ..,. ,, The carrier is not mandatory However, such dry registration material has written) and various disadvantages, for example, in loading _{2, a intens' ives pattern of high D} i e on the _CHT stenen, aaii electrically sensitive registration layer 1, the dry registration material cannot be obtained at a sufficiently high registration speed is sensitive and can, by applying a relatively low voltage 2. The dry registration material becomes unwanted. Sparks and disturbances due to the increase in the applied _. . ,, .- ,. ^ · "· Λ Voltage causes, thereby registering _v ^Em non-conductive substrates, such as paper or a is accelerated 615 Kunststoffohej is compared to an electric conductive carrier, such as aluminum foil or Alu-Ais. Replacement of this dry registration material is minium coated paper, cheap,
The electrically sensitive recording materials are an essential part of this.