DE2301266A1 - RECORDING MATERIAL WITH ELECTRICALLY CONDUCTIVE OR ANTISTATIC LAYER - Google Patents

Description

Recording material with electrically conductive or antistatic Layer.

This invention relates to a recording material, consisting from a carrier made of paper or synthetic polymers, which is covered on at least one side with a layer that acts as an electrically conductive or an antistatic layer can.

Electrically conductive products are used in recording materials for discharging static charges. As is known, the usual supports consisting of plastic films consist of normal photographic material on the basis of silver halide emulsions have the property that they are electrostatically charged, so that the charged films strongly attract dust from the environment and thus become dirty on their surface. Farther are latent discharge images in silver halide emulsions which are applied to such carrier films in the Development visible. Such an electrostatic charge occurs when the carrier film or the photosensitive Photo material is moved quickly during winding or unwinding in the casting, cutting or packaging machines and when the PiIm runs through the camera or the projector. It is also known that the static charge can be reduced if the synthetic resin substrate is covered with a conductive Coating auxiliary layer.

With other recording materials such as electrostatic Copying is used if paper or some other insulating medium is used in a predetermined pattern electrostatically charged, the carrier being conductive or

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must be covered with a conductive layer. For example, in the case of an electrophotographic recording material, there is a photoconductive layer with a conductive layer or a conductive path in contact, the latter serving to the electrostatic charges at those points of the photoconductive layer that are exposed to light rays to lead.

In the case of electrographic material with an insulating layer on which an electrostatic charge pattern is created by image-wise or when charging is built up - e.g. with a modulated electron beam - the conductive material is used (Carrier or layer) to apply a voltage to it, so as to create the electrostatic charge pattern that appears the insulating, top layer, is applied.

In the following description and claims, the term “recording material” includes the materials used in photographic, electrophotographic and electrographic processes in which the surface resistance of the electrically conductive layer is 15 % more relative

11
Moisture must not exceed 10 ohms / square, although according to the studies by Nakao, Sakomoto and Katagiri (page 105 of the preprint of the Tappi First Reprography Conference, St. Charles, 111., USA, 1971), the reverse side is already slightly soiled of the wearer can come if the

10

the value is higher than 4.10 ohms / square.

Electrically conductive layers for dissipating electrostatic charges can also be useful in recording materials, in which light-sensitive semiconductor compounds are activated in the opposite direction by electromagnetic radiation and in which the activated patterns then deliver irreversible images through a chemical redox process.

The invention provides a recording material that consists of a Paper or synthetic polymer carrier and one

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electrically conductive layer on at least one side of the support "consists of" at a relative humidity of 15 %

11 has a surface resistance of no more than 10 ohms / square and consists entirely or predominantly of a water-soluble Polymers consists, which has been obtained by aminoalkylation of polyethyleneimine with an epoxyverbinding, the one terminal, quaternary ammonium group carries.

The epoxy compounds bearing a terminal, quaternary ammonium group correspond to the formula:

E ₀ - NE-CH ₀ -CH-CH ₀ ² ^ - ² \ ' ²

5
in which:

E is a branched-chain or straight-chain alkylene group with up to 4 carbon atoms,

E _x ., Ep and E ₅ , (identical or different) each have an alkyl group with up to 4 carbon atoms, a cycloalkyl group, an aralkyl group or, together with the nitrogen atom, a heterocyclic amine group, such as pyridine, piperidine and morpholine, and

X is an anion such as a halogen atom such as chlorine, bromine and iodine, a sulfate group, a methyl sulfate group, a p-tolyl sulfonate group, an acetate group, and the like.

The anion X can in principle come from any suitable acid. The easier production more and more especially However, because of the better conductivity, the chloride is to be preferred.

Suitable epoxy compounds bearing a terminal, quaternary ammonium group are, for example, N-trimethyl-N-glycidylammonium chloride, N-triethyl-N-glycidyl-ammonium chloride and N-triethyl-N g] ycidyl ammonium p-toluenesulfonate.

This, one terminal quaternary ammonium group bearing Epoxyverbindingen can be produced directly by reacting a compound of formula Ey oxy!:

CH ₀ -CH-EX

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with a tertiary amine of the formula:

can react, as indicated by Paquin in "Epoxyverbindungen und Epoxyharze", page 202 (Springer-Verlag, 1958). In these formulas, X, R, R ^, R ₂ y ⁰¹ ^ & * have the same meaning as given above.

Epichlorohydrin is preferably used, but it is also possible to use other compounds bearing an epoxy group, such as, ^for example, 1-chloro-3, z i-epoxybutane, 1-chloro-1-methyl-2,3-epoxypropane and 1-chloro- 2-methyl-3,4-epoxybutane.

A voi ^s zuziehendes tertiary amine is trimethylamine.

The one terminal quaternary ammonium group-bearing epoxy compounds can also be represented in two reaction stages, where glycidylamines are formed at a first stage, as it were, by Gilman and lullhart in J.Am.Chem.Soc., 71 ■> (194-9) 14-78. To do this, a secondary amine, for example, is allowed to react with epichlorohydrin as follows: T? \ - p _v "OH

^Ä 1., NH + Cl-CH ^ -CH-CH ₀ * · 51 ^ N-CH ₀ -GH-CH ₀ Cl ►

^Ά 2 0 ^d OH

¹ \ -CH _O -CH-CH _O R ₂ N ₀ /

In a second reaction stage, the glycidylamine is alkylated, the one bearing a terminal, quaternary ammonium group Epoxy compound is obtained:.

R'T? "

¹ \ -CH _O -CH-CH _O + R ₂ X> · E ₀ -N-CH ₀ -CH-CH ₀

_E s d. ^ s 2 3 _R 2/2 \ / 2

2 0 ^K 3 0

as described by Eurness and Bayer in J.Org.Chem., 28 C963), 2283-2288 is described.

The alkylating agent R, X can be alkyl sulfonates,

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Sulphates, halides or the like. Act.

The aminoalkylation of polyethyleneimine with a enclständigs, quaternary Aimsoniumgruppe bearing Spoxyverbindunß is preferably carried out in an aqueous medium at relatively low temperatures, eg at about 5O ⁰ C, wherein the concentration of polyethyleneimine and epoxy compound in the aqueous medium as high as possible ₅ since these low temperatures and high concentrations of polymer and epoxy compound the hydrolysis of the epoxy group is reduced to a minimum.

If there is still a high degree of substitution on the amino groups des Polyäthylenimiiis should be achieved, must all reactive amino groups are in the form of free amino units and must not be present as a salt.

If the aminoalkylation takes place in an organic medium, for example in dimethylformamide, there is no fear that the epoxy groups can be hydrolyzed, so that the temperature in the reaction mixture can be much higher, for example above 10O ⁰ C.

It is known that the polymerization of .Ethylenediamine does not lead to a polymer which consists exclusively of units with a straight-chain structure, but which is also branched to a certain extent. According to investigations by Zhuk, Gembitskii and Kargin (Eussian Chem. Rev., J54 (July 1965), No. 7 p.523), the degree of branching in the polyethyleneimine depends on the acid concentration and temperature prevailing during the polymerization. This degree of branching can vary between 12 and 38 % . The structural formula of polyethyleneimine can be written as follows:

CH ₂ OH ₂

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depending on the degree of branching χ between 13.6 and 61.3 Col-% and y represents between 38.7 and 86.4 mole percent.

As can be seen from the above formula, contains polyethyleneimine primary and secondary amino groups. If one now leaves polyethyleneimine with the one carrying a terminal, quaternary ammonium group If the epoxy compound reacts, the first substitutions will probably be on a hydrogen atom of the primary amino groups take place, whereby a secondary amino group is formed will. The further substitution then takes place on these secondary amino groups and also on those to the main chain of the polymer belonging, secondary amino groups. Deodorant can depending on the ratio of.eine terminal, quaternary ammonium group-bearing epoxy compound to polyethyleneimine, the primary amine groups or some or all of the primary and secondary amino groups of the ethyleneimine units in the polymer be aminoalkylated.

The products of the aminoalkylation of polyethyleneimine according to of the invention have significant advantages. No by-products are formed during the reaction, so that the separation of the aminoalkylated Poiyäthyleiiimins from the reaction mixture is not necessary and no further purification is required can. Rather, the reaction mixture itself can be used; this is a very economical process.

The electrically conductive polymers according to the invention consist of repeating units of the general formula:

A-CH ₀ -CHOH-RN 2

in which A represents a single chemical bond or a group with the formula:

-CH ₂ -CH ₂ -NR ₄ -

where R ,, represents a hydrogen atom or a group with

of the formula _ _C H ^ CHOH-RNR ₀ ; X, R, R., R ₀ and R _x have the

2 IVd ^ 1 2 3

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Bedöuti ^ r: v ^r i & olx-i indicated.

The colect does not contain the polyethyleneimine before the aminoalkylation with a terminal, quaternary ammonium group more load-bearing. Epoxy compound has little impact on the electrical conductivity of the polymer after the aminoalkylation, however, it does have an effect on the viscosity of the aqueous adhesive composition that contains the aminoalkyl! er te poly- ^ Contains thyleniisine. Thus one becomes the molecular weight of the Select the material to be used so that the desired final viscosity; is obtained. Experiments have shown that polyethyleneimines with molecular weights between 1200 and about 50,000 amino-alkylated, and that without technical Difficulty applying a continuous layer of these ^ iiio-alkylated Polyäthyleniminsn on a carrier leaves.

Of course, the electrical conductivity of the amino alkylated polyethyleneimines according to the invention is proportional to the degree of substitution of the amino groups in the polymer, the amount of aminoalkylated polymer applied per unit area and the relative humidity of the rail. It has been found that at about 20 ⁰ C and 15% relative humidity from a polyethyleneimine at which 10% of the primary and secondary amino groups with H-Jüthyl-N-glycidylammoniumchlorid have been substituted, at least 2 g / m must be applied, to obtain a layer with a surface resistance that

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is below 10 ohms / square, which has just been adjusted as the limit value above. However, if only 1.5 g / m 2 are applied, polyethyleneimines with a degree of substitution of at least 20 % must be used. Of course, the degree of substitution can also be much higher and be around 100 % , whereby a corresponding improvement in the electrical conductivity is obtained.

The erflridungsgemässen, electrically conductive polymers are water soluble. Your electrical conductivity is determined by that one measures the surface resistance of layers,

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which have been applied as a 10% strength aqueous solution of the polymer. The surface resistance is measured with the aid of a cell, the two poles of which are 0.5 cm wide and are arranged at a distance of 1 cm.

These layers can be used as an electrically conductive layer for a electrographic recording material is only used if their surface resistance does not exceed certain limits. The aforementioned publication by

Ί0 Uakao et al. Gives a value of 4.1O ohms / square as the limit for the contamination of the back of the paper carrier. But the electrical conductivity depends on the relative humidity. It is therefore advisable to have a surface resistance value of less than 10 ohms / square at 15% relative humidity. In such a case, when the relative humidity is very low, slight back marking is inevitable. However, the image retains sufficient quality to be commercially acceptable.

Layers of the electrically conductive, polymeric substances can be applied by spraying, with a brush, with rollers or with the Brush knife, with an air brush or by brushing on different ones Kinds of carrier, such as paper, can be applied. Films made from synthetic polymers such as cellulose acetate, polystyrene, Polyester, polycarbonate, can also be coated with the electrically conductive layers. If required, these carrier films can be provided beforehand with an adhesive layer of a known type, to which the later electrically conductive layer is applied.

The particular amount of electrically conductive polymer material used depends of course on the carrier used. If this carrier consists of paper and, in particular, of highly porous raw paper, more electrically conductive polymer material will have to be applied than in the case of a non-porous synthetic carrier made of polyester, for example. However, in general, an amount of 0.5 to 7 ₅ 5 g / m sufficient to provide a good conductivity to the layer.

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When paper is used as a carrier, they become electrical conductive polymer materials ensure sufficient conductivity even if the paper is thoroughly covered with a aqueous solution of the inventive, electrically conductive polymer materials is impregnated. After drying the so impregnated paper "remains the electrically conductive polymer material evenly distributed throughout the paper carrier. The paper carrier can also be made electrically conductive by by adding a sufficient amount of an aqueous solution of the electrically conductive polymer materials to the paper pulp, wherein the amount of added conductive polymer is determined by the conductivity to be required.

Except for the electrically conductive polymer according to the invention The electrically conductive layer can also contain stabilizers against migration forces, plasticizers, dispersants, pigments and binders}. such as gelatin, starch, casein, polyvinyl alcohol and the like. It should be clear that the addition of such binders increases the electrical conductivity the layer decisively influenced. In particular, it is found that, as can be seen from the specialist literature, -Polyvinyl alcohol and gelatin the conductivity of the layer far stronger lower than e.g. 'strength.

Furthermore, the electrically conductive polymers according to the invention can also be combined with small amounts of inorganic and organic salts compared to the amount of electrically conductive polymers, such as sodium chloride, sodium sulfate, sodium nitrate and the corresponding potassium and ammonium salts, sodium acetate, citric acid amides, hydroxyIpropylsucrosis monolaurate, etc. As is known, these salts are electrically conductive, and inexpensive, but have ^ _en disadvantage that their conductivity is highly dependent on the relative humidity. If they are combined with the electrically conductive polymers according to the invention, the low price of these salts is bound to the excellent electrical conductivity of the electrically conductive polymers at low and high relative humidity.

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When the inventive, conductive. Layer as antistatic Layer for a silver halide photographic recording material "Is used, the electrically conductive layer is generally on this film or this web either on a Surface applied which is different from that surface to which this photosensitive emulsion layer is applied or as an intermediate layer, i.e. between the support and the light-sensitive emulsion layer or the photosensitive emulsion layers.

Intended to be the electrically conductive layer for an electrophotographic Recording material are used, a photoconductive coating is applied to this polymer layer, that by dispersing or dissolving the photoconductive substance, or substances in an organic solution of an insulating Binder and by applying the dispersion or solution in the form of a layer to the electrically conductive surfaces will be produced.

The electrophotographic recording material under Use of the electrically conductive copolymer according to the invention has been produced, is flexible and possesses very good mechanical strength. There is a very good adhesive strength between the paper carrier and the electrical conductive layer.

The electrically conductive polymers can be used in conjunction with coatings of various both inorganic and organic photoconductive substances, such as those in Belgian patent 587,300, in British
Patent Nos. 964 871, 964 873, 964 874, 964 875, 964 876, 964 877, 964 879, 970 937, 980 879 and 980 880 _K in U.S. Pat
German Patent 1,058,836 and Canadian Patent 568,707. These photoconductive substances can be combined with insulating binders such as those described in US Pat 700 502, in the Belgian

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Patents 612 102, 683 145, 711 376 and 714 257 and in French patent 1,485,839 are given.

Suitable dispersants for dispersing photoconductive substances in an aqueous medium are in the "Belgian Patent 703,467 ", and the photoconductive It is known that substances can be spectrally sensitized, as in Belgian patents 708 244 and 714 258 is described.

Description and claims of the present invention are indeed on the aminoalkylation of polyethyleneimine with terminal, epoxy compounds bearing quaternary ammonium groups are limited, however, the same aminoalkylation can also be applied to other polymers containing primary and / or secondary amino groups, such as polyönylamine, polyvinylaniline, polycyclodialkylamine, Polyvinylimidazole and polyvinyl-tetrahydropyrimidine, where electrically conductive polymers are also obtained.

The invention will now be illustrated by the following examples.

example 1

A solution of 43 g of polyethyleneimine in 41 g of water is placed in a with a stirrer, reflux condenser, dropping funnel and thermometer provided and heated to 50 ⁰ C.

The polyethyleneimine has a degree of branching of about 30%, Vias corresponds to the following general formula:

CH ₂

CH ₀ ι <

where χ and y are 42.8 and 57.2 Mo1%, respectively. A 10% by weight aqueous solution of this polyethyleneimine has a at 25 ° C absolute viscosity of 8.12 cP, and its viscosity number

° 7 / c for a concentration c of 1 g / 100 ml is 0.215 dl / g. ^b P

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30.39 S N-Trimethyl-N-glycidylammonium chloride, which "at ordinary Temperature have been dissolved in 9 ml of water added dropwise to the warm polyethyleneimine solution within 90 seconds. This 30.39 g of F-trimethyl-E-glycidyl ammonium chloride id correspond to 0.2 moles of N-trimethyl-F-glycidylaimonium chloride each Moles of ethyleneimine in the polymer.

Despite the fact that the heating is switched off, the temperature in the stirred reaction mixture rises as a result of the exothermic reaction between polyethyleneimine and N-trimethyl-N-glycidylammonium chloride further from 50 to 73 ° C.

The exothermic reaction is over after about 5 minutes and the mixture is heated again in order to keep the mass at 70 ^° C. for 5 hours while stirring.

The viscous solution is diluted with 200 ml of water and from this solution the product of the addition polymerization of Polyethyleneimine and N-trimethyl-N-glycidylammonium chloride Addition of 1 l of acetone isolated with constant stirring. The aqueous acetone solution is poured off and the sticky one The residue was washed out with 0.5 l of acetone, dissolved in water and this solution was then diluted to 350 ml with water. Yield: 73 g of modified polyethyleneimine.

It should be noted that these polymers as a result of their hygroscopic property under the conditions under which they are dried, still contain about 10% by weight of water.

Examples 2-10 ,

With the same amount of polyethyleneimine as the starting material and between 0.1 and 1 mole of ethyleneimine (EI) in the polymer amounts of N-trimethyl-N-glycidylammonium chloride (GAC) will be Procedure according to Example 1 repeated. The results of these experiments are in addition to those obtained by Example 1 in the compiled in the following table;

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Modifi
adorned
Polyethy-
lenimin
example Mole GAC
g'e mol
EGG g GAC in ml of water
43 g of polyethyleneimine Encore
time in
Minutes Yield to
modify
tem poIy-
merem
G* 2 0.1 15.15 g in 4.5 ml 1 58 1 0.2 30.39 g in 4 ml 1 % 73 3 0.3 45.45 g in 13.5 ml 2 88 4th 0.4 60.6 g in 18 ml 5 102 5 0.5 75.75 g in 22.5 ml 15th 118.5 6th 0.6 90.9 g in 27 ml 17th 114 7th 0.7 106.1 g in 31.5 ml 40 149 8th 0.8 121.2 g in 36 ml 47 164 9 0.9 136.4 g in 10.5 ml 35 179 10 1.0 151.5 g in 45 ml 37 194

* As already mentioned in Example 1, the modified polymers are very hygroscopic, so that in these numbers about 10
% By weight of water are contained, despite the fact that the modified polymers under reduced pressure and in the presence of phosphorus

pentoxide to be dried to constant weight.

When the modified polyethyleneimines obtained in Examples 1, 3 and 9 were analyzed, the results were as follows
found:

at
game Mole GAC
per mole
EGG , 20
, 30
, 90 % Analysis results % C. θ / TT
70 M. % N 20th
2
25th substitution
in poly
ethyleneimine
in mol- # 1
3
9 0
0
0 7th
10
16 Cl 49
48
45 , 75
,8th
, 5 11.95
12.0
11.4 21
19
13, 17.7
26.2
89 , 86
, 05
,8th

The results show that in the aminoalkylation of the polyethylenimine an almost quantitative modification of primary and secondary amino groups takes place.

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Aqueous solutions of the aminoalkylated polyethyleneimines Examples 1-10 are applied to a paper support. The coatings are dried and then the surface resistance values of the different layers measured as described above. The surface resistances are also used for comparison uncoated paper and unmodified polyethyleneimine coated paper.

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Moles of GAO each
Mole EI Polymer
ge m.2
paper
in g Surface resistance in 10 ohms / quadtst
at 20 ⁰ C and a relative humidity
ability of 50 % 70% uncoated paper O 0 15 % 21. 5OO 530 with unmodified polyethylene
imin "coated paper 2.0
1.5 * > 42 -000 JOOO 2I.5OO
7I.OOO 193
■ 386 with polymer from Example 2
coated paper
1
3
4th
5 0.1
0.2
0.3
0.4
0.5 2.0
1.5 *
2.0
1.5 *
2.0
1.5 *
2.0
1.5 *
2.0
1.5 * > 42-500 OOO
> 42- 600,000 820
3.54O
354
710
68
152
42.5
89
18.5
53 19.3
35.4
3.86
9.7
4.72
2.36
2.83
2.36
1, 18
2.13 95,000
425-000
28th 300
35,400
3-040
5,3OO
850
1,180
530
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It can be seen that the electrical conductivity of aminoalkylated polyethyleneimine increases with increasing quaternary ammonium salt content and that the surface resistance of ohms / square is never exceeded, regardless of the relative humidity, if at least 20 mol% of quaternary ammonium groups are present.

Example 11

9 g of the same polyethyleneimine as it finds use in Examples 1-10, are dissolved in 4.6 ml of water, charged into a flask and the mixture heated to 40 ⁰ C.

Then a solution of 31 »3 g of N-triethyl-N-glycidylammonium p-toluenesulfonate in 10 ml of water is added with stirring. This reaction is not exothermic; therefore, after the entire amount has been added, the temperature is increased from 40 to 70 ^° C. and the mixture is then stirred for a further hour. The modified polyethyleneimine is separated from the light brown solution by pouring the latter into 1.5 liters of acetone. It is then washed with acetone and ^{dried under reduced pressure at 40 °} C. to constant weight. Yield: 37% of polymer with a nitrogen content of 10.38% and a sulfone content of 763 %. As a result, the degree of substitution of the primary and secondary amino groups together is 46.5 mol%.

If an amount of 2.0 g / m. the aminoalkylated polyethyleneimine coated on a paper support, the layer is dried and the surface resistivity of this layer is measured at 20 ⁰ C, one obtains the following

Results :

at 50 % relative humidity: I.77O.IO ⁶ ohms / square

at 70 % relative humidity: 101.10 ⁶ ohms / square.

What is interesting is a comparison between these numbers and the numerical values given in Example 5, because in the latter case one has for the same amount of modified polyethyleneimine per

ρ
m Papxer received the following values:

hoi 50 % relative humidity: 18.5 x 10 ⁶ ohms / square Loi 70 % relative humidity: 1.18.10 ⁶ ohms / square.

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Since the aminoalkylated poly (dtliylenininii ^T i \ on Boispie] 5 has about the same degree of substitution, this is the proof that a much better electrical conductivity is obtained with a chloride anion than has already been mentioned above.

Example 12

A glassine paper of 70 g / m is made with an electrically conductive Layer of aminoalkylated polyethyleneimine according to the example 3 coated in an amount of 2 g / m 2. The received Surface resistance is:

at 22 ° C and 15% relative humidity: 3-04-0.10 ⁶ ohms / square at 22 ⁰ C and 50% relative humidity: 68.10 ohms / square at 22 ° C and 70% relative humidity: 4,72.10 ⁶ ohms / square .

The electrically conductive layer is coated with a zinc oxide dispersion, which is prepared as follows: 0.45 liters of vinyl acetate / dibutyl maleate mixed polymer is diluted with 5-6 liters of dichloroethane and then mixed with 2 kg of zinc oxide, with the vinyl acetate / dibutyl maleate copolymer consists of about 71% by weight of vinyl acetate, 29% by weight of dibutyl maleate and about 0.5 ml equivalent of acetic acid groups.

The zinc oxide used is a product of The Durham Chemical Group, Birtley, England, and is sold under the brand name ELECTROX traded. The dispersion obtained in this way is ground in a sand mill and then mixed with 1.2 liters of the same copolymer from vinyl acetate and dibutyl maleate, 1.5 liters of dichloroethane and 67 ml of a 1% solution of bromophenol blue in Ethanol mixed with stirring. This dispersion is then applied with a knife coater in an amount of 30 g of zinc oxide applied per m and dried.

The material is then used in an ordinary electrophotographic Copier processed. If you consider the quality of the · bei When comparing copies made with different relative humidity, one can see only slight differences note that all copies have a good sharpness.

For comparison, a similar electrophotographic

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Material made, but with the difference that the electrically conductive layer of aminoalkyliex-tem polyethyleneimine is replaced by a layer of unmodified polyethyleneimine. The quality of the produced at a relative humidity of 15% and "at 2O ⁰ C copy is much worse.

Example 13

A barite photo paper is mixed with an aqueous solution of the amino

alkylated polyalkyleneimines of Example 10 in an amount 2

of 2 g / m (weight of dried material) coated.

Then the zinc oxide dispersion is prepared as follows: First 20 g of the copolymer of vinyl acetate and vinyl stearate (85:15 mol%) are dissolved in 500 ml of ethanol. then 225 g of photoconductive zinc oxide are added and the mass is ground in a ball mill for 24 hours. Below are the the following compounds added with stirring:

2% by weight solution of the copolymer of vinyl acetate and vinyl stearate (85:15 Mol%) in ethanol ■ 500 ml

10% strength by weight solution of monobutyl dihydrogen phosphate in ethanol 10 ml

10% solution of succinic acid in dimethylformamide 10 ml

1% solution of fluorescein (color index 43.35O; in ethanol 10 ml

The dispersion obtained in this way is applied to the electrically conductive

2 layer applied in an amount of 26 g zinc oxide per m

and dried at 35 ° C.

The material obtained in this way is negatively charged and exposed in contact with a positive text original.

The development takes place with a grooved roller that rotates in a 2% by weight aqueous solution of methylene blue, wherein a pressure roller presses the exposed material against the grooved roller, which is moving at a speed of 4 cia / sec. turns.

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This is a clearly legible and sharp positive copy of the original Result -

Example 14

A paper of 60 g / m is made with the aminoalkylated polyethyleneimine soaked in Example 10. A dispersion of 100 g of titanium dioxide, 50 g of starch and 150 g of the same is then aminoalkylated Polyäthylenimines produced and this dispersion

in an amount of 4 g of solid substance per m. on one side applied to both sides of the impregnated paper.

50 g of polyvinyl butyral, which in addition to the vinyl butyral groups contains about 10 % yinyl alcohol groups and about 2 % vinyl acetate groups, is dissolved in 500 ml of ethanol and 25 g of barium sulfate are added to this solution with vigorous stirring. The mixture is ground in a ball mill for 24 hours and this pigment

2 dispersion in a corresponding 8 g solid substance per m Amount applied to one side of the pretreated paper carrier. .

The material produced in this way can be used for recording intermittent, electric charges are used with the help of a row of pens and then developed with an electrophoretic developer will. After treatment in an electrostatic recorder, this material also achieves at high recording speeds excellent results.

Example 15

Following the method described in Example 1 is an aminoalkylated Polyethyleneimine shown, but dabqi the amounts of the individual reactants chosen so that an aminoalkylated Polyethyleneimine is formed, which is 0.66 mol of N-triniethyl-N-glycidylammonium chloride contains per mole of ethyleneimine in the polymer.

Three strips of polyethylene terephthalate film with a thickness of 100 pm with an adhesive layer combination of known Arb vorf: ehcn as described in British patent specification 1 2J4 755 is described.

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The three subbed strips are made with the following measures coated:

Strip 1 strip 2 strip 3

Water gelatin modified polyethyleneimine

20% aqueous solution of formaldehyde

Saponin

87.2 G 82.2 S. 89 , 7 S. 3.8 S. 3.8 S. 3 ,8th S. 2.6 S. 5.2 S. 1 , 3 S. 1.5 δ 1.5 S. 1 , 5 S.

2.5 g

2.5 g

2.5 p

These "coatings are applied in such a way that the three stripes

After drying, 2 g of gelatine per square meter are present.

The following surface resistance values of these layers are measured:

Surface resistance at 20 ⁰ C in 10 ⁶ ohms / square at 50 % EF at 70% EF Strip 1
Strip 2
Strip 3 at 15 % EF 2130
82
7IOO 30-, 4
10.6
9.3 4,250,000
I5.3OO
8.5OO.OOO.

An electrophotographic recording material is produced by coating the electrically conductive strip 2 with a solution consisting of:

Methylene chloride 45 ml

1,2-dichloroethane 45 ml

5 g

Copolymer vinyl chloride / vinyl acetate / maleic anhydride (Molar ratio 86.5 / 13.3 / 0.2)

Ehodamine B (CI. Basic Violet 10) (color index 45.I70)

5 p

0.025

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The dried, containing about 3 1/2 photoconductors per in "undo recording layer is charged with a negative corona discharge and through an original with 100 lux-seconds Contact exposed for 6 seconds with a tungsten filament lamp. That latent image is electrophoresed with a developer for 5 seconds developed by diluting the concentrated developer described below in a volume ratio of 15 / 100O with ISOPAR H (an isoparaffinic hydrocarbon Mixture with boiling range 177-188 ° C, made by the company Esso Belgium N.V., Antwerp, Belgium distributed by wira): Carbon black (mean particle size: 20 nm) 30 g

Zinc monotridecyl phosphate as a dispersing agent 1.5 g

ISOPAR H (trade name) 750 ml -

Resin solution described below 150 g

The binder resin solution is made by heating 500 g of ALKYDAL L 67 (Farbenfabriken Bayer AG, an alkyd resin blended with 67% linseed oil) and 500 ml of turpentine substitute with 11% by weight of aro-. matic compounds at 6O ⁰ C until a clear solution is obtained, and subsequent cooling.

A good transparency copy of the original will be obtained.

GV.600

309830/1084

Claims (6)

Patent claims 1. Recording material containing a support made of paper or synthetic polymer and an electrically conductive layer applied to at least one side of the support, this electrically conductive layer having a surface resistance measured at 15% relative humidity / l / t has less than 10 ohms / square, characterized in that that the electrically conductive layer consists wholly or in large part of a water-soluble polymer, which through Aminoalkylation of polyethyleneimine with a terminal, quaternary ammonium group-bearing epoxy compound has been obtained according to the general formula: R ₀ -NR-CH ₀ -CH-CH ₀ V " ^d \ / ^{d R} 3 °. in which: R is a branched or straight-chain alkylene group with up to 4 carbon atoms, R ^, R ₂ , Rx (identical or different) each represent an alkyl group with up to 4 carbon atoms, a cycloalkyl group or an aralkyl group, or R / |, R ₀ and R, together with the nitrogen atom, a heterocyclic amine group, and X is an anion. 2. Recording material according to claim 1, characterized in that the epoxy compound carrying a terminal, quaternary ammonium group is produced by reaction of an epoxy compound of the formula: CH ₉ -CH-RX with a tertiary amine of the formula: R ₂ -N τ, / ^ΛΓ ' ¹⁰⁶ 9 3 0 9830/1084 GV GOO wherein X, R, R ₁ , R ₂ and R have the same meaning as in claim 1 has been obtained. 3. Recording material according to Claims 1 and 2, characterized in that the one carrying a quaternary ammonium compound Epoxy compound is N-trimethyl-N-glycidylammonium chloride, obtained by reacting epichlorohydrin with trimethylamine. . - 4 * recording material according to claims 1 to 3 »thereby characterized in that it carries a photoconductive layer on the electrically conductive layer. 5. Recording material according to claims 1 to 3, characterized in that it is on the electrically conductive layer carries an electrically insulating layer. 6. Recording material according to claims 1 to 5, characterized characterized in that the electrically conductive layer consists of (V5 to ρ * 7.5 g / m of the aminoalkylated polyethyleneimine. I.
7- Electrically conductive polymers, characterized in that they are made up of repeating units according to the general formula: CH ₂ -CH-N consists in the A represents a single chemical bond or a group of the formula -CH2-CH2-NR4-, in which R ^ represents hydrogen or a group with the formula: -CH ₀ -CHOH-RN- X 3 wherein X, R, R ₁ , R ₂ and R have the same meaning as in claim 1. 309830/1084