DE2234736C2 - Use of compounds of a certain structure as charge control agents for modifying the electrostatic charging properties of the surfaces of photographic materials - Google Patents

Description

3. Use of compounds according to claim 1, characterized in that the compounds correspond to one of the following formulas:

CH ₃

C ₇ F ₁₅ -CONH- (CH ₂ ) JN-CH ₃

CH ₃ CH ₃

CjF ₁₇ -SO ₂ NH- (CH ₂ ) JN-CH ₃

CH ₃

CH ₃

C, H "-CONH- (CHJ ₃ -N-CH ₃

10

15th 20th

30th

• 40

CH ₃

CH ₃ "

C, ₇ H ₃₅ —CONH— (CH ₂ ) ₃ —N — CH ₃

CH ₃

4. Use of compounds according to Claims 1 to 3 for modifying layer supports made of cellulose triacetate or cellulose acetate propionate, which is replaced by rulyl sebacate, methoxyethyl phthalate and / or tri-so phenyl phosphate are plasticized.

5. Use of compounds according to Claims 1 to 3 for modifying adhesive, primer or backing layers containing 0.5 to 1.0 g of compound per 1.0 g of gelatin on a dry weight basis.

6. Use of compounds according to Claims 1 to 3, in the form of a layer on an adhesive or primer layer in concentrations of 0.2 to 4 micrograms / cm ^{2 of support} surface.

7. Use of compounds according to Claims 1 to 3, together with saponin.

In the manufacture and use of photographic materials, especially sensitized, photosensitive, photographic and radiographic materials, create static electricity poses a serious problem. In the case of light-sensitive, photographic and radiographic materials lead to particularly disadvantageous discharges caused by electrostatic charges lilTckcn, since light flashes occur during the discharges, which are undesirable from the light-sensitive Materials are recorded.

The electrostatic discharges can occur during the manufacturing process of the materials, / .. U. in the coating of substrates, the post-treatment of coated materials, the

60 65

packaging of such materials or during the use of such materials, e.g. B. in cameras and Copiers.

Although there are a variety of causes that create static electricity, the occurrence of electrostatic charges, e.g. in the manufacture and use of photographis shear materials, summarized under the general term "triboelectricity". Under this term is understood to be an electrostatic charge caused by friction or contact between two surfaces and subsequent physical separation occurs. Usually, but not always, the two are in contact surfaces different from each other.

The level of charges generated in this way depends on several factors, of which the ίο the most important are:

1. the intensity of the contact,

2. the duration of the contact and

3. the nature of the two surfaces brought into contact.

It is disadvantageous that only very few photographic film supports and photographic recording materials composed of polymers themselves have such a high electrical conductivity that, owing to this conductivity, the accumulation of electrostatic charges can be prevented. In the case of a polymer support, for example a cellulose acetate support, with a conventional photographic emulsion layer whose binder consists primarily of gelatin, electrostatic electricity is discharged when a triboelectric charge of the order of +8 to +10 Esu, ie electrostatic units per cm ² (+26.5 to +33.2 microcc. iomb / m ² ) is achieved. Of course, the figures given depend on the composition of the recording materials used and the humidity conditions. When using emulsions whose binder consists primarily or mainly of gelatin, the emulsions have a tendency to develop positive triboelectricity when they come into contact with various surfaces which come into contact with the emulsion layer during the production process of photographic recording materials. Most of the publications dealing with the triboelectric phenomenon deal with the dissipation of accumulated electrostatic charges, especially those charges that can be generated on the surface of layers made from polymers.

The most common method of discharging electrostatic charges is based on the Additives food τ of certain compounds, which eliminate electrostatic charges or the buildup of electrostatic charges reduce, namely by increasing the conductivity of the layers. Although many of the conductive compounds heretofore used for this purpose remarkably improve the conductivity of the surfaces of polymers, they tend to generate large amounts of electrostatic charge by cleaning or contact with a surface other than the surface of the polymer being used. As a result, the amount of electrostatic charges on such polymer surfaces containing conductive compounds can be so great that the conductive compounds are unable to dissipate the accumulated charges quickly enough to prevent sudden discharges.

Furthermore, it has been shown that many of the compounds which increase the conductivity only in one environment relatively high humidity work satisfactorily. In the rain! lose such connections their conductive properties at relative humidity values of 10% or below. The dependence the effectiveness of these compounds on the degree of relative humidity is based on the fact that such

Conductive compounds predominantly consist of hygroscopic substances and are often more ionic Are nature, weshi'lb they dissociate at relatively high humidity. Lots of these conductive connections furthermore have the disadvantage that the surfaces of the materials to which they are added get sticky. Sticky surfaces, however, are particularly common in the case of photographic recording materials very disadvantageous because Hie / u a partial withdrawal of z. B. adhesive or priming layers built up from gelatin of the substrate materials during the manufacturing process. So can In particular, defects occur due to the fact that small particles of the gelatin of the adhesive or primer layers on the transport rollers or transport rollers or other rollers with which the materials during come into contact with their manufacturing process, stick. The use of hygroscopic conductive Connections have therefore not proven effective.

To avoid the disadvantages caused by the use of hygroscopic * pis, .h; r conductive connections, to bypass it has continued to become known, e.g. B. from US-PS 30 82 087, by rubbing or sudden Separation of two contact surfaces caused by electrostatic support To reduce charges by equipping the materials with anti-static layers which are made up of substances which (a) have a tendency to charge, that of AuI-charging tendency of the material to be modified is opposite or (b) have a tendency to charge, which is of the same polarity as that of the material to be modified, but less.

One of the main disadvantages of this process is that it is purely qualitative in nature. According to the US-PS 30 82 087 described method is first determined the tendency of a carrier surface to charge, whereupon a layer of a styrene copolymer is applied to the support surface

with the aim of reducing the tendency of the carrier material to become charged. However, the US PS does not open one Way that makes it possible to determine the degree of charging of a carrier surface by applying a styrene polymer to be controlled quantitatively and reliably. From US-PS 35 01 653 a device is known learners, The photographic materials move electrostatically using a so-called "impact electrification method"

can be charged and can be determined the tendency of the materials to be charged. The determination method known from US Pat. No. 3,501,653 is based on the fact that a wide (comparative) surface is opened on a certain equal surface and separated again from the first surface, in a precisely controllable and repeatable manner. The electrostatic charges generated by the impact and the separation of the two surfaces are precisely measured and recorded. The values obtained are then expediently expressed in so-called electrostatic units per cm ² (Esu / cm ² ).

It is the object of the invention. Find compounds that are particularly advantageous as charge control means to modify the electrostatic charging properties of photographic surfaces Materials are suitable.

It has been found that the compounds or mixtures thereof characterized in the claims can be used to achieve this object.

The invention makes the electrostatic charging properties of surfaces more photographic Modify materials in such a way that they prevent, or at least substantially, the tendency towards charging is decreased.

According to the invention, one proceeds in an advantageous manner such that one

(a) First, under standardized conditions, the degree of electrostatic charge on the surface

of the photographic material to be modified ”is measured by the diirrh row of the upper surface with a other, in particular different, surface and / or caused by separation of the two surfaces becomes that one

(b) on the basis of the results of step (a) through experiments one of the specified compounds or a corresponding one Mixture of compounds, the or that the degree of electrostatic charge of the to be modified Able to change the surface of the photographic material in the desired sense, selects and that one

(C) on and / or in the surface to be modified as much of the selected compound, or of the selected Compound mixture as "charge control agent" applies or brings in that the desired Modification occurs.

According to the invention, the charging properties of the surfaces of pholographic materials are thus determined changed quantitatively with the compounds called "charge control means", with the Charge control means modify the charge tendency of the surfaces to the desired extent r.u. capital. The compounds used according to the invention can be in or on one or more layers photographic recording materials are incorporated or applied.

In the given formula (I), the hydrocarbon radical represented by A preferably has 1 to 20 carbon atoms. In the radical D, the ^{alkyl radicals represented by R 1} , R ² and R ³ preferably have 1 to 5 carbon atoms. Stand R ¹ . R ² and R ^{3 for} aryl radicals, these preferably consist of optionally substituted phenyl or naphthyl radicals. The anion X ^s preferably consists of a chloride, bromide, iodide, nitrate or phosphate ion.

In the given formula (II), the aromatic radical represented by Z is preferably composed of one Phenyl residue, on which up to 4 benzene rings can optionally be fused. If the one represented by Z exists A radical consisting of an alicyclic hydrocarbon radical, this preferably consists of a cycloalkyl radical, e.g. a cyclohexyl radical or a decalinyl radical. The alkyl radical represented by R preferably has 1 to 20 carbon atoms. If R stands for an aryl radical, this preferably consists of a radical of the phenyl or naphthyl series.

If M stands for a metal cation, this is preferably a metal cation of groups 1 and II of the periodic System of elements.

The following is a distinction between manufacturing-related and processing-related charging problems can be distinguished.

Manufacturing-related charging problems are to be understood as those that occur during the manufacturing process of photographic materials occur. This includes charging problems, for example, those on the charging of rollers and emulsion coaters, cutters and packers are due. In contrast, the term processing-related Charging problems are all the problems that arise after the recording materials are made. in the In the case of photosensitive recording materials, most of the processing-related charging problems arise in cameras and developing devices in which the exposed recording materials processed on.

Manufacturing-related charging problems can often be eliminated or corrected by removing the Manufacturing apparatus or equipment in contact with the photographic materials to be manufactured is modified so that charging effects are reduced to a minimum. Such modifications however, the manufacturing devices are often very difficult to implement and also costly and as a rule often require a redesign of the devices used. In case of Processing-related charging problems, such modifications are usually impossible, and indeed for example, because a manufacturer of photographic materials has no control over the exact construction and has the structure of the devices in which the material made by the manufacturer is later used will.

The charge control means used according to the invention are of so-called conductivity compounds or to distinguish conductive compounds, i.e. compounds that are due to their hygroscopicity and / or

Their ionic character tend to have static charges generated by bringing two surfaces into contact will be derived.

An essential difference between the charge control means used according to the invention and the known conductive connections is based on the fact that the charge control means used according to the invention can be used to reduce or increase the properties of surfaces, to generate static electricity, or to reduce them to a specific: n degrees, whereas the conductive compounds of the prior art are essentially used to minimize the accumulation of electrostatic charges after they are formed.
In order to determine the optimal charge control means in each individual case, the surface to be modified, which is charged by physical contact with another, in particular different, surface is tested for its chargeability, preferably in a device from the US Pat 35 01 653 known type, wherein the electrical charges are determined that are generated when the surface is brought into contact with a second, in particular different, surface. Certain test conditions are adhered to, in particular with regard to the time, the impact strength, the intimacy of the contact between the surfaces and the relative humidity. After the degree of charging has been determined in this way, the charging control means, which can either be incorporated into the surface to be tested or applied to the surface to be tested, can be tested. The modified surfaces are always tested in the same way, ie under the same conditions with the same, generally different, contact surface. Depending on the results of the tests, such a charge control agent is then selected which has charging characteristics which, when the control agent is introduced onto or into the surface of the material to be modified, leads to the desired surface charge modification, whereupon a sufficient amount of the control agent is achieved the desired modification is applied to the surface of the material to be modified or incorporated into the surface.

Advantageously, those charging control means are selected which have triboelectric charging properties which are of approximately the same order of magnitude as those of the surfaces whose charging tendency is to be modified, but whose polarity is opposite to the polarity of the charges on the surface to be modified. Then such amounts of this charge control agent, which are able to neutralize the charges of the surface to be modified or be able to return them to zero, selected and incorporated or applied in or on the surface of the material to be modified, for example by a casting or extrusion operation or by applying a very thin, continuous or discontinuous layer of the charge control agent on the surface, the charging properties of which are to be changed.
In the production of photographic recording materials based on silver halide, the light-sensitive silver halide is suspended, for example, in a gelatin solution which is then applied, generally at very high speed, to a support, for example a support made of a cellulose ester, a polycarbonate or a polyester, e.g. B. polyethylene terephthalate. The layer supports consisting of cellulose esters can optionally have been treated with a wide variety of known plasticizers, for example with butyl sebacate, methoxyethyl phthalate, triphenyl phosphate or mixtures thereof.

In the case of polyester substrates, e.g. B. supports made of polyethylene terephthalate, it is due to the hydrophobic properties of these substrate materials required, the substrate with an emulsion adhesion to coat improving adhesive or intermediate layer, for example a gelatin adhesive layer. This adhesive or intermediate layer is either applied directly to the substrate or, if necessary, using an undercoat, followed by drying the adhesive layer. The precoated substrates are coated with one or more emulsion layers, in particular at high temperatures, e.g. B. in a roller conveyor coating machine or other conventional coating devices, in which triboelectric charges can be generated. With each contact of the surface of the substrate provided with an adhesive layer with a transport roller, for example stainless steel or anodized aluminum during emulsion coating, charges are generated, so that the accumulated electrostatic charges can finally be discharged when the Charge strength exceeds a certain level.

If the surface of such a gelatin adhesive layer is now tested for its impact electrification potential in the device known from US Pat. cm ² at a relative humidity of 5% and a temperature of 21 ° C as well as other specific process conditions that will be listed later, leads to a charge of about +20 Esu / cm ² , if the impact or Impact material, ie in this case for example the roll material, consists of stainless steel.
Experiments carried out under the same conditions with the compounds used according to the invention

gave strong negative charging properties on the order of about -30 Esu / cm ² .

On the basis of the test results obtained, small amounts of these "negative charging agents" can now are introduced into the gelatin adhesive layer, the amount of added compounds being varied can. In this way it can be determined, for example, that by concentrations of 1 to 2 g of the compounds per gram of gelatin of the adhesive layer, only charges of the order of 0 ± 0.5 Esu /

cm ² occur when the modified surfaces are tested according to the method known from US Pat. No. 3,501,653.

Further experiments showed, for example, that there was already relatively small amounts in the Order of magnitude of z. B. about 0.005% by weight of the fluorocarbon compounds falling under the formula I

fertilizing in the gelatin adhesive layer is possible to produce layer supports that lead to practically no charges when tested in the manner described. They are modified in this way coated in the usual way with an emulsion, for example using stainless steel existing device rollers, then at most only minor static charges occur in the most varied of them Humidity.

Although the charging tendency inherent in the charge control means is preferably the same as the charging tendencies / the surface whose charging tendency is to be modified (with the exception, of course, that the Polarity (.'er charges are opposite), such an approximation of the charging tendency is not necessarily required because a relatively smaller amount of a charge control agent with a larger charge coolant or charging tendency incorporated into or applied to the surface to be modified can be to reach a potential of about 0. Such a combination of charge control agents with high charging capacity or high charging tendency and a chargeable surface opposite Polarity and relatively low charging potential leads to the additional advantage that only very small amounts of charge control agent to be introduced into the sensitive photographic material need, whereby the occurrence of adverse sensitometric effects is avoided, which then sometimes occur when additives are incorporated into photographic materials.

The selection of the most advantageous charge control agent in the individual case depends, of course, on it the surface to be modified. This means that in addition to the electrostatic charge properties and the polarity of the charges also the compatibility of the charge control agent with that to be modified Material is to be observed. For example, the charge control means, after being incorporated into Polymer layers remain uniformly distributed in these. Furthermore, for example, is of particular importance the compatibility of charge control agents with silver halide emulsions, provided they do so be incorporated.

When applying toners to exposed areas of electrophotographic recording materials it is necessary to strongly charge the surface of the toner particles in order to ensure that they are removed from the ent-:> speaking or similarly charged non-image areas and repelled by the oppositely charged Image districts are attracted. In these cases, for example, appropriate charge control means incorporated into the toner particles or applied in the form of coatings to the toner particles to to produce a greater chargeability of the toner particles of the same polarity.

It follows that the described charge control means can also be used for this purpose to increase as well as to decrease the electrostatic charging capacity, the latter effect is of particular importance in the case of radiation-sensitive recording materials.

As a further alternative, because of the distinctions to be made between manufacturing-related charging problems and processing-related charging problems, it may be desirable to add a conventional one to the surface or in the surface of a photographic material in addition to one or more of the charge control means To add conductivity-increasing compound, which has the property of dissipating electrostatic charges, in particular triboelectric charges, or of providing additional charges.

For example, according to the method of the invention, a charge control means or a Combination of different charge control agents selected and incorporated into the gelatin adhesive layer that is on top a layer support is applied, incorporated in order to reduce the production-related charging problems to eliminate, for example, to avoid electrostatic charges that occur during manufacture photographic recording materials by bringing them into contact with stainless steel Transport rollers occur. The recording material produced can then, however, after the sale processing-related charging problems are subject to, for example by rubbing - »5 Exercise or contact with plastic, rubber or aluminum surfaces for which this was used in the manufacture of the Recording materials used offers little or no protection. In these cases, for example the use of a conductive connection and a charge control means of particular Be an advantage and ensure that the product produced even under processing-related charging problems does not have to suffer. so

The amounts and concentrations of the charge control agents used to modify the charge characteristics Photographic materials can be applied depending on the nature of the charging Surface can be very different. The charge control agents used in the present invention can des further in the form of discontinuous punctiform, dot-shaped or continuous layers towards the Modifying surfaces are applied.

Uses the process of the invention for modifying photographic materials having silver halide emulsion layers applied, these emulsion layers can contain the usual known silver halides, namely silver chloride, silver bromide, silver bromide iodide, silver chloride iodide and silver chloride bromide iodide as well as mixtures thereof. In the case of the emulsions used to produce the recording materials can be, it can be coarse or fine-grained emulsions according to customary known Methods can be produced. Surface image and interior image emulsions can also be used.

The emulsions used for the production of the recording materials can furthermore by means of chemical sensitizers and compounds that increase sensitivity contain.

The silver halide emulsions used to prepare the recording materials can also be used Protected against the occurrence of slivers and against a loss of sensitivity to the Storage to be stabilized.

The photographic and other curable layers of a modified by the process of the invention

Able prn'ographischen material can also with the usual known organic and / or inorganic Hardening agents are hardened.

The photographic emulsions and recording materials can finally be made using the various common colloidal binders are produced.

Hydrophilic binders suitable for producing the emulsion layers and other layers can be of natural origin and, for example, made of proteins, e.g. B. gelatin, Gelatinederivatcn, cellulose derivatives, polysaccharides, z. B. dextran and gum arabic, consist or of synthetic polymeric substances, e.g. B. water-soluble polyvinyl compounds such as polyvinylpyrrolidone and Acrylamic'polymeren. The individual emulsion layers and other layers of photographic materials modifiable by the process of the invention can further contain, alone or in combination with hydrophilic, water-permeable colloidal binders, other synthetic polymeric compounds, e.g. B. dispersed polyvinyl compounds, e.g. B. in latex form, in particular those which contribute to increasing the dimensional stability of the photographic materials.
The photographic recording materials which can be modified according to the process of the invention can, in addition to the described charge control agents, have conductive layers and / or contain any compounds which are derived from soluble salts, e.g. B. chlorides and nitrates can exist. Furthermore, the recording materials can have vapor-deposited metal layers and / or contain ionic polymers, as are known, for example, from US Pat. No. 2,861,056 and 3,206,312, or insoluble inorganic salts, for example of the type known from US Pat. No. 3,428,451.

The individual photographic layers and other layers of the photographic materials can be applied to the most varied of customary known layer carriers, for example on foils made of cellulose nitrate, Polyvinyl acetate. Polystyrenes and other resinous materials, as well as glass, paper and Metal. Typically, the support consists of a flexible material, e.g. B. made of a polyester, Polycarbonate or cellulose ester. The layer support can, however, also consist of paper, which if necessary can be partially acetylated or have a barite layer and / or a layer of an α-olefin polymer can, in particular a layer of a polymer with an α-olefin with 2 to 10 carbon atoms, e.g. made of polyethylene, polypropylene or an ethylene-butene mixed polymer.

The photographic materials which can be modified by the method of the invention can furthermore optionally contain customary known matting agents, e.g. B. starch, titanium dioxide, zinc oxide. Silica and polymer particles, for example those from US-PS 29 92 101 and 27 01 245 known type, also ai.:alosoluble polymeric particles, e.g. of the type known from US Pat. No. 2,992,101.

The customary known coating processes can be used to apply the individual photographic layers to the support.
The photographic materials modifiable according to the process of the invention can furthermore be intended, for example, for colloid transfer processes, for example of the type known from US Pat , 30 20 155 and 28 61 885 can be described. The materials can also be intended for color image transfer processes, such as those disclosed in US Pat. No. 3,087,817, 3,185,567,

The recording materials can be intended for absorbent transfer processes, for example for processes of the type known from US Pat. No. 2,882,156.

The invention is also important for the production of recording materials for the Recording of auskopbaren images are intended and for example in US-PS 23 69 449 and 34 47 927, as well as for the production of recording materials that are used for the 11er-

-45 position light-developable images are determined, as for example in US Pat. No. 3,033,682 and> 2,87,137 to be discribed. The modifiable photographic materials can also be used for heat development processes be determined, as for example in US-PS 31 52 904, 34 57 075, 33 12 550, 34 18 122, 33 92 020, 33 01 678 and 35 31 285. The invention is also suitable for the modification of such photographic recording materials, which are intended for the production of color photographic images.

The modified photographic recording materials can be prepared by conventionally known methods are developed, especially in alkaline developer solutions with common developer compounds, z. B. hydroquinone, catechols, aminophenols, 3-pyrazolidones, phenylenediamines, ascorbic acid derivatives, Hydroxylamines, hydrazines and reductones. Optionally, the drawing photographic materials can be used can also be developed in so-called hardening developers, for example in the US-PS 32 32 761 are described, and also in roller transport devices as they are, for. B. from US-PS 30 25 779 are known, or by surface development processes such as, for example, from Example 3 of US-PS 34 18 132 is known.

The modifiable recording materials can also be used, for example, for developing development processes be determined or copy-out exposure methods, such as those from the US-PS 23 69 449 are known, or for light development processes, for example that from US-PS 30 33 678, 32 87 137 and 34 18 122 of known type.

In the following there are given some charge control agents which can be used in accordance with the invention and which appear as have proven particularly effective, for example in the manufacture of photosensitive recording materials using gelatin in the light-sensitive emulsion layer or layers or in the form a separate gelatin layer, e.g. 3. Adhesive layer. These charge control means have the properties to generate electrostatic charges which are considerably less positive than those of gelatin. Of course The compounds can also be used to increase the positive charge properties or

The tendency of such polymer surfaces as gelatine to increase in charge.

p-nitrobenzoic acid; 2,4,6-trinitrobenzoic acid; Sodium benzoate; p-nitrobenzenesulfonic acid; 3-nitrophthalic acid; p-nitrocinnamic acid; p-nitrobenzenesulfonic acid, sodium salt; p-nitrophenylacetic acid; p-nitrophenoxyacetic acid; 3-nitrochalcone; 2,4-dinitro-1-naphthol-7-sulfonic acid; 4-nitrophthalic acid; p-nitrobenzamide; 2,4,6-trinitrobenzenesulfonic acid: m-nitrobenzenesulfonic acid; Sodium salt; p-nitrobenzenesulfonic acid, Dibulylamine salt; 4-chloro-m-toluene isulfonic acid; p-fluorobenzenesulfonic acid; p-chlorobenzenesulfonic acid; Sodium salt; p-bromobenzenesulfonic acid, sodium salt; 2,5-dichiorbenzenesulfonic acid; p-Hydroxybcn / .olsullbic acid; Sodium salt; o- (carboxymethoxy) benzoic acid; p-hydroxybenzoic acid; p-chlorophenylacetic acid; Sulfosalicylic acid; 4-sulphophthalic acid, monosodium salt; 2,2'-diphenic acid; Trimellitic acid; 4-sulfophthalic acid, dibutylamine salt; Pyromellitic acid; Terephthalic acid; Phthalic acid; Mellitic acid; Salicylic acid; Pyromellitic acid, monosodium salt; Pyromellitic acid-NHf, pH = 4.3; Pyromellitic acid-NH®, pH = 8.2; 5-sulfoisophthalic acid, sodium salt; 5-sulfosalicylic acid; Trimesic acid and compounds of the following formulas:

CH ₃ ""

C ₇ F ₁₅ -CONH- (CHz) ₃ - N-CH ₃

CH ₃

CH ₃

C ₅ F ₁₇ -SO ₂ NH- (CH ₂ ) JN-CH ₃

CH ₃

15th 20th 25th

CH ₃

C, H "-CONH- (CH ₂ ) ₃ - N-CH ₃

CH ₃

and

CH ₃

C ₁₇ H ₃₅ -CONH- (CHj) ₃ -N-CH ₃

CH ₃

On the photographic materials, which cause special problems due to triboelectric effects, include, for example, X-ray materials and so-called aero-film materials. Because of the special Nature of the manufacturing and processing charging problems encountered with these photographic Materials occur, the use according to the invention for these materials is of particular Meaning. It enables the production of particularly promising photographic materials from described types, although they can be modified and improved in a correspondingly advantageous manner of the other known photographic materials.

The following applies to X-ray materials:

In the manufacture of X-ray materials at high coating speeds, considerable discharges generally occur. Particularly in the production of such photographic materials it happens that, due to the relatively high humidity conditions under which the production of these materials takes place, a so-called "gelatin loss effect" occurs, which can become a serious coating problem. In order to solve this problem, measurements were carried out using the device known from US Pat. No. 35 Ol 653, with the aim of determining the maximum tolerable amount of electrostatic charge which occurs in the event of a simple impact (impact) between a polymer made of a polymer Support material with a gelatin adhesive layer, which is intended for the production of X-ray film material, and rollers, which convey the layer support material through the loading device, which are made of stainless steel and aluminum. The measurements carried out showed that a maximum single shock charge of + IO to + 12 Esu / cm ^{3 was} the maximum tolerable charge, since above this charge value at relatively low humidity levels, which were necessary to prevent the described gelatin loss effect, even when using the conductivity increasing compounds, the cumulative charge build-up could not be sufficiently prevented and possibly destructive and often particularly conspicuous discharges in the coating device with a length of about 0.6 m

30th 35 40 45

50

55

60

65

led. This maximum charge value of a simple shock or impact charge naturally depends very much on the The number of rollers or transport rollers in a device depends on the coating speed and the relative humidity The basis for the following considerations.

S Under the specified conditions, the problem of reducing the degree of charge to a value below +10 Esu / cm ² can be solved.

On the basis of the measurement results described, it was possible to determine when carrying out the invention that compounds of class (II) in particular are suitable for solving production-related charging problems, whereupon small amounts of these compounds were incorporated into the X-ray materials.

As already stated, the charging control means can be incorporated in various ways into the surface whose charging tendency is to be modified.

In the present case it was found to be particularly advantageous to coat the gelatin adhesive layer leading to the charging problems with a thin layer of 0.2 to 4 micrograms / cm ^{2 of} the charge control agent by applying the charge control agent from a suitable solvent , at-

for example ethyl alcohol. Equally beneficial results have been obtained when the charge control means in the gelatin coating composition used to coat the support (intended for producing the adhesive layer) was incorporated. In the case of using this method, it has been found to be appropriate to increase the concentration of the compounds to 0.4 to 1 g per gram of dry gelatin, by one To achieve sufficient surface concentration of the compounds and to reduce the charging tendency of the Ge to depress the latin layer to a desired low value in order to avoid charges caused by I n- Cor.taktkorarr.en the gelatin surface is locked rollers made of stainless steel and / or anodized aluminum be evoked. The increase in concentration to 0.5 to 1.0 g was necessary because it was the compounds of class (II) are those that are not strong or particularly effective surface-active compounds.

A third advantageous method of incorporating the charge control agents has been by a solution to bring these compounds into contact with the surface to be modified in order to achieve adsorption of the compounds, whereupon excess liquid was removed. This method was found to be particularly advantageous when used as a solvent for the application of the charge control agent for example a short chain alkanol, e.g. Methyl or ethyl alcohol was used, d. H. a solution agent which is itself a swelling agent for gelatin or, if a solvent containing a Swelling agent for gelatin was used, which opened pores of the gelatin surface. This allows the Facilitate penetration of the charge control agent into the gelatin, which in turn ensures that a discontinuous or continuous layer of the charge control agent is achieved on the surface of the gelatin and thereby further ensures that the compounds are firmly in the gelatin top- surface to be anchored.

The following applies to aero footage:

The problems encountered with these photographic materials are largely processing-related charging problems. So these materials are well known, often under extremely unfavorable, t humidity conditions used in high altitude. Furthermore, the transport speed with which | j

this material is transported through the cameras, often very high. The rubber and ύ

Existing plastic camera parts contribute to a strong electrostatic charge of the materials. i ⁽ In most aero film cameras, the transport rollers are either made of stainless steel, anodized | 3 Aluminum, clad metals and / or a wide variety of elastomeric materials, whereby electrosta-! §

table charges by contacting the emulsion side or the rear side of the material with the j, |

Transport rollers are generated. As a result, the surface of the photosensitive material has to be modified, either on the emulsion side, which is generally covered with a protective layer, For example, with a layer of gelatin and a coating aid, and / or the Rückschichi m, which may contain a lubricant, and the known materials in conventional ER a conductivity 'h höhende compound of the type described contains. jfc

so the modification of this type of a photographic material can for example take place in that fii a charge-control agent is used from the class of surface-active compounds, said 'ß compound in the lowest possible concentration in the Emulsionsdsckschichi or coating layer and / |; or incorporated into the backing layer. As a result, compounds of class (I) M , for example, can be used, although compounds of the other classes are also suitable for modifying the materials ψ,

are. ijj

As particularly advantageous compounds for carrying out the method of the invention in the case of both ', 1

For example, aerofilms from Class I have proven to have the structural formula given, where A _s j!

is a partially or fully fluorinated carbon chain and also Z is a radical of the formula _:; j

OO Ü

Il Il I

- S —NH or —C —NH lh

ί Ϊ

J

and further wherein η - 3 and X is a halogen atom. ^ j

As a particularly advantageous compound from this class, which is characterized by a particularly strong negative _; j

10 ΐ?

Charging tendency is characterized, and which is furthermore easily accessible, has a connection of the proved the following formula:

It should be noted that a single recording material can be used in many different cameras, which differ from one another in that their transport rollers have different surfaces, the number of transport rollers is different, that the transport speed in the camera is different and that the markings others are. This means that the processing-related charging problems in different cameras can be different, since each of the specified variables influences the processing-related charging effects to a greater or lesser extent it is exposed in the camera X, whereas the protective effect of the charge control means used can be relatively poor if the same material is exposed in a camera Y whose transport rollers consist of a material different from the transport rollers of the camera X. Material is transported at a higher speed and is intended for use at a greater height. As a result, it may be advantageous, in addition to the charge control agent, to use a compound that increases the conductivity in order to dissipate electrostatic charges. In such cases it may have been found to be advantageous to combine the use of a charge control agent with a customary compound which increases the conductivity. It must be taken into account that the conductivity-increasing compounds have their own charging or electrification characteristics.

From what has been said, it follows that mixtures can also be used to carry out the use according to the invention from charge control agents and conductivity-increasing compounds can be used to reduce the charge values of surfaces to 0 or to a value close to 0. Finally For carrying out the method of the invention, combinations of 2 or more charge control means can also be used be used when a particularly precise match of the surface charging characteristics is desired.

The following examples serve to explain the invention in more detail.

example 1

First, a Stanuard test surface was prepared by a Polyäthylenterephthalatschichtträgcr a thickness of 0.18 mm mi '· a pure gelatin topcoat was coated. The dry weight of the gelatin toppers was 1 mg / cm ".

Sections of the coated polyester backing were now at a temperature of 21 ° C and a 51% relative humidity conditioned.

Solutions with a concentration of 1 mg / ml in ethyl alcohol (ÄTOH) were prepared from the charge control agents to be tested. One drop of each of the solutions obtained was applied to a -4 cm ² area of the gelatin top layer. Thereby, about 4 µg of the charge control agent to be tested ^{accounted for 1 cm 2 of the gelatin surface.}

The metallic Tec 'head (or another comparative material) was then applied to the test surface a test method, as described in US-PS 35 01 653, pitched, whereupon the generated Charge has been determined.

In some cases, a polyethylene terephthalate support without an applied gelatin topcoat was used as a Tcst surface used.

The test values obtained are listed in Tables Ia to Id below. In the majority of cases it was Ethyl alcohol (ÄTOH) used as a solvent.

The abbreviations MeOH and PrCl also used in the following tables mean:

MeOH = methyl alcohol and
PrCl = propylene chloride

The values given in Tables Ia to Id are to be regarded as relative values. When cleaning the hammer or impact head of the test device, small amounts of compounds contaminating the surface of the head can remain, which can change the size of the charge generated when the impact is applied. It has proven to be useful to use the solvent of the test solution used to clean the impact head and then to clean the impact head again with absolute alcohol. Such cleaning produces a value of approximately +30 Esu / cm ² in the case of the untreated comparison material. As a result, the values given in Tables Ia to Id below must be compared with the charging values which were obtained with the untreated comparison material (gelatin control sample) in the same test series. In the following tables, the individual test series are separated from one another by a space.

Impact charging values, determined with different charging control means on gelatin layers, using different comparison surfaces (hammer or impact head) in Esu / cm ³ at an impact or impact pressure of 1.4 kg / cm ² :

Table Ia Surface treatment with Solution Comparison surface *) rubber RulS layer **) Attempt no. middle metal + 12.4 +4.0 no ATOH + 4.6 Control sample, ± 0 -3.3 average value p-nitrobenzoic acid ATOH -19.2 + 11.4 +3.2 1 Benzoic acid ATOH + 2.1 -15.3 -5.4 2 2,4,6-trinitrobenzoic acid ETOH -28.8 + 8.7 +0.7 3 Sodium benzoate ATOH + 5.1 -17.7 -4.0 4th P-nitrobenzenesulfonic acid ETOH -32.0 - 3.8 -2.7 5 3-nitrophthalic acid ETOH -27.3 -14.1 -5.6 6th p-nitrocinnamic acid ETOH -15.6 7th

*) = Material of the impact head of the test device used.

**) = layer of cellulose acetate hexahydrophthalate and carbon black dispersed therein, i.e. H. the butt head was with one layer of the specified composition of the type customary for film backing layers.

Table Ib

Attempt no.

Surface treatment with

solvent

Compared to metal Uuinmi

Control sample, average value

9 10 Π 12 13 14 15 16

Table Ic

no

p-nitrobenzenesulfonic acid, sodium salt

p-nitrophenyl acetic acid

p-nitrophenoxyacetic acid

3-nitrochalcone

2,4-Dinitro-1-naphthol-7-sulfonic acid

4-nitrophthalic acid

p-nitrobenzamide

2,4,6-trinitrobenzenesulfonic acid

m-nitrobenzenesulfonic acid, sodium salt

ETOH

+ 8.4

+ 9.3

ATOH -32.1 - ETOH -13.4 + 1.9 ETOH -26.7 - 7.6 ETOH + 0.4 + 11.5 ETOH -23.0 -13.1 ETOH -39.6 -12.0 ETOH - 4.3 + 0, p ETOH -39.0 + 7.1 ETOH -29.0 + 6.0 Solution
middle Comparative object
Gelatine *) blank **)

Attempt no.

Surface treatment with

Control sample,

average value

no

p-Nitrobenzoic sulfinic acid, dibutylamine salt p-Niirobenzoic sulfinic acid, dibutylamine salt p-toluenesulfonic acid

4-chloro-m-toluenesulfonic acid, sodium salt p-Fluorobenzenesulfonic acid, sodium salt p-Chlorobenzenesulfonic acid, sodium salt p-Bromobenzenesulfonic acid, sodium salt 2,5-dichlorobenzenesulfonic acid p-llydroxybenzenesulfonic acid, sodium salt (! - (Carboxy met hoxy) -benzoic acid

ETOH

+ 8.5

- 0.3

ATOH -24, c - PrCl - 3.0 - ETOH -18.6 -20.5 ETOH - 3.0 - 3.0 ETOH -22.0 -14.0 ETOH -35.0 -22.0 ETOH -10.0 - 8.5 ETOH + 5.0 - 8.0 ETOH -22.0 -15.5 ETOH -35.0 -24.5

12th

continuation

Attempt no.

Surface treatment with

solvent

Comparison surface Gelatine *) blank **

p-hydroxybenzoic acid p-chloropheny! acetic acid Sulfosalicylic acid

*) Polyester strips made of polyethylene terephthalate coated with gelatine. *) Uncoated polyester strips made of polyethylene terephthalate.

ATOH -30.0 -10.0 ETOH -13.0 - 0.6 ETOH -45.0 -36.0

Table Id

Attempt no.

Surface treatment with

solvent

Comparison surface

ueiaime- /

Control sample, no ATOH + 11.5 - 0.5 average value 30th 4-sulfophthalic acid, monosodium salt ETOH -25.0 -16.0 31 2,2'-diphenic acid ETOH -11.0 - 3.0 32 Trimellitic acid ETOH -32.0 -28.0 33 Benzenesulfonic acid ETOH -32.0 - 0.4 34 4-sulfophthalic acid, dibutylamine salt ETOH -14.0 -14.0 35 Pyromellitic acid MeOH -40.0 - 5.5 36 Terephthalic acid MeCH + 18.0 -10.0 37 Phthalic acid MeOH + 20.0 - 4.0 38 Phthalic acid ETOH -34.0 -15.5 39 Mellitic acid MeOH -40.0 - 8.0 40 Salicylic acid ETOH + 3.0 - 41 Pyromellitic acid, monosodium salt ETOH -15.0 -

*) Polyester strips with a gelatin layer to which the charge control agent was applied from a solution. *) Polyester strips to which the charge control agent has been applied directly from a solution.

Table Ie

Attempt no.

Surface treatment with

solvent Surface*) 45 H ₂ O + 4.0 H ₂ O + 13.0 50 60:40 MeOH / HjO + 1.4 60:40 MeOHZH ₂ O + 0.9 MeOH - 7.0 MeOH + 1.2 55

42 Pyromellitic acid, ammonium salt, pH 4.3, 1%

43 Pyromellitic acid, ammonium salt, pH = 8.2, 1%

44 mellitic acid

45 pyromellitic acid

46 5-sulfoisophthalic acid, sodium salt

47 5-SuIfosaIicylic Acid

*) Ccllulose acetate layer carrier with gelatine-cellulose nitrate adhesive layer.

Several of the charge control agents under test were further applied from aqueous solutions.

The molecular size of many of the simpler compounds allows them to be swollen from the Gelatin topcoat can be absorbed because the gelatin topcoat does not contain a hardener. Some fabrics can furthermore from the surface in the course of longer periods of time at higher relative humidity, which allow a considerable swelling of the gelatin layer, are absorbed. In these cases the compounds are no longer present on the surface, unless they are surface-active compounds, and the surface has the characteristics of an untreated gelatin layer.

/ JU

Example 2

In order to change the charging properties of gelatine surfaces, it is also possible to use charging agents, especially simple structure, together with gelatin in the form of mixtures to apply aqueous solutions to substrates. In these cases, however, is a comparatively larger one Amount of charge control agent required than when applied to the surface of the gelatin layer will.

Mixtures of gelatin and the charge control agents listed in Table II below were applied to cellulose acetate propionate substrates having a propionyl group content of 14% and an acetyl group content of 30%. and butyl sebacate as a plasticizer sprayed on or applied by hand coating. A gelatin-cellulose nitrate adhesive layer was previously applied to the substrate using a conventional gelatin-cellulose nitrate solution (1% gelatin, ^x h ° k cellulose nitrate [11% N ₂ ], 2% acetic acid) in methanol and acetone.

The charging values obtained in detail are summarized in Table II below.

Table II

Experiments with gelatin layers containing charge control agents on cellulose acetate propionate supports - Electrostatic charge, generated by one-sided impact with a stainless steel impact head Esu / cnv at impact pressure of 1.4 kg / cm "

Attempt no.

Charge control means

Ratio of gelatin to charge control agent

t: 1 no

I: 2

Adhesive layer control without - sample Gelatin control sample without - 48 5-sulfosalicylic acid + 5.0 -, 9 Pyromellitic acid +3.5 50 Sodium salt of a naphthalenesulfonic acid - condensation product (Tamol N) 51 Mellitic acid -9.0 52 Saponin +0.2

+ 22.0

+ 17.0

-2.0
-0.4

An examination of the values determined shows a considerable reduction in the high positive charging capacity the gelatin.

Example 3

On the basis of the data obtained in Example 2, machine coatings were carried out around the coating thickness to control, with other comparison surfaces tested and other humidity levels were applied. A 12.7 cm wide coater was used.

The coating solutions consisted of: 1% and 1.5% pyromellitic acid and 1% gelatin.

A specially purified gelatin was used as the gelatin.

The pyromellitic acid and gelatin control samples contained 0.19% saponin as a coating aid.

The five solutions prepared were applied to cellulose triacetate and cellulose acetate propionate layers using a coating funnel using conventional coating methods. The cellulose triacclate supports had an acetyl group content of 41%. The cellulose acetate propionate carriers had a propionyl group content of 14% and an acetyl group content of 30%. The supports had a customary adhesive layer made of gelatin and cellulose nitrate. The supports were coated with a) 123 and b) 154 ml of solution per 9.29 m ^{2 of support} surface.

The specimens were then tested as described using two comparison surfaces made of stainless steel and a carbon black dispersion in cellulose acetate hexahydrophthalate.

The values obtained are summarized in Table III below.

Table III

Experiments with cellulose acetate propionate layer carriers with gelatin-cellulose nitrate adhesive layers and gelatin layers containing charge control agents applied to them under electrostatic charging by one-sided impact of 1.4 kg / cm ² with an uncovered metal hammer head or with a hammer head covered with carbon black dispersion.

attempt
No.

treatment

Coating thickness of 5% metal

5%

Soot dispersion *)

15%

Soot dispersion *)

50%

Soot dispersion ··)

53 untreated adhesive layer

54 control sample, 1% gelatin

55 control sample, 1% gelatin

56 1% gel. + 1% PMS *)

57 1% gel. + 1% PMS *)

58 l% gel. + 1.5% PMS *)

cn ι ο / / -! "ι ι ι c oj m / c * \

_ / • 1 / OW * -i. I L ^ J / 0 I IVAkJ /

60 1% gel. + 1% saponin

61 1% gel. + 1% saponin

62 1% gel. + 1.5% saponin

63 1% gel. + 1.5% saponin

*) Pyronicllitic acid.
**) Dispersion of carbon black in cellulose acetate hexahydrophthalate.

+ 30.0 + 5.9 + 5.5 + 5.8 123 + 3.8 + 3.2 + 3.7 + 3.6 154 + 2.0 + 2.4 + 2.9 + 3.4 123 - 1.2 +0.52 + 1.1 + 0.87 154 - 2.0 +0.5 +0.8 + 0.4 123 - 2.0 + 0.52 -0.1 +0.5 154 - ·>< ^Δ +0.2 -0.03 +0.4 123 + 2.0 + 1.4 + 2.4 + 3.2 154 + 1.0 + 1.2 + 2.1 + 2.7 123 + 0.3 + 1.3 + 2.0 + 2.6 154 + 1.0 + 1.1 + 2.4 + 2.0

From Table III it can be seen that pyromellitic acid is significantly more effective than saponin and so on is relatively independent of the humidity, whereas saponin has a positive trend (less effectiveness) shows at humidity. The lower values obtained in the case of comparative samples 1 and 2 result from 0.19% saponin, which was used as a coating aid.

Example 4

Layer support of polyethylene terephthalate and Celluloseestern were first coated with a 5% gelatin solution such that a m Trägerfiäche of ^9.29: ό 15 ml of the gelatin solution accounted for. In this way, gelatin layers were produced which formed insulating layers to which a further special gelatin layer was subsequently applied, ie a layer of gelatin that was modified in contrast to the first layer.

For this purpose, a 2.9% gelatin solution was first used using low concentrations a fluorinated surfactant of the formula:

[C ₁ F ₁₇ SO ₂ NH (CH ₁ ) JN (Me) ₃ ] * I ⁹

manufactured.

This gelatin solution was then applied in layer thicknesses, corresponding to 175 ml and 350 ml of solution per 9.29 m ^{2 of} support surface, to the layer support already provided with a gelatin layer. The test specimens obtained were then initially conditioned at a relative humidity of 5% and a temperature of 21 ^° C. for carrying out the charge test.

The impact load values were determined at an impact load of 1.4 kg / cm ² at a relative humidity and a temperature of 21 ° C. The results obtained are summarized in Table IV below:

Table IV Impact charge Esu / cm ² Concentration of surface-active Coating A Coating B Connection in g / 0.45 kg melt + 18.0 +23.5 0.0001 + 18.5 +22.0 0.0005 + 19.0 +25.5 0.002 + 19.0 + 17.5 0.008 + 18.0 + 13.5 0.01

15th

continuation 22 34 736 Esu / cm ²
Coating B Concentration of
surface-active
Connection in
g / 0.45 kg melt Impact charge
Coating Λ - 7.5
-21.0
-29.0 0.02
0.03
0.04 + 9.8
-10.0
-10.7

Coating A corresponds to 175 ml of solution per 9.29 m ^{2 of support} surface and coating B to 350 ml of solution per 9.29 m.

The results compiled in Table IV show that the two gelatin layers of different thicknesses have a charge value of 0 at a concentration of surface-active compound of 0.025 or 0.015 g per 0.45 kg. In the case of coating B, impact charges in the range of 0 ± 8 Esu / cm ^{2 are achieved} at concentrations of 0.012 to 0.02 g per 0.45 kg.

In the manner described, additional layers were made with other charge control agents from that in the CoI Table V indicated constitution tested. The additives were used in concentrations of 0.05; 0.1; 0Λ 0.4 and 0.8 wt .-% added.

The thickness of the coating corresponded to 175 ml of solution per 0.29 m ^{2 of} support surface. The impact load was 0.70 kg / cm ² . The relative humidity was 5%. The temperature was 21 ° C.

25 Table V

% By weight of additives 0 0.05 0.1

0.2

0.4

CH ₃ C ₇ F ₁₅ -CONH- (CH ₂ ) JN-CHj

CH ₃

+ 13.8 +25

-12.4 -13.7

CHj

C ₉ H ₁₉ -CONH- (CHj) ₃ -N-CH ₃

CH ₃

+10.5 + 0.6

- 5.5 - 6.5 -5.5

CH ₃

C ₁₇ H ₃₅ -CONH- (CHa) ₃ -N-CHj

CH ₃

OH

Il

₅₅ C ₁₆ H ₃₃ -OP-OK

OH

C ₁₂ H ₂₅ -OP

OH

J® +10.5 + 2.2

+ 10 + 5.5

- 4.2 - 5.8 - 7.0

+ 6.6 + 6.2 +4.8

+ 10 + 1.4 +1.6 + 1.2 - +1.2

Example 5

This example shows that mixtures of surface-active compounds can advantageously be produced of impact charging values close to 0 can be used within a wide range of concentrations.

16

In the following table VI, the measurement results are compiled when using a sapcinin-fluorocarbon mixture were obtained.

The impact electrification values or impact electrification values were determined at an impact pressure of 0.70 kg / cm ² , at a relative humidity of 5% and a temperature of 21 ° C

Table VI

Impact electrification when using saponin

Fluorocarbon mixtures.

Fluorocarbon saponin concentration in

substance concentration in g / 0.454 kg melt

g / 0.454 kg melt _{QW QJgQ}

0.02 +1.7 0.0 ^li

0.04 +0.5 -0.6

0.08 -0.6 -1.5

0.16 -2.4 -2.5

The data were determined as described in Example 4.

A comparison of the data compiled in Tables IV and VI shows the extent of the effective Working concentration for the fluorocarbon by using a mixture of charge control agents and coating aids. Through the use of combinations of charge detergents and coating aids, the charging characteristics of surfaces can be very 2 < set exactly.

The use of anionic surfactants, e.g. E. Alkylaryl polyoxyethylene sulfonate salts and triisopropylnaphthalenesulfonate sodium salts, as a coating aid is used in photographic applications Industry has become common. Such surface-active compounds, however, contribute greatly to the formation of static Film product markings. The use of mixtures of fluorocarbons 3C with surface-active compounds and coating aids enables the manufacturer to be photographic Products the static charge properties of various surfaces, in particular Layer surfaces to be kept within the required limits. The use of such mixtures allows it also uses the best available surface-active compounds as coating aids to be used, so that the quality of the layers produced is not affected by adverse charging effects the coating aids used needs to be impaired.

In addition to the specified anionic surface-active compounds, a wide variety of others can be used Surface-active compounds for the preparation of adhesive or primer layers, backing layers, emulsion layers and in top layers over emulsion layers to control the charging properties of these Layers and the end product comprising such layers can be used. 4c

Example 6

Similar results as described are obtained in the treatment of X-ray materials, although with such materials usually a double protection through the incorporation of a charging 4: Stcucrmittel and a conductive connection to modify the electrostatic charge properties of X-ray materials is usually not required, since such products are usually only comparatively few surfaces come into contact and the production-related and processing-related Problems are a little less here.

In a conventional loading device, film supports with an X-ray material were applied borrowed adhesive layer, the adhesive layers having various concentrations of a charge control agent were added.

To prepare the adhesive layers, a customary coating composition made of gelatin, saponin, a Fungicide, a hardening agent such as chromium aluminum sulfate, and a matting agent are used.

The following table VII shows the influence of saponin additives on the impulse electrification of the s: Adhesive layers.

Table VIl

Impact electrification of modified adhesive layers by stainless steel and anodized :; Aluminum in one

Impact pressure of 1.4 kg / cm ² and a temperature of 21 ° C ^w

Test item No. Total amount 5% relative humidity 50% relative humidity Saponin in% _{S (ah |} anodized steel anodized Aluminum aluminum

0 + 28.0 + 12.5 + 26.0 + 16.0 0.01 + 24.0 + 11.0 + 22.0 + 12.7

continuation

Test item no. total quantity 5% relative humidity 50% relative humidity Saponin in% stole anodized stole anodized aluminum aluminum 3 0.15 + 5.9 + 6.0 + 8.4 2.4 4th 0.20 2.0 3.5 - 0.3 - i, o 5 0.25 - 1.6 + 2a - 4a - 1.8 6th 0.30 - 3.0 + 0.8 - 5.0 - π commercially available + 16.5 + 10.5 + 17.0 + 7.3 X-ray material

From the data compiled in Table VII it can be seen that higher concentrations of saponin in can advantageously be used to reduce the charging characteristics of the adhesive layers.

In further experiments, mixtures of saponin and p-chlorobenzenesulphonic acid, sodium salt, hereinafter referred to as p-Cl.S.S., Na-Salz, were used as additives in adhesive or primer layers. Included the results compiled in Table VIII below were obtained:

Table VIII

Impact electrification of modified adhesive layers using stainless steel and anodized aluminum.ninium at an impact pressure of 1.4 kg / cm ²

Test item no. Additions in%

Saponin p-Cl.SS-Na-Salt steel

7th 0.01 0.4 8th 0.01 0.45 9 0.01 0.5 10 0.10 0.45 H 0.10 0.50 12th 0.10 0.60 13th 0.10 0.70 14th 0.13 0.50 i5 0.15 0.50 16 0.18 0.50 17th 0.13 0.60 18th 0.15 0.60 19th 0.18 0.60 Comparative sample

5% relative humidity anodized 50% relative humidity stole aluminum stole anodized + 9.0 aluminum + 16.0 + 2.6 -22.0 - 9.0 + 7.2 - 6.5 -25.0 - 10.0 - 9.5 + 9.0 -27.0 -13.3 + 13.8 - 2.5 - 8.0 - 5.4 + 5.0 - 1.2 - 8.0 - 1.2 - 5.0 - 2.5 -11.7 - 5.0 - 5.0 + 1.2 -10.0 - 5.0 + 5.3 + 1.0 -11.4 - 6.0 + 2.6 + 0.8 -12.0 - 8.0 + 5.4 - 5.1 - 6.0 - 4.0 - 4.2 - 4.9 -14.4 - 8.5 - 5.6 - 4.5 -14.0 - 7.0 - 2.5 + 10.5 - 9.0 - 4.5 + 16.5 + 17.0 + 7.3

The data compiled in Table VIII resulted in four mixture concentrations at which the general criterion of 0 ± 10 Esu / cm ^{J is achieved} under all conditions tested. The compiled data also shows that 10 of the mixture concentrations correspond to the general criterion of 0 ± Esu / cm ² compared to the anodized aluminum roller surface in both moisture ranges.

It should also be noted that in those cases where saponin is normally used as a coating aid is used is used in combination with a charge control agent, a better one Addressing the control of the charge properties of surfaces is achieved because of smaller deviations occur in the charge behavior with corresponding quantitative additions of a charge control agent.

Example 7

Saponin and p-chlorobenzenesulfonic acid, sodium salt, (p-CI.S.S .. Na-Salz) were used as mixtures at the Used in the production of adhesive or primer layers.

Adhesive layers were applied to four production spools of substrates made of polyethylene terephthalate, which contained 0.2 ".-. saponin and 0.45% p-Cl.-S.-S., sodium salt.

Ib

The values determined during shock electrification are compiled in the following table:

Table IX

Production rolls with saponin and p-CI.S.S., Na-SaIz - additives to the polyethylene terephthalate adhesive layer (Gelatine, matting agent, fungicide).

Sample no. Push electrification Al *) 50% relative humidity 5% relative humidity - 6.4 stole Al *) stole -10.2 -20.0 -8.4 1 -10.0 - 6.3 -20.0 -7.5 2 - 9.1 - 7.0 -23.0 -7.6 3 - 5.4 -20.0 -7.5 4th - 9.0

*) Al = alloy with predominantly aluminum.

Two of the production spools were then coated with an emulsion in the usual manner. No evidence of static build-up defects was observed in the development of this material. The emulsion adhesion was good and furthermore there was no evidence of peeling of the gelatin due to the tacky adhesive layers during emulsion coating.

It is essential that all, with the exception of one sample, which were produced in the production facilities, were very close to the general criterion of 0 ± 10 Esu / cm ² for anodized aluminum surfaces.

The results of Table VIII also show that there is still enough room for concentration changes in order to reduce the charge to the 0 value.

Additions of p-CI.S.S.-Na salt to adhesive layer or primer compounds in concentrations of e.g. B. 0.45% up to 4.5% showed no adverse sensitometric effects.

Although the examples apply the method of the invention to the treatment of polymers built up Illustrate substrate materials that may have an adhesive or primer layer or backing layer have, the process of driving, as already explained, can also be applied to other objects for which undesirable triboelectric effects occur. So, to name just a few examples, according to the procedure the invention also includes the known, coated with photosensitive polymers and synthetic resins, Recording materials and papers which are widely used in the photographic field Find use. Furthermore, adhesive or primer layers of this type can also be used, for example Materials can be modified according to the method of the invention. The charge control means optionally over halide emulsion layers and other light-sensitive layers, i.e. silver halide and are not made on the basis of gelatine.

Although in the examples primarily the addition of charge control agents with relatively high negative charge characteristics on surfaces which show a relatively high positive charge, can be described but in the same way charging control center! positive charging characteristics using the same methods can be used to reduce or increase the charging tendency of surfaces.

The most favorable amounts of charge control agents to be obtained by the method of the invention from the to Modifying surfaces absorbed, applied to the surfaces to be modified or in to be modified Surfaces that can be incorporated depend on many different factors which the Affect the charging of the surfaces to be modified.

As can be seen from the above examples, the following points in particular must be observed:

1. The static charging properties of surfaces are obviously a direct result of them chemical structure. In particular, the strong positive ones can be obtained by the method of the invention Charge characteristics of gelatin and gelatin-cellulose nitrate adhesive layers or primer layers or "neutralize" backing layers, as used in the case of photographic materials or "cancel" by adding a negative charge control agent to these surfaces w-rd, e.g. B. by applying from a suitable solvent or in some other way with training a continuous or discontinuous layer having a thickness, measured dry, of preferably less than 300 angstrom units.

2. The effect of this technique depends on the thickness of the coating or covering, which is what it is

the charge or the surface potential of the object to be modified within a wide range Can vary within the scope.

3. The charging properties of unmodified surfaces, the surface of a charge control agent as well as a surface modified with a charge control agent can be used with Security does not predict why it is necessary if the loading characteristics of a particular one Surface should be modified, first the charging properties or charging characteristics To examine the unmodified surface to be modified, a number of charge control agents are used to test in terms of their charge properties, from the tested compounds to select a suitable compound and to add this in various concentrations to the

Work in or apply the surface until the desired degree of charge and polarity is achieved.

Such a method is even in the case of using homologous groups of charge control agents required, since connections that are very similar to one another, even from a structural point of view, are often quite S have different charging properties, as can be seen from Example 1, for example.

Although the surfaces of objects have always been modified in the description and examples, which needs to be modified, it should be pointed out that similar results will then also be achieved can, if the surface causing the charge, d. H. for example in the case of aviator films that Camera rollers or rollers or in an emulsion coater made of stainless steel or

ίο anodized aluminum existing rollers are treated. Such a treatment can for example be done in such a way that the surface of such rollers or cylinders with suitable charge control means impregnated or that such agents are layered on the surface of the rollers or cylinders in this way or can be applied so that a 0 charge or a very low charge is obtained when the rollers or Rollers, for example, with a layer support or the

15 emulsion or film carrier side of a special light-sensitive material come into contact.

As has been explained in detail, the generation of triboelectric charges is based on bringing them into contact and the separation of two usually different surfaces. The method of the invention enables the reduction of triboelectric charges to an acceptable level by treatment or modification of one or both of the surfaces in contact with one another. In the event of

20 of the charging problem that occurs when using aviator films can thus, for example, be a Reduction of the triboelectric charge can already be achieved in that the Kar ^ ratransportwalzen or KarneraroHen with a suitable charge control center! coated or impregnated.

Claims (1)

Patent claims: 1. Use of compounds of the general formulas: [AZ- (CH ₂ ^ D] * Χ ^θ (I) where mean: A is an optionally partially or fully fluorinated hydrocarbon radical; Z is a remainder of the formulas: O O O O Il Il Il Il —S — NH- —C — NH- —S — NH- or —P — NH- Il I O OH a remainder of the formula: R ¹ - N —R ² in which R ¹ , R ² and R ^{5 represent} hydrogen atoms, short-chain alkyl radicals or aryl radicals, X® is an anion and
η is a number from 1 to 8; or Ζ — Χ —Υ —Μ (Π) where mean: Z those required to complete an aromatic or alicyclic hydrocarbon radical Atoms which can be substituted by one or more halogen atoms and / or one or several nitro, nitroso, hydroxyl, carboxy, cyano, alkoxy, aryloxy and / or substituted alkoxy residues and / or residues of the formula: Il - C -OR ⁴ wherein R ^{4 is} an optionally substituted alkyl or aryl radical; X is a remainder of one of the following formulas: OO O O \ Il Il Il Il C = O —S— —P — OH - (CHz) -C- - O- (CH ₇ * -C- / Il I O O Il -CH = CH-C- or -CH = CH- with the proviso that η is a number from 1 to 10; M represents a hydrogen atom, an ammonium radical, a metal cation or an amine salt radical or an optionally substituted phenyl radical and Y 1. an oxygen atom when M is a hydrogen atom, an ammonium radical, a metal cation or an aniinsalzrcsl or
2. an imino radical (-NH-) when M is a hydrogen atom or 3. a carbonyl radical (= C = O), when M is an optionally substituted phenyl radical, or a mixture of the compounds listed under (I) and (Ii) as a charge control agent for modi Determination of the electrostatic charging properties of the surfaces of photographic materials. 2. Use of compounds according to claim 1, characterized in that they correspond to the formula (I), in which: A is a partially or fully fluorinated hydrocarbon chain,
7. a remainder of the formula O O 11 Il —S — NH— or —C — NH—, Il π = 3 and X is a halogen atom.