DE2234736A1 - PROCESS FOR MODIFYING THE ELECTROSTATIC CHARGING PROPERTIES OF OBJECTS - Google Patents

Description

PATENTANWÄLTE DR-ING. WOLFF, H. BARTELS, DR. BRANDES, DR.-ING. HELD Dipl.-Phys. Wolff

8 MONKS 22 ..2.6..f..J.UnJL.19..7

THIERSCHSTRASSE «*,.

TELEPHONE: (0811) 29 32 97 Z 5 / Z

Registration number. 123 392

EASTMAN KODAK COMPANY, 343 State Street, Rochester, New York State, United States of America

Process for modifying the electrostatic charging properties of objects.

20908 5/12

The invention relates to a method for modifying the electrostatic charging properties of objects » in particular of photographic materials, the surfaces of which become electrostatically charged when they come into frictional contact with another, especially different, Surface can be brought.

In the production and use of films and support materials made up of polymers, in particular of sensitized radiographic and photographic products the generation of electrostatic charges is a serious problem. In the case of sensitized materials, especially sensitized radiographic and photographic materials, lead by electrostatic charges caused discharges to particularly serious effects by the fact that flashes of light occur during the discharges, which are undesirably recorded by the photosensitive material. In the case of magnetic tapes or magnets Tapes that are sensitized to invisible electromagnetic radiation can make themselves noticeable by electrostatic discharges through unpleasant noises.

The electrostatic discharges can occur in the course of the manufacturing process of the materials, e.g. during the coating of substrates, the post-treatment of coated materials and the packaging of such materials, or during the use of such materials, e.g., in cameras, copiers, tape recorders and the like.

Other adverse effects which may be caused by the buildup electrical charges on polymer layers

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have materials, both coated and uncoated substrate materials, occur in the production of these materials and can be recognized, for example, by coating defects, e.g. B * due to non-uniform coating _{quantities, i.e. coatings of various thicknesses are obtained (} which in turn can cause problems with winding.

These undesirable effects are based on the undesired one Accumulation of localized "electrical" charges, e.g., on the Surfaces of the various products that make film * p> run through the process »

In the manufacture of photographic and radiographic Recording materials lead to such areas of localized charges, in particular, to disturbances when applying sensitized ones or light-sensitive layers, whereby the uniformity of the layer structure is disturbed »

Although there are a variety of causes, generated by which such undesirable electrostatic charges "the occurrence of electrostatic charges is z, B ₁ sensibilisjerter in the manufacture and use of photographic materials under the general term | ^f Triboelektrizltät "summarized. This term is an electrostatic charge is to be understood that two by friction or contact surfaces and subsequent physical separation does not always occur" In general, _t, however, the two together screened Tenden contacting surfaces are "different from each other.

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/ If

The level of charges generated in this way depends on several factors, the most important of which 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 also important that by friction and multiple contacting and separating different surfaces during the During the manufacturing process of an object, there is often a strong accumulation of electrostatic charges in and on the process products and parts of the products used to manufacture the process products The devices used are carried out, the charge effect generated by rubbing two surfaces together is referred to as the triboelectric effect. The formation of electrostatic Charging by separating two different surfaces in contact can be explained by the fact that a contact between two surfaces obviously leads to a specific charging effect on the surfaces involved, in general with a cumulative accumulation of charges on the surfaces leads in an additive manner, the conductivity of the surfaces in question being generally for that actually observed The amount of the charge is decisive.

Disadvantageously, only very few film materials composed of polymers and coated photographic film materials themselves have such a high electrical conductivity that due to this conductivity the accumulation of electrostatic Charges can be prevented.

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It has. There has been no lack of attempts by electrostatic discharge To eliminate charge-induced defects or to reduce them to a minimum, namely so-called "electrostatic" Defects "and" electrostatic marks "which express expressions of triboelectricity. Under electrostatic characters are to be understood those characters that are used in photographic Materials caused by a discharge and recorded in sensitized layers. It has shown, that minimal electrostatic. Top-ups are required, in order to lead to discharges of such intensity and duration that they can be recorded by sensitized layers.

In the case of a film material composed of a polymer, for example a cellulose acetate base with a conventional photographic In the emulsion layer, the binder of which is primarily gelatin, there is a discharge of electrostatic electricity already when a triboelectric charge in the order of +8 to +10 Esu, i.e. electrostatic input

2 2

units per cm (+26.5 to +33.2 microcoulombs / m) is achieved, Of course, the specified numerical values depend on the materials used in the individual case, the humidity conditions and like that. When using emulsions whose binder consists primarily or mainly of gelatin, have the emulsions have a tendency to develop positive triboelectricity, when they come into contact with a wide variety of surfaces that are used during the photographic manufacturing process Materials come into contact with the emulsion layer.

The main body of publications dealing with the triboelectric Deal with phenomenon deals with the dissipation of accumulated electrostatic charges, especially those Charges that can be generated on the surface of layers made from polymers.

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The most common method of deriving electrostatic r Charging is based on the introduction of certain compounds into the polymer layers which eliminate electrostatic charges or reduce the build-up of electrostatic charges by increasing the conductivity of the layers.

Although many of the conductive compounds used hitherto for the purpose described affect the conductivity of the surfaces of polymers improve remarkably as they tend to generate larger amounts of static electricity from friction or to produce contact with a surface different from the surface of the polymer used »As a result the amount of electrostatic charges on such polymer surfaces that contain conductive compounds, so be large that the conductive connections are not able to dissipate the accumulated charges quickly enough, to prevent sudden discharges.

It has also been shown that many of the conductivity increasing compounds only work satisfactorily in an environment of relatively high humidity. Usually lose such compounds maintain their conductive properties at relative humidity levels 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 ionic in nature, which is why they are used in dissociate relatively high humidity. Many of these conductive connections also have the disadvantage that the surfaces of the polymers to which they are added become sticky. The appearance of sticky surfaces is particular disadvantageous in the case of photographic recording materials and can result in a partial removal of gelatine Adhesive or primer layers from the substrate

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materials during the manufacturing process. So In particular, defects can occur due to the fact that small particles of gelatin form the adhesive or primer layers stick to the transport rollers or rollers or other rollers with which the materials come into contact during their manufacturing process. You use hygroscopic conductive connections has therefore not proven itself "

To the disadvantages caused by the use of hygroscopic conductive connections are created, to bypass, it has also become known, e.g. from US Pat. No. 3,082,087, which by rubbing or suddenly separating two film surfaces in contact with one another to reduce electrostatic charges by equipping the materials with antistatic layers which are built up from substances which are characterized in that they (a) have a tendency to become charged, that of the charging tendency of the film material to be modified is opposite or (b) which have a charging tendency which is of the same polarity as that of the one to be modified Footage is less, however.

One of the major drawbacks of this process of modifying electrostatic charges is' that it is purely qualitative in nature. According to the method described in Patent Specification 3,082,087, the charging tendency of a film surface is first determined, followed by a layer of a film Styrene copolymer is applied to the film surface in the hope of reducing the tendency of the film to become charged. , The patent specification does not open up a way that makes it possible to to control the degree of charging of a film surface quantitatively and reliably by applying a styrene polymer.

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The object of the invention is to provide a method for modification the electrostatic charging properties of such objects indicate whose surfaces become electrostatically charged when they come into frictional contact with another, in particular different, surface, the method of the invention should in particular for the production of photosensitive or photosensitive, photographic and radiographic materials may be suitable so that their surfaces either (a) practically free of static electricity remain when the surfaces' with other, in particular different, Surfaces come into rubbing contact or are separated from one another again after being brought into contact, or (b) only accumulate such small amounts of charge that are not sufficient to cause discharges.

The invention thus relates to a method for modifying the electrostatic charge properties of the various objects which, surface charge electrostatically when particular various surface are brought into rubbing contact with another _#, which is characterized in that:

(a) First, under standardized conditions, the degree of electrostatic Charge of the surface of the object to be modified measured by rubbing the surface with a other, in particular different, surface and / or is caused by the separation of the two surfaces that one

(b) based on the results of stage (a) through test trials a Compound or a mixture of compounds, the or the degree of electrostatic charge of the surface to be modified is able to change in the desired sense, selects and that one

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and / or in the (c) on the surface to be modified, as much of the selected Compound or the selected mixture of compounds as "Charge control agent" applies / that the desired modification occurs.

The method of the invention thus enables the charging properties of surfaces ^{to be changed quantitatively by suitable selection of compounds or substances referred to herein as "charge control agents 11} , these charge control agents being able to modify the charging tendency of the most varied of surfaces to the desired extent. From The process of the invention is of particular importance, for example, for the modification of the surfaces of polymers, in particular hydrophobic polymers, for example molded articles made of synthetic hydrophobic polymers such as films and substrates, textile structures, for example carpets, but also for the modification of objects made of glass, ceramic materials, leather and metal, which can be coated with a wide variety of polymers. The process of the invention is of particular importance for the production of photographic and radiographic materials, especially those with surfaces containing gelatin, since gelatin is known is actually used in large quantities for the production of photographic materials «The degree of electrostatic chargeability can be prevented, for example, from being below the threshold value at which» adverse effects due to discharges can occur »

The process of the invention thus enables, in particular, the production of radiation-sensitive photographic materials and photographic support materials whose tendency to electrostatic charging is greatly reduced or even eliminated by using as a charge control means designated compounds or compound mixtures, namely by incorporation in or on one or more layers of such materials.

/ "or, brings in

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* t

According to a particularly advantageous embodiment of the method of the invention, compounds of the following type are used as the charge control means!

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YES

I. a surface-active compound of the following formula:

A Z -— eCH ₉ * - D_ / X

where mean:

A is an optionally partially or fully fluorinated, (perfluorinated) hydrocarbon radical with preferably 1 to 20 * carbon atoms;

Z is a remainder of the formulas:

0 0 0 0

ι - ι η ι

-S-NH-; -C-NH-; -S-NH- or -P-NH-OH

a remainder of the formula:

-N- R ₂ , in which R., R ₂ and R _{3 are} hydrogen atoms,

x _D short-chain alkyl radicals with preferably

se 1 to 5 carbon atoms or aryl radicals, preferably optionally substituted Phenyl or naphthyl radicals, i.e. Radicals of the phenyl or naphthyl series represent;

X is an anion and

η is a number from 1 to 8;

II. A compound of the following formula:

Z-X-Y-M

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where mean:

Z the atoms required to complete an aromatic hydrocarbon radical, in particular a phenyl radical, to which up to 4 benzene rings can optionally be fused, or an alicyclic hydrocarbon radical, especially a cycloalkyl radical, e.g. a cyclohexane radical or a decalin radical, where: that these aromatic and alicyclic radicals can be substituted, e.g. B. by one or more halogen atoms and / or one or more nitro, nitroso, hydroxyl, carboxy, cyano, alkoxy, aryloxy and / or alkoxy substituted alkoxy and / or radicals of the formula: Ο

-C-öR, where R is an optionally substituted Alkyl radical with preferably 1 to 20 carbon atoms or aryl radical, in particular of the phenyl or naphthyl series is;

X is a remainder of one of the following formulas:

O O O

Ml Il

: c-0; -S-; -P-OH; - (CH ₂ ^ -C

O O

JL

or -CH = CH-

with the proviso that η is a number from 1 to 10;

M is a hydrogen atom, an ammonium residue, a metal catalyst of groups I and II of the Periodic Table of the Elements or an amine salt radical or an optionally substituted phenyl radical and

Y 1) an oxygen atom, when U is a hydrogen atom,, a

Ammonium residue, a metal cation of groups I and II 209 885/1209

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of the Periodic Table of the Elements or a Is amine salt residue, or

2) an imino radical (-NH-) when M is hydrogen is or

3) a carbonyl radical (= C = 0), if M is optionally is substituted phenyl;

III, a carboxylic acid of the following formula:

HOOC-R-COOH
in which R represents a residue of the following formulas:

2) - {- en, - * -— ec, "

2 m ^ n

R ₂

3)

4)

f f

^R 2

with the proviso that when Pv is a radical of the formula 1) or 2), R _{1 is} a hydrogen atom and R- is a halogen, nitro, optionally substituted aryl or hydroxyl radical , with the further proviso that when R is Radical of the formula 3), R ₁ and R ₂ each represent a hydrogen or halogen atom, a nitro, carboxyl, optionally

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substituted aryl or optionally substituted Represent alkyl radical and where it also applies that when R. is a hydrogen atom, R- is a hydrogen or Halogen atom, a hydroxyl, nitro, carboxyl, optionally substituted aryl or optionally substituted Alkyl radical, all alkyl radicals preferably having 1 to 20 carbon atoms and the aryl radicals preferably from phenyl radicals to which up to 4 benzene nuclei can be fused, d, h, z. B, leftovers the phenyl, naphthyl or anthryl series can exist, and η and m represent integers, preferably from 1 to 30;

IV, a carboxylated polymer with free carboxyl groups;

V. a compound of the formula:

OM

R ₁ 0-jO

where mean:

1) R _{1 is} a radical of the formula CH ₃ - (CH. ^ -, in which η is a number from 1 to 19, then R _{2 is} a hydrogen atom or a radical of the formula CH ₃ - (CH ₂ J _n , - with n ¹ - 1 to 19, where n ¹ ■ η or can be different from η;

2) R ₁ and R- unsaturated hydrocarbon radicals with preferably up to 20 carbon atoms or optionally substituted aryl radicals, in particular phenyl radicals with up to 4 fused benzene rings, d, h, z, B, radicals of the phenyl, naphthyl or anthryl series;

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3) Ra is a polymer radical, ζ, B. the radical that completes a cellulose phosphate or a polyvinyl alcohol phosphate, with the rule that in these esters the degree of phosphate esterification of the hydroxyl groups can be very different, and R _{2 is} a hydrogen atom or a radical for R- below 1) urid 2) given meaning and

4) M is a hydrogen atom, an ammonium radical or a Älkalimetaiikatiörti

VI, a polymer or copolyiner with negative charges extending over the polymer chains, iridüzieiren the substitute, as well

VII. Mixtures of the listed compounds I to VI.

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The anion Χ "of the formula /" AZ- (CH ₂ ) _n -D_7 ^e Χ ^θ preferably consists of a chloride, bromide, iodide, nitrate or phosphate ion.

The following is between manufacturing-related charging problems and processing-related charging problems will.

Manufacturing-related charging problems are those that occur during the manufacturing process of objects, especially photographic materials occur. This includes, for example, charging problems that affect charging from rollers and emulsion coaters, cutters and packers. In contrast fall under the concept of processing-related charging problems all the problems that arise after the items are manufactured and packaged. In the case of photosensitive or photosensitive materials encounter most of the processing-related charging problems for example in cameras and developing devices in which the exposed Recording materials are processed on.

Manufacturing-related charging problems can often be eliminated as a result fix or correct that manufacturing apparatus or equipment that is involved with the materials being manufactured comes into contact, is modified so that charging effects are reduced to a minimum. Such modifications or changes in manufacturing facilities are, however often only very difficult to implement and also costly and often require a redesign of the devices used. In the case of processing-related charging problems, such modifications tend to be impossible, for example because a film maker

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no control over the exact construction and structure who has devices in which the material made by the film manufacturer is later used.

The term "charge control means" is used here thus substances with known electrostatic charging properties understood, which can be determined, for example, by method and using a device, such as they are described, for example, in U.S. Patent 3,501,653.

According to the invention, such charge control means can be used in Surfaces are incorporated or applied to surfaces in order to modify their electrostatic charging properties.

The method of the invention enables electrostatic charges to be generated through the use of charge control means switched off or reduced to a minimum, for example in the case of radiation-sensitive film materials and other polymeric articles such as films and foils and Layer supports, as well as, for example, in carpet production. However, the method of the invention still enables one Enhancement of the charging properties of objects or an adjustment of the charging properties to certain values.

The charge control means used according to the invention are furthermore of so-called conductivity compounds or conductive ones To distinguish compounds, i.e. substances which, due to their hygroscopicity and / or ionic character, tend to to dissipate static charges that are generated by bringing two surfaces into contact.

2 0 9 8 B fj / 1 2 0 9

/ f.

An essential difference between the charge control means used according to the invention and the known conductive compounds is based on the fact that the charge control means used according to the invention can be used to improve the properties of
Surfaces to generate static electricity, to reduce, to increase or to adjust to a certain degree, whereas the described conductive connections of the state of the art
Technique can essentially be used to minimize the accumulation of electrostatic charges ex post facto, i.e. after they have formed.

Various methods are known which allow the
To determine the degree of electrostatic charges that are generated when different substances are brought into contact with one another or are removed from one another. In the known methods, the contact potential between different substances, the
so-called blocking potential, and the accumulation of charges
determined on the basis of friction caused by rolling up or sliding onto one another.

Most of the known procedures are variable by so many
Factors in the system to be tested characterize that in many cases anomalous results or results which are not a correct measure of the real charging properties of the surfaces to be tested are obtained.

One method of determination which eliminates many of the variable factors and produces results that depend on the actual surfaces used, the contact time and the contact pressure is known as the "impact electrification method"
become. A device with which such impact or impact electrifications can be determined is described, for example, in the USA patent

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3 501 65 3.

The determination method known from US Pat. No. 3 501 65 3 is based on the fact that a second (comparison) surface has hit a certain comparison surface and then off again the first surface is separated, and in precisely controllable and in a repeatable manner, doing so, the electrostatic generated by the impact and separation of the two surfaces Loads accurately measured and recorded. The one with it values obtained are then expediently in so-called, electro-

2 Expressed 2 static units per cm (Esu / cm).

With the aid of the device known from US Pat. No. 3,501,653 tried to establish the relationship between chemical structure and electrical charging behavior through impact electrification to investigate. It was assumed that, should Such a relationship could be determined, it would be possible to use this relationship to create compounds or substances to choose or to determine what the electrical charging behavior of surfaces, especially that of photographic Materials could be controlled in such a way that no static Discharges would occur more. It was found that the asked Object can be achieved by the method of the invention. In particular, it has been found that via the control of the Surface charging the coating uniformity of the seasibilized Parts of a photographic material can be improved by reducing the adhesion of the photosensitive Layers or sensitized parts is improved.

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_{l <r}

According to the method of the invention, the first to be modified Surface- produced by physical contact with Another, in particular different, surface is charged, tested for their chargeability, preferably in one Apparatus of the type known from U.S. Patent 3,501,653, wherein the electrical charges are detected which are generated when the surface is in contact with a second, in particular different, surface is brought. Be there certain test conditions have been met, in particular with regard to the time, the impact strength, the intimacy of the contact Surfaces and the relative humidity. After the degree of charge has been determined in this way, the Charge control agents are tested, e.g. B. antistatic effective Compounds that are either incorporated into the surface to be tested or applied to the surfaces to be tested can. The modified objects are always tested in the same way, i. E. under the same conditions as the same, generally different, contact surface. Ever then, according to the results of the experiments, such a charge control means is used is selected which has charging characteristics which when the control means is on or into the surface of the to Modifying article is introduced, leads to the desired surface charge modification, whereupon a sufficient Amount of the control agent to achieve the desired modification on the surface of the object to be modified applied or incorporated into the surface.

According to a preferred embodiment of the method of the invention to reduce the property of surfaces of radiation-sensitive film substrates and radiation-sensitive Elements generate electrostatic charges when they come into contact with other surfaces, e.g. B. special comparison surfaces come into contact, such charge control means are selected, which have triboelectric charging properties ranging from about

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are of the same order of magnitude as that of the surfaces whose Charging tendency is to be modified, but its polarity is the polarity of the charges on the surface to be modified is opposite. Then such quantities of this charge control agent that are able to neutralize the charges on the surface to be modified or reduce them to zero are used. 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 manufacture of photographic recording materials on the basis of silver halide, the light-sensitive silver halide is suspended, for example, in a gelatin emulsion then, generally at very high speed on one Layer support is applied, for example on a ^ layer support made of a cellulose ester, a polycarbonate, a polyester, e.g. polyethylene terephthalate or the like. From Layer supports consisting of cellulose esters can optionally be mixed with a wide variety of known plasticizers plasticized, e.g. with butyl sebacate, methoxyethyl phthalate, triphenyl phosphate or mixtures thereof.

In the case of polyester substrates, e.g. substrates made of polyethylene terephthalate, the hydrophobic properties of these substrate materials require the substrate with an adhesive layer which improves the emulsion adhesion or to coat an intermediate layer, for example a gelatin subbing layer. This adhesive layer or intermediate layer is used either applied directly to the substrate or optionally using an undercoat, followed by the adhesive layer is dried. The precoated substrate can then

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are coated with one or more emulsion layers, in particular at high temperatures, e.g. in a roller sports coating machine or other conventional coating devices in which triboelectric charges are generated can be. Each time the surface of the substrate provided with an adhesive layer comes into contact with a transport roller, for example stainless steel or anodized aluminum during emulsion coating, charges are generated, see above that finally a discharge of the accumulated electrostatic charges can take place when the charge strength a certain Degree exceeds.

If the surface of such a gelatin adhesive layer is now tested for its impact electrification potential in the device known from US Pat. No. 3,501,653 using the methods specified, these tests show that an impact pressure or an impact pressure of , 4 kg / cm at a relative humidity of 5 % and a temperature of 21 ⁰ C as well as other specific process conditions, which will be listed later, leads to a charge of about +20 Esu / cm, if the impact used to carry out the test - or impact material, ie in this case, for example, the roller material consists of stainless steel.

Tests carried out under the same test conditions with a wide variety of charge control agents showed that, for example, the compounds described under I. and II. Have strong negative charging properties of the ^{order of about -30 Esu / cm 2 «}

On the basis of the test results obtained, it is now possible to Amounts of these "negative charging agents" are introduced into the gelatin adhesive layer, it being possible for the amount of added compounds to be varied. In this way it can be determined, for example, that by means of concentrations of about Ig to

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up to about 2 g of the compounds per gram of gelatin of the adhesive layer, only charges of the order of about O + 0.5 Esu /

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

Further experiments showed, for example, that it was already ingested relatively small amounts in the order of e.g. about 0.005% by weight of the fluorocarbon compounds falling under the formula I in the gelatin adhesive layer it is possible to produce layer supports which lead to practically no charges when tested in the manner described, Will In this way modified support coated in the usual way with an emulsion, for example using of stainless steel jig rollers, so step at most only minor static charges in the most diverse Humidity.

Although according to an advantageous embodiment of the method of the invention, the charging tendency inherent in the charge control means about the same is the charge tendency of the surface, whose Should be modified (with the exception of course, that the polarity of the charges is opposite) such an approximation of the charging tendency is not necessarily required because of a relatively smaller amount of a charge surfactant with greater charging capacity or tendency to charge incorporated into or applied to the surface to be modified in order to achieve a potential of approximately zero. Such a combination of charge control agent with high charge capacity or high charging tendency and a chargeable surface of opposite polarity and relatively low Charging potential, leads to the additional advantage that only

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very small amounts of charge control agents need to be introduced into the sensitive photographic system, thereby avoiding the adverse sensitometric effects that sometimes occur with photographic systems Additives are incorporated.

Although the most varied of charge control means to carry out of the process are suitable, e.g. ionizable salts, acids, alcohols, esters and ethers, as detailed later to be described in more detail below, it has often proven particularly advantageous as a surface-active charge control agent Compounds to be used, since they allow the formation of a "hybrid surface" of the charge control agent and the charge surface even when using relatively low concentrations of charge control agents, thereby increasing the amounts of charge control agents required to achieve certain charge levels are required can be further reduced.

The selection of the charge control agent to be used in the individual skin naturally depends on the surface to be modified. This means that besides the electrostatic Charge properties and the polarity of the charges as well Compatibility of the charge control agent with the material being modified should be noted. For example, the charge control agent should remain uniformly distributed therein after being incorporated into polymer layers. from Also of particular importance is, for example, the compatibility of charge control agents with silver halide emulsions, as long as they are incorporated into them.

However, the method of the invention is not only suitable to reduce the occurrence of electrostatic charges on surfaces, but rather also to reduce the charge size or charge strength on a surface due to friction or

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'22 * 4736

To increase separation from contact with another / in particular different surface »

This is the case, for example, with the application of toners to exposed areas of electrophotographic recording materials required to strongly charge the surface of the toner particles in order to ensure that they are of the corresponding or similar charged non-image areas are repelled and that they are attracted to the oppositely charged image areas. In these cases the method of the invention enables Increasing the surface charging capacity of the toner particles and of the image-forming materials to a predeterminable high Degrees of charge. In these cases, for example, appropriate charge control agents can be incorporated into the toner particles or are applied to the toner particles in the form of overcoats in order to increase the chargeability of the toner particles of the same polarity.

Consequently, it follows that the method of the invention is equally suitable for increasing the electrostatic charging capacity as well as reducing it, the latter being the case Effect is particularly important in the case of radiation-sensitive recording materials.

As a further alternative, due to the differences to be made between manufacturing-related charging problems and processing-related charging problems, the it be desirable on the surface or in the surface of a certain material, in addition to one or more of the charge control means, to add a customary, conductivity-increasing compound which has the property of dissipating or dissipating electrostatic charges, in particular triboelectric charges.

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For example, according to the method of the invention, a charge control means or a combination of various charge control means selected and included in the Gelatin subbing layer, which is applied to a layer support, can be incorporated in order to eliminate the production-related charging problems, for example in order to avoid electrostatic charges which are brought about during the production of photographic recording materials by contact the same occur with transport rollers made of stainless steel. The recording material produced can then however, post-sale processing-related charging problems such as friction or contact with plastic, rubber or aluminum surfaces for which the charge control agent used in the manufacture of the recording materials has little or no effect Protection fries. In these cases, for example, the use of a conductive connection and a charge control device can be of particular advantage and ensure that this is the case manufactured product does not suffer from charging problems caused by processing.

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The amounts and concentrations of the charge control agents, those used to modify the charging characteristics of surfaces can be applied according to the invention, depending on the nature the screen charging surface can be very different. The charge control agents used in the present invention can furthermore in the form of discontinuous punctiform or potted layers or continuous layers on the surfaces to be modified are applied.

If the method of the invention is used for modifying photographic Products with silver halide emulsion layers applied, so can these emulsion layers contain the customary known silver halides contain, namely silver chloride, silver bromide, silver bromide iodide, Silver chlorobromide, silver chloride iodide and silver chlorobromide iodide and mixtures thereof. In the case of the emulsions that can be used to produce the recording materials, it can be coarse-grained or fine-grained emulsions, which can be prepared by customary known methods, for example, according to the single inlet process, as described, for example, in the magazine "The Photographic Journal", Volume LXXIX, May 1939 (pages 330 to 338), or double enema emulsions, for example Lippmann emulsions, ammoniacal emulsions, in the presence of thiocyanates or thioethers ripened emulsions such as those in the United States patents 2,222,264, 3,320,069 and 3,271,157. For the production of the recording materials, for example So-called surface image emulsions or internal image emulsions can also be used, as they are, for example, in the USA patents 2,592,250, 3,206,313, 3,367,778, and 3,447,927. If appropriate, mixtures of surface-forming emulsions can also be used and internal grain emulsions such as from U.S. Patent 2,996,382. The emulsions can also be emulsions with regular silver halide

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- It

genid grains of the type, for example in the J. Phot. Sci., Volume 12, No. 5, September / October 1964, Pages 242-251 will be described. Also emulsions of the negative type as well as direct-positive emulsions can be used, as for example in the USA patents 2,184,013, 2,541,472, 3,367,778, 3,501,307, 2,563,785, 2,456,953 and 2,861,885 and British Patent 723 019 and the French patent 1,520,821.

The emulsions used to produce the recording materials can furthermore be prepared by means of chemical sensitizers be sensitized, for example with reducing agents, sulfur, selenium or tellurium compounds, gold, platinum or Palladium compounds or combinations of such sensitizers. Processes such as those described in US Patents 1,623,499, for example, can be used here. 2,399,083, 3,297,447, and 3,297,446.

The silver halide emulsions can furthermore contain compounds which increase sensitivity in a conventional manner, for example polyalkylene glycols, cationic surface-active compounds and thioethers or combinations thereof Compounds such as are known from U.S. Patents 2,886,437, 3,046,134, 2,044,900 and 3,294,540.

The silver halide emulsions used for the production of the recording materials can also be compared to the Occurrence of veils are protected and stabilized against a loss of sensitivity during storage, fixkc this the conventionally known antifoggants and stabilizers can be used alone or in combination with one another. Cited his, for example, thiazolinium salts, e.g. of the type known from U.S. Patents 2,131,038 and 2,694,716 »

209 885/120 9

also azaindenes from US Patents 2,886,437 and

2,444,605 known type, furthermore mercury salts, for example that from the U.S. Patent No. 2,728,663, urazoles, e.g., of the type known from U.S. Patent No. 3,287,135 SuIfobrenzkatechin, for example that from the USA patent 3,236,652, oximes, e.g. of the type known from British patent specification 623,448, also nitrone and Nitroindazoles and also mercaptotetrazoles, for example that from US Patents 2,403,927, 3,266,897 and

3,397,987 known type, furthermore polyvalent metal salts, for example of the type known from US Pat. No. 2,839,405, thiuronium salts, for example that from US Pat 3,220,839 known type, also palladium, platinum and gold salts of the US Pat. Nos. 2,566,263 and 2,597 known type.

The photographic and other curable layers one after the other the process of the invention modifiable photographic material can with the usual known organic and / or inorganic hardeners are hardened, for example with aldehydes and / or blocked aldehydes, such as those for example in US Patent 3,232,764, ketones, carboxylic acid and carboxylic acid derivatives, sulfonate esters, SuIfony halides and vinyl sulfonyl ethers, such as those used, for example in U.S. Patent 3,539,644 are active Halogen compounds, epoxy compounds, aziridines, active ones Olefins, isocyanates, carbodiimides », polymeric hardeners, e.g. oxidized polysaccharides, e.g. dialdehyde starch and oxyguargum and the like.

The photographic emulsions and recording materials can eventually using the most varied of usual colloidal binders.

20988571209

For making the emulsion layers and other layers Suitable hydrophilic binders can be of natural origin and, for example, from proteins, e.g. gelatin, gelatin derivatives, cellulose derivatives, polysaccharides, e.g. dextran, Gum arabic and the like consist of synthetic ones polymeric substances, e.g. water-soluble polyvinyl compounds, e.g., polyvinyl pyrrolidone, acrylamide polymers, and the like.

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. dispersed polyvinyl compounds, e.g. in latex form, namely especially those which contribute to increasing the dimensional stability of the photographic materials. Suitable synthetic polymers are, for example, from the USA patents 3 193 386, 3 0.62 674, 3 220 844, 3 287 289 and 3 411 911 are known. Polymers of alkyl acrylates and alkyl methacrylates, acrylic acid, sulfoalkyl acrylates and sulfoalkyl methacrylates that are insoluble in water have proven to be particularly effective, as well as those with crosslinking centers that facilitate curing, such as are known, for example, from US Pat. No. 3,488,708 and those with repeating sulfobetaines such as e.g. from Canadian Patent 774 054.

The photographic recording materials which can be modified by the method of the invention can additionally to the described charge control means have conductive layers and / or contain compounds that are made of soluble Salts, e.g. chlorides and nitrates. That goes on The recording materials could be vapor-deposited metal have and / or contain ionic polymers, as they are

209885/1209

• ft

from U.S. Patents 2,861,056 and 3,206,312 are known 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 conventionally known layer supports, for example on foils made of cellulose nitrate * polyvinyl acetals, Polystyrenes and other heart-shaped fabrics »like, also made of Glass, paper, metal and the like. Typically the supports are made of a flexible material, e.g. a polyester, polycarbonate or cellulose ester. The layer support can, however, also consist of paper, which optionally can be partially acetylated or can have a barite layer and / or a layer made of an α-olefin polymer, in particular a layer of a polymer with an o-olefin with 2 to 10 carbon atoms, e.g. from polyethylene, polypropylene or an ethylene-butene copolymer.

The photographic materials produced by the process of Invention can be modified, can further optionally contain common known matting agents, e.g. starch, titanium dioxide, zinc oxide, silica, polymer particles, for example, that of U.S. Patents 2,992 and 2,701,245 of the known type, as well as alkali-soluble polymeric particles such as that known from U.S. Patent 2,992,101 Type.

The customary known coating processes can be used to apply the individual photographic layers to the support are used, for example, dew ^^ coating process or coating processes using air knives, curtain coating processes and extrusion coating processes,

2 0 988 5/1209

JL

using coating devices, for example of the type known from U.S. Patent 2,6S1,294. If necessary, two or more layers can also be used at the same time be applied to the substrate, for example by methods such as those from the USA patents

2,761,791, 3,508,947 and British Patent 837 095 are known.

The photographic ones modifiable by the process of the invention Materials may also be intended, for example, for colloid transfer processes, for example that of US Pat USA patent specification 2,716,059, also for silver salt diffusion transfer processes, for example, as described in U.S. Patents 2,352,014, 2,543,181, 3,020,155, and 2,861,885 to be discribed. The materials can also be used for dye image transfer processes such as those described in U.S. Patents 3,087,817, 3,185,567, 2,983,606,

3,253,915, 3,227,550, 3,227,551, 3,227,552, 3,415,644, 3,415,645 and 3,415,646 are known. Finally, the recording materials be intended for absorbent transfer processes, for example for processes described in U.S. Patent 2,882 known type.

The invention is also applicable to the manufacture of recording materials of importance, which are intended for the recording of images that can be copied and which are, for example, in the US patents 2,369,449 and 3,447,927 are described * and also for the production of recording materials dii ' are intended for the production of images that can be printed out directly, as described, for example, in U.S. Patents 3,033,682 and 3,287,137. The photographic materials modifiable by the process of the invention can furthermore be intended for heat generation processes, such as

20988 5/1209

-η-

wise in U.S. Patents 3,152,904, 3,457,075, 3,312 3,418,122, 3,392,020, 3,301,678, and 3,531,285.

The invention is also suitable for the modification of such photographic recording materials for the Production of color photographic images are intended, for example recording materials that contain color couplers, such as for example, in U.S. Patents 2,376,679, 2,322,027, 2 801 171, 2 698 794, 3 227 554, 3 046 129, 2 360 290 and 2 701 197. Furthermore, such recording materials can be modified by the method of the invention which are developed in solutions with color couplers, such as those described in U.S. Patents 2,252,718, 2,592 and 2,950,970. After all, after the Process of the invention also so-called false-sensitized color photographic recording materials are modified, such as they are described, for example, in U.S. Patent No. 2,763,549.

The photographic recording materials modified by the process of the invention can be prepared according to conventionally known ones Methods are developed, especially in alkaline developer solutions with common developer compounds, e.g. hydroquinone, Pyrocatechols, aminophenols, 3-pyrazolidones, phenylenediamines, ascorbic acid derivatives, hydroxylamines, hydrazines, reductones and the like. The recording materials optionally developed with developing tapes, as is known, for example, from US Pat. No. 3,179,517 is. Finally, so-called stabilization processes can be used as they are for example in the magazine "PSA-Journal", Volume 16B, dated August 1950. Single bath development processes can also be used, such as, for example in the magazine Phot. May be. and Eng., Vol. 2, No. 3, October 1978 and U.S. Patent 3,392,019.

20988 r, / 1209

■ / ■

If necessary, the photographic recording materials can also be developed in so-called hardening developers. as described, for example, in US Pat. No. 3,232,761 and also in roller transport devices, as known, for example, from U.S. Patent 3,025,779 or by surface development processes as known, for example, from Example 3 of US Pat. No. 3,418,132 is.

The recording materials which can be modified according to the method of the invention can furthermore be intended, for example, for developing development processes or for copy-out exposure. procedure as described, for example, in the USA patent 2,369,449 or for photodevelopment processes, for example that of U.S. Patents 3,033,678, 3,287 and 3,418,122 of known type.

- 32 -

20988 5/1209

In the following some that can be used according to the invention are: Äuflah. Application control means 1 of classes I to VI, which have proven to be particularly effective, for example in the production of photosensitive recording materials with twisting of gelatine in the photosensitive emission layer (s) or in the form of a separate gelatine layer, e.g. adhesive layer.

These classes of charge control means have the property To generate electrostatic charges on them which are considerably less positive than those of gelatin, of course the compounds of these classes can also be used for this the positive charge properties or charge tendencies of such polymer surfaces as gelatin.

20988h / 1209

I. Compounds of the formula:

") _n -D_7® Χ ^θ

wherein A is a partially, in particular fully fluorinated Hydrocarbon residue, i.e. a partial or complete one is fluorinated hydrocarbon chain;

II. Sodium and potassium salts of substituted benzenesulfonic acids;

III. multifunctional or polyvalent carboxylic acids, e.g., citric acid, tartaric acid, and succinic acid;

IV * Connections of the structure given below:

A. (CH - CH}

COOH COOH

where Z means:

(a) -CH ₇ -CH--

(b) -CH, -CH-

OR

wherein R is a short-chain alkyl radical having 1 to 5 carbon atoms or

(C) -CH ₂ -CH-

Cu ο

O 4

wherein R is a short-chain alkyl radical, a halogen atom, a hydroxyl or nitro radical;

20988 5/1209

R ι

3-COOH

wherein R is a hydrogen atom or a methyl radical or

c. -tc-f Vc - iy-

(COOH) _n

wherein Z represents the atoms necessary to complete a polyester molecule, ie a diol radical; of a polyamide or a polycarbonate molecule are required, and η is a number from 1 to 4;

^D * ^v ~ "" - "' (COOH)

0-C- ""

It

0 T

where η is a number from 1 to 4 and

E. Polymers having both hydroxyl and aromatic carboxyic acid groups;

V. Alkyl phosphates with alkyl radicals with 1 to 5 carbon atoms and

VI. substituted by halogen atoms, nitro and / or hydroxyl radicals Polymers and

VII. Mixtures from I to VI.

20988 5 / 12Ö0

Carboxylated polymers of the type described under IV. Have already been used in the form of their salts to increase conductivity Connections used. It has now been found that when using carboxyl group-containing polymers in which the Carboxyl groups are present in free form, e.g. in the case of gelatin-containing photographic materials desired negative charge influence is achieved. On the other hand, these polymers can with Free carboxyl groups should not be used as compounds that increase the conductivity, since in this form they increase the electrical conductivity Only insufficiently increase the conductivity of the surfaces. In addition, these polymers, in which the carboxyl groups in their salt form do not have the desired negative charge influence of the polymers with free carboxyl groups.

Class V compounds include several compounds which can be used as coating aids or surface-active compounds, but which, when used as "charge control agents" in the process of the invention, are employed in far lower concentrations, generally in concentrations of less than about 0.1 g of ester per gram of gelatin, or 4 micrograms per square centimeter, i.e. z, B, in concentrations of about 0.0001 to 0.1 e; per gram of gelatin,

As for the compounds of Class VI, this includes Class the most diverse known copolymers with substituents which are able to influence the charging properties of polymers, namely in the direction of a negative charge to any desired degree of charge - which can be achieved by changing the Ratio of negative charge-inducing substituents to the polymer can be achieved.

Some charge control means which can be used according to the invention and which have proven to be particularly advantageous for carrying out the method of the invention are listed below:

20988 5/12 O β

■ / -

prnitrosophenol, sodium salt; p-aminobenzoic acid; p-nitrobenzoic acid; 2,4,6-trinitrobenzoic acid; Sodium benzoate; p-nitrophenol; Picric acid; Trinitroresorcinol · p-nitrobenzenesulfonic acid; 3-nitrophthalic acid; P-nitrocinnamic acid; Benzene dihydrogen phosphonate; p-nitrobenzene sulfonic acid »sodium salt; p-nitfophenylacetonitrile; p-Nitropheftylacetic acid ■; "p-Nitrophenoxyacetic acid; 3-Nitiocfeaicon; 2,6-Mnitrothymol; 2,4-Dinitro-1-naphthol-7-sulfonic acid j 4-Kitrophthalic acid; p-Nitrobenzamic acid; 2,4,6-TrinitrobenzT- sulfonic acid; itt-nitrobenzenesulfonic acid, sodium salt; p-nitrobenzenesulfonic acid, dibutylainin salt; 4-chloro-m-toluenesulfonic acid; p-fluorobenzenesulfonic acid; p-toluenesulfonic acid (hereinafter referred to as pT * SS for short) jp ^ chlorobenzene sulfonic acid; _p-t BrombenzölsülfOftsäure sodium alz; 2,5-dichlorobenzenesulfonic acid _p-t Hydroxybenztlxxiffnisulf oic acid sodium alz · ο ⁽¹ carboxy methoxy) benzoic acid; p-Hydröxybenzoesäure; p'-Chlorpiienylessigsäure;4,4'-biphenyldisulfonicacid; ZJS-Dichloräulftniisäure, Sodium salt; sulphosalicylic acid; 4-sulphophthalic acid, monosodium salt; 2,2 »-diphenic acid ·,. SS, didodecylamine salt; pT.SS «, tridodecylamine salt; pT. SS, didodecylamine salt; pTSS, triethylamine salt; 4-sulfophthalic acid, dibutylamine salt; BSS, tridodecylamine salt; BSS, tridodecylamine alz; BSS, tributylamine salt; pT.SS, triethylamine salt; pT.SS, tributylamine salt; Pyromellitic acid; Terephthalic acid j phthalic acid; Mellitic acid; Citric acid; Salicylic acid; d-tartaric acid; Succinic acid; Oxalic acid; Malonic acid; Malic acid; Maleic acid; Adipic acid; Fumaric acid; Hydroquinone; Glutaric acid; 1-tartaric acid; d-,! -tartaric acid in a ratio of 50:50; Pyromellitic acid, monosodium salt; 1,3-dicarboxymethyl 1-5-benzenesulfonic acid, sodium salt; Pyromellitic acid NH., PH -4.3; Pyromellitic acid NHv, pH-8.2; 5-sulfoisophthalic acid, sodium salt; 5-sulfosalicylic acid; Trimellitic acid; Trimesic acid and compounds of the following formulas;

20988 5/1209

^ Me

--N-Me \ Me

.Me - (CH ₂ ) ₃ -N-Me

Me

, Me

C ₁ -H - CONH- (CH -) - N-Me

I / 03 Λ Λ ν

.θ

CiftH ίο

OH Me

• 0-P-OK, CH-C

c «o

CH ₀ CH, -0-Ρ-0Η ^Ν 0Η

0 C ₉ H ₁₇ -OP-OH

and

0Η

209885/1209

Cellulose acetate phthalates; Hexahydrophthalates; Trimellitate; Polyvinyl chloride, polyvinylidene chloride, polychlorostyrenes, polynitrostyrenes, polyvinylphenols, polyvinylchlorobenzoates, Polyvinyl nitrobenzoates and polyvinyl nitrophthalates.

Among the photographic materials, which have particular problems cause due to triboelectric effects include, for example X-ray materials and so-called aero film materials. Due to the special nature of the manufacturing and processing-related charging problems associated with these photographic materials occur, the method of the invention is of particular importance for these materials. That Processes of the invention have enabled the manufacture of particularly promising photographic materials of those described Types, although the method of the invention is in a correspondingly advantageous manner also for modification and improvement of the other known photographic materials.

The following applies to X-ray materials:

In the production of X-ray materials with high coating speeds considerable discharges generally occur. Especially in the manufacture of such photographic Materials, it happens that due to the relatively high humidity conditions at which the manufacture of these materials takes place, a so-called "Gelatineveflusteffekt" (gel pickoff) occurs, which leads to can become a serious coating problem. To solve this problem have been made using the US patent 3 501 653 known device measurements are carried out with the aim of the maximum tolerable amount of electrostatic charge to determine which occurs in the event of a simple impact (impact) between a film base material made of a polymer

2 0 9 8 8 F, / 1 2 0 9

with a GElatine adhesive layer, which is used for the production of X-ray film material is determined and rollers that convey the layer support rmate rial through the coating device, which consist of stainless steel and aluminum. The measurements carried out showed that a maximum simple shock charge from about + 10 to +12 Esu / cm was the maximum tolerable charge, since above this charge value at relatively low Humidity that was necessary to prevent the described gelatin loss effect, even when in use of 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 of an order of magnitude a length of about 0.6 m. This maximum charge value of a simple shock charge or impact charge of course depends a lot on the number of rollers or 'transport rollers in a device, also on the coating speed, the relative humidity and the like. The following is the maximum charge or threshold value can, however, be used as a basis for the following considerations.

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

On the basis of the measurement results described, it was possible to carry out the method of the invention can be determined that in particular compounds of class II are suitable for production-related To solve charging problems, whereupon small amounts of these compounds are incorporated into the X-ray film materials became.

209885/1209

As already stated, the charge control means can on can be worked into the surface in various ways, the tendency of which 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 about 0.2 to about 4 micrograms / cm of the charge control agent by applying the charge control agent from one suitable solvent, for example ethyl alcohol. Equally favorable results were obtained when the charge control agents were incorporated into the gelatin coating compound used to coat the substrate (the fiche coating compound used to form the adhesive layer). If this method is used, it has been found to be expedient to increase the concentration of the compounds to about 0.5 to about 1 g per gram of dry gelatin in order to achieve a sufficient surface concentration of the compounds and to reduce the tendency of the gelatin layer to become charged to a desired level Set the value down to avoid charging caused by the gelatin surface coming into contact with stainless steel and / or anodized aluminum rollers. The increase in concentration to about 0.5 to about 1.0 g was necessary because the compounds of class II are those which are not strong or particularly effective surface-active compounds.

A third advantageous method of incorporating the charge control means consisted in bringing a solution of 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 proved prove to be particularly advantageous when two solvents are used as the solvent for applying the charging control agent.

209885/1 2 ÖÖ

for example a short-chain alkanol, e.g. methyl or ethyl alcohol was used, i.e. a solvent which is itself a swelling agent for gelatin or if a solvent used with a content of a solvent for gelatin which opens the pores of the gelatin surface. This allows the penetration of the charge control agent into the Facilitate gelatin, which in turn ensures that there is 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 be firmly anchored in the gelatin surface.

The following applies to aero footage:

The problems encountered with these photographic materials are largely processing-related charging problems. It is well known that these film materials are often used under extremely unfavorable moisture conditions at extreme altitudes. Furthermore, the transport speed at which this film material is transported through the cameras is often very high high. The camera parts made of rubber and plastics can generate a strong electrostatic charge Contribute footage.

Most aero film cameras have the transport rollers either stainless steel, anodized aluminum, plated Metals and / or a wide variety of elastomeric materials, whereby electrostatic charges come into contact with the Emulsion side or the back of the film material with the transport rollers. As a result, the surface to modify the photosensitive film material, either the emulsion side, which is generally with a protective layer is covered, for example with a layer

2 0 9 8 8 B / 1 2 0 9

made of gelatin and a coating aid and / or the backing layer, which can contain a lubricant and which is included in customary known materials containing a conductivity-increasing compound of the type described.

The modification of this type of photographic material can be done, for example, by having a charge control means from the class of surface-active compounds is used, this compound in the least possible Concentration in the emulsion topcoat or topcoat and / or is rushed into the back layer. As a result, for example, Class I compounds can be used, although compounds of the other classes are also suitable for modifying the materials.

As particularly advantageous compounds for carrying out the method of the invention in the case of, for example, aerofilms from class I those of the structural formula given have been found, in which A is a partially or completely fluorinated te carbon chain and also Z is a radical of the formula:

0 0

-S-NH or -C-NH,

Il

Il

and further where η * 3 and X is a halogen atom.

As a particularly advantageous connection from this class, which by a particularly strong negative tendency to charge and which is furthermore easily accessible, a compound of the following structural formula has been found:

20988fi / 1209

It should be noted that a single film product can result in many different Cameras, e.g. 100 different cameras can be used, which differ from each other in that the transport rollers have different surfaces from each other, the number of transport rollers is different, that the film speed in the camera is different and that the film orientations others are. This means that the charging problems due to processing will be different in different cameras may be because each of the specified variables to a greater or lesser extent the processing-related charging effects influenced. As a result, a specific concentration of a charge control agent can be selected on a case-by-case basis a film material adequately protects charges when it is exposed in the camera X, whereas the protective effect of the charge control means used may be relatively low, when the same film material is exposed in a camera Y, the transport rollers from one of the transport rollers of the Camera X consist of different material in which the film material is transported at a higher speed and which is intended for use at a greater height. Consequently It can optionally be advantageous, in addition to the charge control agent, to additionally increase the conductivity Use connection to dissipate electrostatic charges. In such cases it may have to be Proven to be advantageous, the use of a charge control agent with a conventional, conductivity increasing compound to combine. 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 of charge control agents can also be used to carry out the method of the invention and conductivity enhancing compounds can be used

20988 5/12 0 θ

can change the charge values of surfaces to O or to to push down a value close to 0. Finally, combinations of FIG. 2 can also be used to carry out the method of the invention or more charge control means may be used if a particularly precise match of the surface charge characteristics is desirable.

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

- 45 ~

209885/1209

example 1

First, a standard test surface was produced by using a polyethylene terephthalate support Thickness of 0.18 now with a pure gelatin top layer The dry weight of the gelatin topcoat was coated

2 was 1 mg / cm.

Portions of the coated polyester film carrier were now conditioned at a temperature of 21 ⁰ C tive humidity.

now at a temperature of 21 ⁰ C and a 5Ugen rela

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 area of the gelatin top layer. Approximately / [x g of the charge control agent to be tested was accounted for on 1 cm of the gelatin surface.

The metallic test head (or another comparative material) was then placed on the test surface using a Device and a test method as described in US Pat. No. 3,501,653, impacted, whereupon the generated charge was determined.

In some cases, a polyethylene terephthalate support with no gelatin topcoat applied was used as the test surface used.

The test values obtained are listed in Tables Ia to Id below. In the majority of cases, ethyl alcohol (ETOH) was used as the solvent.

2 0 9 8 B B / 1 2 0 9

The abbreviations MeOH and PrCl mean:

MeOH = methyl alcohol and PrCl ₇ - propylene chloride

The values given in Tables Ia to Id must be used as relative Values are considered. When cleaning the hammer or Small amounts of compounds contaminating the surface of the head may be left behind on the impact head of the test device. whereby the size of the generated charge can be changed somewhat when the impact occurs. As functional it has have been found to use the solvent of the to use the test solution used and then to clean the impact head again with absolute alcohol. A cleaning in

Figure 2 in this way produces a fourth of approximately + 30 Esu / cm for the untreated control material. As a result, the fourths given in Tables Ia to Id below must be compared with the charging values 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,,

Table Ia

Irapakt charging values, determined with various charge control means on gelatin layers, when using different

2 comparison surfaces (hammer or hammer head} in Esu / cm for one

2 '

Impact or impact pressure of 1.4 kg / cm

Surface treatment solution comparison surface search with medium ■ ■ ■ -

No. Metal rubber soot layer ***

1 sodium p-nitrosophenol AETIL - 3.4 + 7.5 -1.1

2 p-aminobenzoic acid "- 3.1 +11.1 -0.4

3 p-nitrobenzoic acid "-19.2 0 -3.3

20988 5/1209

-28.8 -15.3 - 5.4 + 5.1 + 8.7 + 0.7 - 8.1 + 10.2 + 3.2 -36.0 -13.7 - 4.0

Continuation of Table Ia

untreated gelatin control ETOH + 5.9 +12.6 + 3.5 sample, average value

4 Benzoic acid AETOH * 2.1 +11.4 +3.2

5 2,4,6-trinitrobenzoic acid "

6 sodium benzoate "

7 p-nitrophenol "

8 trinitoresorcinol "

untreated gelatin control sample, mean value "+3.5 +12.1 +4.5

10 p-nitrobenzenesulfone

acid ATOH

11 3-nitrophthalic acid "

12 p-nitrocinnamic acid *

untreated gelatin control sample, mean value "+4.3 +12.4 +4.1

13 Benzene dihydrogen phosphate AETOH

14 ethyl dihydrogen phosphate "

15 butyl dihydrogen phosphate "

16 dibutyl hydrogen phosphate "

untreated gelatin control sample, mean value "+ 6.8 +11.9 +4.1

+ ■ Material of the impact head of the test device used

+++ «11I) MMlKtSchicht of cellulose acetate hexahydrophthalate and dispersed _{therein carbon black fc} ie the fabric head was covered with EAXtittt a layer of the specified composition of the type customary for film backing layers.

20988B / 1209

-32 , 0 -17, 7th - 4th , 0 -27 , 3 - 3, 8th - 2 , 7 -15 , 6 -14, 1 - 5th , 6

- 2.6 + 11 8th + 2.4 -13.0 + 3, 7th 0 -12.5 - 1, 2 0 - 1.3 0 0

Table Ib

Experiment surface treatment, solution equalization surface no, with medium metal rubber

17 p-Nitro-Na-benzenesulfonate XTOH -32.1

untreated gelatin control sample, mean +3.1

18 ρ-nitrophenylacetonitrile AETOH +0.1 +8.0

19 p-nitrophenyl acetic acid

acid "-13.4 + 1.9

20 p-nitrophenoxyacetic

acid ·· -26.7 - 7.6

21 3-nitrochalcone "+0.4 +11.5

-control sample

untreated GElatineKk «ftttk«, Average value. . + 8.1 +12.0

22 2,6-dinitrothymol AETOH -18.4 + 4.0

23 2,4-dinitro-1-naphthol-7-sulfonic acid "

24 4-Nitrophöial acid "

25 p-nitrobenza "id"

untreated gelatin control sample, mean value + 9.2 + 10.5

26 2,4,6-trinitrobenzene

sulfonic acid ETOH -39.0 +7.1

untreated gelatin control

prob ·, mean value + 9.7 +8.9

-23 , 0 -13 "1 -39 , 6 -12 »0 - 4th , 3 + 0 , 5

209 88S / 12U9

Continuation of table Ib

2 7 m-nitro-Na-benzene sulf

fonat ÄTOH -29.0 +6.0

untreated gelatin control sample, mean value +12.1 +6.0

Table Ic

Impact charging values of various charge control agents polyester strips coated with gelatine and uncoated

th polyester strip in Esu / cm at an impact pressure of 1.4

2
kg / cm (experiments with metal bumpers)

Attempt surface treatment solution gel. _{Poly ++++} no. With medium ester

28 p-nitro-RSS, dibutylamine-

stlz ⁺ AETOH -24.0

29 p-nitro-E & S, dibutylamine-

salt ^PrC1 2 " ³ » °

zn «τ cc ⁺⁺ Α

jU P "* ^» d.O.

untreated gelatin control sample, mean value

31 4-chloro-m-toluene-Na-sulfonate ATOH

32 p-fluoro-Na-benzenesulfonate "

-18 »6 -20 , 5 + 8 ,1 - -3, O - 3 , 0 -22 , 0 -14 , 0

2 0 9 8 B h / 1 2 0 9

Continuation of Table Ic

33 p-chloro-Na-benzenesulfonate AETOH -35.0 -22.0

34 p-bromo-Na-benzenesulfonate "-10.0-8.5

untreated GElatinum and polyester control, mean + 8.0. - 0.3 value

35 2,5-dichloro B.S.S. AETOH +5.0 -8.0

36 p-Hydroxy-Nt -benzenesulfonate "-22.0 -15.5

37 o- (carboxyl thoxy) benzoic acid "-35.0 -24.5

38 p-hydroxy-benzoic acid "-30.0 -10.0

untreated gelatin and polyester control sample, mean value + 10.0 - 0.3

39 p-Chlophenylacetic acid AETOH

40 4,4-biphenyldisulfonic acid "

41 2,5-dichlorosulfanilic acid, Na-SaIz "

42 sulfosalicylic acid "

untreated gelatin and polyester control sample, mean value + 8.0-0.3

+ »B.S.S. = »Benzenesulfonic acid

++ «p-T.S.S. = Toluenesulfonate

+++ - gelatin-coated polyester strips made of poly-

ethylene terephthalate

++++ »uncoated polyester strips made of polyethylene terephthalate

-13.0 - 0.6 -37.0 -18.0 -13; 0 - 2.0 -45.0 -36.0

2 0 9 8 8 S / 1 2 over 9

Table Id

Impact charging values for SiXIXIKiXX) UiI polyester strips -

Esu / cm at some

Metal butt head.

2 2

Esu / cm at an impact pressure of 1.4 kg / cm - tests with

Attempt surface treatment solution gel. Polyester no. With medium

43. 4-sulfophthalic acid, mono-

Na salt ETOH -25.0 -16.0

44 2,2'-diphenic acid "-11.0-3.0

45 trimellitic acid "-32.0 -28.0

untreated gelatine and polyester control sample, mean value +10.0 - 0.4

46 Benzenesulfonic acid AETOH -32.0 - 0.4

47 B.S.S., Didodecylamine Salt "# 3.2 +2.0

48 benzenesulfonic acid PrCl ₂ -22.0 -1.2

49 B.S.S., didodecylamine salt "+ 3.7 + 2.4

untreated gelatine and polyester control sample, mean value +9.5 - 0.4

50 BSS, dibutylamine salt PrCl _{2 +3.0-1.1}

51 p-T.S.S., tridodecylamine-

salt ^ TOH +2.0 +3.1

52 p-T.S.S., didodecylamine-

S "+ 4.2 + 3.3

53 p-T.S.S., tridodecylamine-

salt PrCl ₂ + 3.0 + 1.7

+ * Polyester strips with a celatin layer to which the charge control agent was applied from a solution;

++ = polyester strips on which the charging control means applied directly from solution;

209 8 8 F, V 1209

2234733

Continuation of table Id

54 p-T.S.S.iDidodecylamine-

salt PrCl- + 6.7 + 2.0

untreated gelatin and polyester control sample, mean value + 13.0-0.5

55 p-T.S.S., triethylamine salt, AETOH +35.0 +35.0

56 4-SuIf © phthalic acid, di-

butylamine salt "-14.0 -14.0

5 7 B.S.S., tridodecylamine salt "+ 0.8 + 0.8

58 BSS, tridodecylamine salt PrCl ₂ + 3.0 + 1.5

59 B.S.S. , Tributylamine salt MeOH +14.0 +16.0

untreated gelatine and polyester control sample, Average value + 10.5 + 0.5

60 B.S.S., triethylamine salt MeOH + 11.0 + 2.2

61 p-T.S.S., triethylamine salt "+2.1 +9.0

62 p-T.S.S. , Tr ibu ty !, amins al ζ "+ 23.0 + 8.5

untreated gelatine and polyester control sample,

average value Pyromellitic acid MeOH + 11.0 - 0.4 63 Terephthalic acid MeOH -40.0 - 5.5 64 Phthalic acid .1" + 18.0 -10.0 65 Phthalic acid ETOH +20.0 . -4.0 66 -15.5

209085/1209

Continuation of table Id

untreated gelatine and polyester control sample, through-

see lttswert MeOH + 13.0 - 0.6 67 Mellitic acid ETOH -40.0 -8.0 68 citric acid (I. -32.0 - 69 Salicylic acid tf i 3.0 - 70 d-tartaric acid ff -33.0 -16.0 71 Succinic acid It -14.0 -10.0 72 Oxalic acid ff - 1.0 -12.0 73 Malonic acid ft + 12.5 - 7.0 74 Malic acid If -16.0 - 4.0 75 Maleic acid ft -19.0 -14.0 76 Adipic acid ft - 6.0 - 4.0 77 Fumaric acid ft -16.0 - 2.5 78 Hydroquinone ft - 1.0 - 9.0 79 Glutaric acid ft - 1.6. - 80 1-tartaric acid ETOH -40.0 -24.0 81 50-50 d-, 1-tartaric acid ti -46.0 - 82 Pyromellitic acid, mono-Na
SaIz dd -15.0 - 83 1, S-dicarboxymethyl-S-Na-
benzenesulfonate - 1.6 - 4.0

84 pyromellitic acid NH ₄ pH 4.3

85 pyromellitic acid NhJ pH »8.2

Cellulose acetate layer transparent with treated gelatin-cellulose nitrate adhesive layer

11 in H ₂ O

dd dd

+ 4.0 + 13.0

20988 5/1209

Continuation of table Id

Cellulose acetate backing with treated gelatin-cellulose nitrate adhesive layer

Mellitic acid

60
40 MeOH-
H ₂ O ♦ 1.4 MeOH + 1.8 60
40 MeOH-
H ₂ O ♦ 0.6 MeOH + 0.25 60
40 MeOH-
H ₂ O + 0.4 60
40 MeOH- '
H ₂ O + 0.9 MeOH - 7.0 MeOH + 1.2

87 citric acid.

88 citric acid

89 d-tartaric acid

90 d-tartaric acid

91 pyromellitic acid

92 5-sulf © isophthalic acid, sodium salt

93 5-sulfosalicylic acid

Several of the charge control agents to be tested were des further applied from aqueous solutions.

The molecular size of many of the simpler compounds allows them to be removed from the swollen gelatin topcoat because the gelatin topcoat did not contain a hardener. Some substances can also be affected by the Surface over longer periods of time at higher relative humidities, causing considerable swelling allow the gelatin layer to be absorbed. In these cases the joints are no longer on the surface present, unless there are surface-active compounds,

209885/1209

and the surface has the characteristics of an untreated one Gelatin layer,

Example 2

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

Mixtures of gelatin and the charge control agents listed in Table II below were sprayed or hand-coated onto cellulose acetate propionate film base with a propionyl group content of 14 L, an acetyl group content of 30 L and butyl sebacate as plasticizer. Onto the film support, a gelatin subbing layer of cellulose nitrate was applied using a conventional gelatin cellulose nitrate solution (1% gelatin, 1/2 I cellulose nitrate I "11% N ₂ _7, 2% acetic acid in methanol, and acetone before.

The charge values obtained in detail are summarized in the following Table II, »

209885/1209

Table II

Experiments with gelatin layers containing charge control agents on cellulose acetate film supports - electrostatic Charging generated by one-sided impact with a stainless steel impact head - Esu / cm at an impact pressure of 1.4 kg / cm

attempt
No. Charge control agent Ratio of gelatin to
Charge control agent
1: 1 1: 2 +5.0 -2.0 - untreated adhesive layer
control sample ' +22.0 + 3.5 -0.4 - untreated gelatin
control ip robe + 17.0 94 S-SuIf © salicylic acid -9.0 95 Pyromellitic acid +4.0 96 Na salt of a naphthalene
sulfonic acid condensation
product (Tamol N) +0.2 97 Mellitic acid 98 citric acid 99 Saponin,

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

Example 3

Based on the data obtained in Example 2, machine Coatings run through to control coating thickness, with other comparative surfaces being tested and others Humidities were used. * A 12.7 cm wide coating device was used.

209885/1209

The coating solutions consisted of:

1% and 1.54 pyromellitic acid and 11 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 by means of a coating funnel using conventional coating methods. The cellulose triacetate supports had an acetyl group content of 41%. The cellulose acetate propionate supports 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 in the manner described using two comparison surfaces stainless steel and a carbon black dispersion in cellulose acetate hexahydrophthalate.

209.885 / 1209

The values obtained are summarized in Table III below. ,

Table III

Experiments with cellulose acetate propionate substrates with gelatine-cellulose nitrate adhesive layers and applied thereto, gelatin layers containing charge control agents - electrosta-

2 tables are charged with a one-sided surcharge of 1.4 kg / cm metal hammer head uncovered or covered with soot dispersion Hammer head,

Treat- ment Coating 5i] Me- Slfkuss- 15% soot- SOl / kusssuch t- tall 'disper- disper- disper-

No. strength sion ++ sion ++ sion **

100 untreated
Adhesive layer 123 + 30.0 + 5.9 + 5.5 + 5.8 101 Kontrolipro
be U Gela
tine 154 + 3.8 + 3.2 + 3.7 + 3.6 102 Control pro
be, 1t Ge
latine 123 + 2.0 + 2.4 + 2.9 + 3.4 103 11 gel. + U PMS ⁺ 154 - 1.2 +0.52 ⁺ 1.1 +0.87 104 11 gel. + 1%
PMS ⁺ 123 -2.0 + 0.5 + 0.8 + 0.4 105 il gel. +
1.5% PMS ⁺ 154 - 2.0 +0.52 - ο, ι + 0.5 106 It gel. +
1.5 * PMS ⁺ 123 - 3.2 + 0.2 -0.03 + 0.4 107 1t gel. +
Jt Saportin 154 + 2.0 + 1.4 + 2.4 + 3.2 108 1t gel. +
1t saponin 123 + 1.0 + 1.2 + 2.1 + 2.7 109 1t gel. +
1.5t saponin 154 + 0.3 ♦ ■ 1.3 ♦ 2.0 + 2.6 110 1 * gel. #
1.5 * saponin + 1.0 + 1.1 + 2.4 + 2.0

209 885/1209

+ = Pyroraellitic acid.

++ = dispersion of carbon black in cellulose acetate hexahydrophthalate From Table III it can be seen that pyromelic acid is significant is more effective than saponin and furthermore is relatively independent of the air humidity, whereas saponin shows a positive trend (less effectiveness) with air humidity, The lower values, which were obtained in the case of comparative samples 1 and 2, result from 0.19% saponin which was used as a coating aid.

Example 4

Many of the smaller organic molecules of the compounds tested in Example 1 come off gelatin surfaces easily absorbed when the compounds are absorbed from aqueous media due to the swelling capacity of the gelatin. As a result, the resulting charging properties of the surface can be difficult to control or control.

A charge control agent of larger molecular size was produced which could not be absorbed in larger amounts or in excess, namely a copolyester consisting of Polyethylene pyromellitate.

Equiaolar amounts of ethylene glycol and pyromellitic dianhydride were mixed in a flask using a sufficient amount of Ν, Ν-dimethylformamide (DMF) as solvent to achieve a homogeneous solution at 60 ^° C. The temperature was then increased to 90 ^° C., whereupon the dimethylformamide was distilled off under reduced pressure. Heating was continued at reduced pressure until the temperature of the flask contents reached 175 ⁰ C. This temperature was maintained for about an hour.

20988 5/1209

2234738

A viscous, almost white polymer was obtained which solidified on cooling and formed a glass-like mass. The polymer was hard and brittle, dispersible in water, and soluble in dilute alkali.

The Polyäthylenpyromellitat could be from aqueous solutions Apply to layers of gelatin while maintaining the negative charge characteristics of the polymer.

A 1lige aqueous solution which is applied to a gelatin adhesive layer on a cellulose acetate support with an acetyl group content of 43.31 and methoxyethyl phthalate and triphenyl phosphate applied as a plasticizer produced a charge value of -33 Esu / cm under an impact pressure of 1.4 kg / cm ' at a relative humidity of 5.

A wide variety of mixtures can be prepared from gelatin and polyethylene pyromellitate, for example as described in Example 3. Depending on the ratio of the two components of the mixture, charge values can be achieved that lie between the charge value for x a gelatin (approximately +30 Esu / cm) and the charge value of pure polyethylene pyromellitate (approx

2 -30 Esu / cm).

If a 0.1 liter solution of polyethylene pyromellitate in 60 parts of methyl alcohol and 40 parts of water is applied to a gelatin adhesive layer on a cellulose triacetate carrier in a

2 ke of about 4 Mg / cm is applied, an impact-charging

2 2

value of +0.2 Esu / cm with a shock load of 1.4 kg / cm and a 5ligen relative humidity determined. In contrast, the charge value for a corresponding, non-pretreated test item is included with identical test conditions

2 + 30 esu / cm.

0 9 8 8 5/1209

The charging properties of gelatin can be modified by chemical reaction of the gelatin. In the following examples ¹ Player 5 and 6. Such modification methods are described,

Example 5

20 g of a gelatin prepared by acid hydrolysis of collagen were dissolved in 100 ml of water, and 100 ml of dimethylformamide were added, the solution was heated to 8O ⁰ C, after which 5.0 g of ß-propiolactone was added under vigorous stirring. After 1/2-hour heating to 80 ^° C., the reaction mixture was cooled, whereupon it was diluted with a mixture of one part by volume of acetone and one part by volume of methyl alcohol and a precipitate was formed in the process. This was extracted with an ethyl alcohol-methyl alcohol mixture and finally, after addition and trituration with ethyl alcohol, left to stand overnight, filtered and dried. In this way, 24.9 g of dry chemically modified gelatin was obtained. The gelatin was soluble in water, a 6% solution formed a gel at room temperature,

A 6% solution of the modified gelatin was measured in a layer thickness of 0.0762 mm, wet, on the adhesive layer applied to a cellulose triacetate support. The impact charge value of this surface was +6 Esu / cm, for one Charge value of the cellulose triacetate carrier with only one adhesive layer from +30 Esu / cm,

Example 6

Another chemically modified gelatin was made as follows:

20988 5/1209

Γ '

40 g of a gelatin produced by MämwmvS® & i® $$ ö3täSL were slurried in 250 ml of dry dimethylformamide. 19.2 g (0.1 mol) of trimellitic anhydride, dissolved in 40 ml of dimethylformamide, were then added to this slurry. The mixture was then ^{brought to 50 °} C. in a thermostat, where it was kept in motion for 30 hours. The gelatin reaction product slowly dissolved to form a homogeneous solution. The resulting solution was then cooled, whereupon the reaction product was precipitated in 1500 ml of isopropyl alcohol. Subsequent washing with isopropyl alcohol and drying gave 50.1 g of reaction product, corresponding to 84.61 of the theoretically possible amount. The remaining 15.4 S reaction products were lost due to their solubility in the isopropyl alcohol / dimethylformamide mixture.

The reaction product had limited water solubility but was dispersible in water. Starting from oily Dispersions could be produced with matt layers.

A 6 ige dispersion of the reaction product had a pH of approximately 2. By adding alkali up to a pH of approximately 4, a clear solution was obtained.

The impact charge values of this reaction product depend on the Condition of the carboxyl groups of the modified gelatin. If the reaction product has free carboxyl groups, it shows the material has a lower positive charge than unmodified gelatin. However, the carboxyl groups are replaced by alkali neutralized, the charge values come closer to the charge values of unmodified gelatine.

/ "* by acid hydrolysis of collagen

209885/1209

oily solutions of modified with trimellitic anhydride Gelatin of various pH values was coated on cellulose triacetate support. The impact load values were found at an impact load of 1.4 kg / cm and one relative humidity of 51. The results obtained are summarized in Table IV below.

Table IV

pH value alkali shock load value

Pen Irm *

Esu / cm '

2 - + 14 4th NaOH + 30 4th NH ₄ OH + 16 8.5 NH ₄ OH + 19 unmodified gelatin + 30

The reduction in the positive charge of gelatin through the chemical modifications of gelatin described is usually not sufficient to completely switch off the static chargeability of the gelatin layers. the However, examples show that chemical modification of the gelatin structure with active negative charge groups is possible is. Optionally, negative charge groups that are more effective can be introduced into the gelatin backbone. on however, chemically modified gelatin is often of great value. Mixtures of chemically modified gelatin with a negative charge substance can be reduced to a charge value by adding smaller amounts of charge substances from 0 or close to 0. The addition of small amounts of charge control agents may then be of particular advantage if such additives are sensitometrically active or expensive and only in limited ways for the reasons given Concentrations can be applied.

20988 5/1209

? 23A736

Although the examples given deal with the surface modification of gelatine-containing layers, the charge properties of all the substances can be determined by the Invention can be modified, which are subject to triboelectric effects, i.e. by. Addition of a charge control agent the most varied of surfaces can be modified with regard to their charge properties according to the method of the invention. ■ "■ - '.

Example 7

At first layer supports made of polyethylene terephthalate and cellulose esters were coated with a 5ligen gelatin solution in such a way that 615 ml of the gelatin ^{solution accounted for a support area of 9.29 m 2.} In this way, gelatin layers were produced, which formed insulating layers, to which a further special gelatin layer was subsequently applied, ti. That is, a layer of gelatin modified in contrast to the first layer. For this purpose, a 2.9% gelatin solution was first prepared using low concentrations of a fluorinated surfactant of the following formula:

CnF ₁₇ SO ₉ NH (CH ₉ ), N (Me).

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 coated with a gelatin layer. The samples were then conditioned initially at a relative humidity of 51 and a temperature of 21 ⁰ C for carrying out the Ladungsjitestes.

20988 5/1209

-fif-

The impact charge values were determined in the event of an impact

2
utilization of 1.4 kg / cm at a relative humidity and a temperature of 21 ⁰ C. The results obtained are summarized in the following Table V:

Table V Concentration of - 2
Impact charge Esu / cm + 18.0 I A Coating B Compound in g / 0.45 kg coating uni + 18.5 + 23.5 + 19.0 + 22.0 0.0001 + 19.0 + 25.5 0.0005 + 18.0 + 17.5 0.002 + 9.8 + 13.5 0.008 - 1o, 0 - 7.5 0.01 - 10.7 - 21.0 0.02 - 29.0 0.03 0.04

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

The data compiled in Table V shows that the two gelatin layers of different thicknesses have a charge value of 0 is achieved at a concentration of surface-active compound of 0.025 or 0.015 g per 0.45 kg. in the In the case of coating B, impact charges are in the range of 0 _ + 8 Esu / cm at concentrations of 0.012 to 0.02 g per 0.45 kg achieved.

In the manner described, further layers with different

the
ren charge control agents / m the constitution indicated below in Table VI tested. The additives were used in concentrations of 0.05; 0.1; 0.2; 0.4 and 0.8% by weight were added.

20988 5/1209

The thickness of the coating corresponded to 175 ml of solution per section, 29 m of support area. The impact load was 0.70 kg / cm ² . The relative humidity was 51. The temperature was 21 ^° C.

Table VI

Me

C ₇ F ₁₅ CONH (CH ₂ ) ₃ N-Me I "

Me

Weight! of additives 0 0.05 0.1 0.2 0.4 0.8

+13.8 +25

-12.4-13.7

C _n H ₁

Me

₅ i5-Me I "^ Me

+10.5 +0.6 - -5.5 -6.5 -5.5

Me

C ₁₇ H ₃₅ CONH (CH) ₃ ^ -Me I "

Me

+10.5 +2.2 -4.2 -5.8 -7.0

OH

C _1n H -, - OP-OK
33 υ

+10 +5.5 - +6.6 +6.2 +4.8

OH OH

+ 10 +1.4 +1.6 +1.2 -r- +1.2

20988 5/1209

Example 8

This example shows that mixtures are advantageous Have surface-active compounds used to generate impact charging values close to 0 within a wide range of concentrations.

The following table VII summarizes the measurement results which were obtained using a saponin-fluorocarbon mixture.

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

Table VII

Impulse electrification when using saponin-fluorocarbon mixtures.

Fluorocarbon concentration in g / 0.454 kg melt

0.02 0.04 0.08 0.16

Saponin concentration in g / 0.454 kg melt

0.10 0 , 80 + 1.7 0 , 0 +0.5 -0 , 6 -0.6 -1 , 5 -2.4 -2 »5

The data were transmitted as described in Example 7.

A comparison of the data compiled in Tables V and VII shows the extent of the effective working concentration for the fluorocarbon by using a mixture of charge control agents and coating aids. Through the

209885/1209

- ρ * - ΨΚ

Use of combinations of charge control agents and coating aids the charging characteristics of QbeT surfaces can be set very precisely.

The use of anionic surfactants such as alkylaryl polyoxyethylene sulfonate salts and triisopropylnaphthalene sulfonate sodium salts as a coating aid has become common in the photographic industry. Such surface-active However, compounds contribute greatly to the formation of static macerations of film products. The usage of Mixtures of fluorocarbons with surface-active compounds and coating aids make this possible Manufacturers of photographic products assess the static charge properties of various surfaces, especially layer surfaces to be kept within the required limits. The use of such mixtures also enables the best available surface-active compounds as coating auxiliaries to use, so that the quality of the layers produced is not affected by adverse charging effects of the coating aids used to be impaired needs.

Except for the specified anionic surface-active compounds can fertilize the most diverse other surface-active verb ib for the preparation of adhesive or primer layers, backing layers, Emulsion layers and in top layers over emulsion layers to control the charge properties of these layers and the such layers having end product can be used.

Example 9

Similar results as described are obtained in treating x-ray materials, albeit with such Materials usually provide double protection through incorporation

20 9'8 85/1209

a charge control agent and a conductive compound for modifying the electrostatic charge properties of X-ray materials is usually not required, since such products are usually only with comparative few surfaces in contact pe long and the manufacturing-related and processing-related problems a little less here are.

In a conventional coating device, film supports with an adhesive layer customary for X-ray materials were produced coated with various concentrations of a charge control agent added to the adhesive layers.

A customary coating compound was used to prepare the adhesive layers from gelatin, saponin, a fungicide, a hardening agent such as chromium aluminum sulfate and a matting agent.

The following table shows the influence of saponin additives on the impact electrification of the adhesive layers.

Table VIII

Impact electrification of modified adhesive layers using stainless steel and anodized aluminum at an impact pressure of 1.4 kg / cm and a temperature of 21 ^° C.

Test total 5Uge relative air 50Uge relative air humidity moisture amount Ling

^Steel anodized steel anodized aluminum aluminum

1 0 +28.0 +12.5

2 0.01 +24.0 +11.0

3 0.15 + 5.9 + 6.0

4 0.20 2.0 3.5

5 0.25 - 1.6 + 2.2

6 0.30 - 3.0 + 0.8 commercial +16.5 +10.5 x-ray

material

20988 5/1209

+ 26.0 + 1 6.0 + 22.0 + 1 2.7 + 8.4 2.4 - 0.3 - 1.0 - 4.2 - 1.8 - 5.0 - 3 , 2 + 17.0 + 7.3

- jar-

From the data summarized in Table VIII, it can be seen that higher concentrations of saponin can be used to advantage to improve the charging characteristics to reduce the adhesive layers. .

In further experiments, mixtures of saponin and p-chlorobenzenesulfonic acid, sodium malt, hereinafter referred to as p-Cl.S.S., nasal salt, were used as additives in adhesive or primer layers used. The results compiled in Table IX below were obtained:

Table IX

Impact electrification of modified adhesive layers with rustproof ones Steel and anodized aluminum at an impact pressure of 1.4 kg / cm.

Check Additions in % p-Cl.SS-
Na-SaIz 5Uge relative anodizing
tes aluminum
nium 50Vige relative air anodized
aluminum ling Sapo
nin 0.4 humidity + 9.0 humidity - 9.0 No. 0.01 0.45 stole + 2.6 stole -10.0 7th 0.01 0.5 + 16.0 - 6.5 -22.0 -13.3 8th 0.01 0.45 + 7.2 + 9.0 -25.0 - 5.4 9 0.10 0.50 - 9.5 - 2.5 -27.0 - 1.2 10 0.10 0.60 + 13.8 - 1.2 - 8.0 - 5.0 11 0.10 0.70 + 5.0 - 2.5 - 8.0 - 5.0 12th 0.10 0.50 -5.0 + 1.2 -11.7 - 6.0 13th 0.13 0.50 - 5.0 + 1.0 -10.0 - 8.0 14th 0.15 0.50 + 5.3 + 0.8 -11.4 - 4.0 15th 0.18 0.60 + 2.6 - 5.1 -12.0 - 8.5 16 0.13 + 5.4 - 6.0 17th - 42 -14.4

20988 5/1209

Continuation from Table IX

18 0.15 0 , 60 - 5th , 6 - 4th , 9 -14 , 0 - 7th • 9 19 0.18 0 , 60 _- 2 , 5 - 4th , 5 - 9 , 0 - 4th , 5 Comparison
sample + 16 »5 + 10 , 5 + 17 .0 + 7 .3

The data compiled in Table IX would result four mix concentrations at which the general criterion of 0 + _ 10 Esu / cm under all conditions tested is achieved. From the compiled data it can also be seen that 10 of the mixture concentrations correspond to the general Criterion of 0 + _ Esu / cm compared to the anodized aluminum roller surface in both moisture ranges.

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

Example 10

Saponin and p-chlorobenzenesulfonic acid, sodium salt, (p-Cl.S.S., Na-Salz) were added as additives to mixtures for the production of adhesive HXi or primer layers, whereupon these mixtures were applied in the usual way to the substrate. The coated supports were then used for the production of photographic recording materials, which then were examined for the occurrence of static defects.

. 209885/1209.

In a series of experiments 1, the emulsions were applied to the substrate in the usual way, that is, initially one was Side of the substrate with an emulsion, coated and dried, whereupon the other side was coated and dried in a second coating station. The material was thus not wound after the first coating.

In a further series of experiments 2, the first emulsion layer was first applied applied and dried up, whereupon the footage wound up and then a second time to coat the other side of the substrate by the coating device was conducted. This means that the test used in Series 2 is a considerably heavier test in view of the above is due to the occurrence of electrostatic charges on the adhesive layers.

The tests were carried out on a technical scale, i.e. with film material and machines customary in practice,

The results obtained are summarized in Table X below:

Table X

Trials on a production basis with mixtures of saponin and p-Cl.S.S., Na-SaIz; .

Additives to polyethylene terephthalate adhesive layers; Shock charging of the adhesive layers,

5/1209

Trial additives 5% relative humidity

Anodized steel

aluminum

1 0.2 * saponin +5.5 + 5.4

0.2% saponin +5.5

0.45 p-Cl.S.S. + 8.5 +9.5 Na salt

like experiment 1 +11.0

1 0.2 ». Saponin +12.0 +9.0

2 as in experiment 1 +15.0

50% relative humidity

Anodized steel
aluminum

+13.0 + 5.7

static results

+16.0 + 6.0
+ 10.0

+23.0 + 8.4
+ 18.5

marks caused by triboelectric charges, scattered over a length of 9.144 m; remaining part without markings;

branched static markings of roller grooves, some distributed static Charge spots

distributed static charge spots caused by electrostatic discharges

Distributed charging spots due to electrostatic discharges

no static markings

minor charging defects, distributed over a length of 9,144 m

Table X continued

1 control sample

2 control sample

+23.0

+ 12.2

+24.0 + 14.0 no static markings

Static Discharge Spots

branch-like markings caused by electostatic Discharges

From the data compiled in Table X, it can be seen that the combination of 0.21 saponin and 0.4% p-Cl.-S.-S. nasalt leads to superior results. The heavier test, Run 2, shows that this sample is the only one obtained from static defects is free over the entire length of the roll, with the exception of approximately 9,144 m at the beginning of the Sample.

On four production spools of substrates made of polyethylene terephthalate Adhesive layers were applied which contained 0.2% saponin and 0.451 small p-Cl.-S.-S., sodium salt.

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

Table XI

Production rolls with saponin and p-Cl.S.S., Na-SaIz additives for the polyethylene terephthalate adhesive layer (gelatine, matting agent, fungicide).

Sample no. Impact electrification

51 relative air humidity moisture 501 relative

Steel Al ⁺ steel Al ⁺

1 -10.0 - 6.4 -20.0 - 8.4

2 - 9.1 -10.2 -20.0 - 7.5

3 - 5.4 - 6.3 -23.0 - 7.6

4 - 9.0 - 7.0 -20.0 - 7.5

⁺ Al ■ aluminum alloy, manufacturer Martin Hart Company, USA

20988 5/1209

Two ^{4 of} the production spools were then coated with an emulsion layer 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 sticky adhesive layers during emulsion coating,

It is essential that all but one sample included in the Production fixtures were produced, compared to anodized aluminum surfaces, very close to the general criterion of

2 O + 10 Esu / cm.

The results in Table IX also show that there is still enough room for concentration changes for the purpose of reduction charging to the O value.

Additions of p-Cl, S, S, -Na salt to adhesive layer or primer compounds in concentrations of, for example, 0.45 I to 4.5 I did not show any adverse sensitometric effects,

Although the examples apply the method of the invention to the treatment of polymeric substrate materials, optionally an adhesive or primer layer or .Back layer, the procedure is as before outlined, also applicable to other objects in which undesirable triboelectric effects occur. So can just to to name a few examples, according to the method of the invention, also those known with photosensitive polymers and synthetic resins coated, recording materials and papers are treated, which are widely used in the photographic field. Furthermore, adhesive or primer layers can also be used, for example such materials can be modified according to the method of the invention. The charge control means can also optionally silver halide emulsion layers and other light-sensitive layers which do not contain and do not have silver

209885/1209

S (T

made on the base of gelatin, can be added.

Although in the examples primarily the addition of charge control agents relatively high negative charge characteristics to surfaces that have a relatively high positive charge show, can also charge control means positive charging characteristics can be applied by the same methods to reduce the tendency to charge to reduce or increase surfaces,

The cheapest amounts of Charge Control Funds that can be obtained after the method of the invention can be absorbed by the surfaces to be modified or the surfaces to be modified Surfaces are applied or in surfaces to be modified can be incorporated, depend on many different factors, which the charging of the to be modified Affect surfaces.

As can be seen from the preceding examples, in particular observe the following points:

1. The static charging properties of surfaces are obviously a direct result of their chemical structure, In particular, the method of the invention reveals the strong positive charge characteristics of gelatin and gelatin-cellulose nitrate adhesive layers or undercoat or backing layers such as those used in photographic materials can be used to "neutralize" or "cancel" by adding a negative charge control agent to these surfaces will, e.g. B, by application from a suitable solvent

20988 5/1209

or in some other way with the formation of a continuous or a discontinuous layer having a thickness, measured dry, of preferably less than about 300 Angstrom units.

2. The effect of this technique depends on the thickness of the coating or coverage, whereby the charge or the surface potential of the object to be modified can be varied within a wide range.

3. The charge properties of unmodified surfaces, the surface of a charge control agent and a surface modified with a charge control agent cannot be predicted with certainty why it will be necessary if the charging characteristics of a particular Surface should be modified, first the charging properties or charging characteristics of the unmodified surface to be modified, to test a number of charge control agents with regard to their charge properties, one suitable from the compounds tested to select the appearing compound and to work or apply it in different concentrations into the surface until the desired degree of charge and polarity is achieved.

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

Although the surfaces of objects to be modified have always been modified in the description and the examples, it should be pointed out that similar results are obtained

2 0 9 B 0 H / 1 2 0 9

can also be achieved if the surface causing the charge, i.e. for example in the case of Aerp films, the camera rollers or camera rollers or in an emulsion coater treated rollers made of stainless steel or anodized aluminum. Such Treatment can be done, for example, by impregnating the surface of such rollers or cylinders with suitable charge control agents, or by impregnating such agents be layered or applied to the surface of the rollers in such a way that a charge or very little Charging is obtained when the rollers or rollers, for example, with a layer support having an adhesive or primer layer or the emulsion or layer support side a special photosensitive material come into contact.

As has been explained in detail, the generation of triboelectric charges is based on bringing into contact and separation of two usually different surfaces. The method of the invention enables triboelectric charges to be reduced to an acceptable level by treatment or Modification of one or both of the surfaces in contact with one another. In the case of the charging problem that occurs when using aerofilms, a reduction in triboelectric charges can already be achieved, for example can be achieved by having the camera transport rollers or rollers with an appropriate charge control means coated or impregnated.

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Claims (21)

Claims 1. Process for modifying the electrostatic charging properties of objects whose surfaces become electrostatically charged when they come into frictional contact with a other, in particular different, surface are brought, characterized in that one a) initially the degree under standardized conditions
the electrostatic charge on the surface of the too
modifying object that measures by friction
the surface with another, in particular different, surface and / or by separating the two
Surfaces is caused that one b) on the basis of the results of stage a) through test experiments, a compound or a mixture of compounds which or
that is able to change the degree of electrostatic charge of the surface to be modified in the desired sense, and that one and / or in c) on / the surface to be modified so much of the selected compound or the selected compound mixture as a charge control means that the desired modification occurs, / or, brings in 2. The method according to claim 1, characterized in that a compound of the following type is used as the charge control means used: T. a surface-active compound of the following formula: Γ AZ (rCHj-i- —D J ⁹ Χ ^θ 209885/1209 where mean: A is an optionally partially or fully fluorinated hydrocarbon radical; Z is a remainder of the formulas: 0 0 0 0 Ii I I R -S-NH-; -C-NH-; -S-NH- or -P-NH- I! 0 OH D is a remainder of the formula: -NR ₂ , in the R., R ₂ and Represent hydrogen atoms, short-chain alkyl radicals or aryl radicals; X is an anion and η is a number from 1 to 8; II, a compound of the following formula: Z-X-Y-M 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 more Nitro, nitroso, hydroxyl, carboxy, cyano, 20988B / 1209 Alkoxy, aryloxy and / or substituted alkoxy residues and / or residues of the formula: Q -C-OR, where R is an optionally substituted Is alkyl or aryl; X is a remainder of one of the following formulas: 0 0 0 Ii Il Il ; -S-; -POH (CH ^ C 0 * Il = O; -S-; -P-OH; 0 HHO II -III C-; -C = C-C-; -0-fCH ₂ - ^ Jj-C-; -C = CC-; or -CH = CH- with the proviso that η is a number from 1 to 10; M is a hydrogen atom, an ammonium residue, a metal cation or an amine salt radical or an optionally substituted phenyl radical and Y 1) is an oxygen atom when M is a hydrogen atom, is an ammonium residue, a metal cation or an amine salt residue, or 2) an imino radical (-NII-) when M is hydrogen is or 3) a carboxyl radical C = C = O), if M is optionally is substituted phenyl; " III, a carboxylic acid of the following formula: HOOC-R-COOH
in which R represents a residue of the following formulas: "2 0988 5/1209 D (-C> _η 2) -4-CH ₂ - * 3) - H H ⁽ \: ⁽ t I. - C = = C - 4) with the proviso that when R is a radical of the formula 1) or 2), R _{1 is} a hydrogen atom and R _{2 is} a halogen atom, a nitro, aryl, substituted aryl or hydroxyl radical, it also being true that when R is a radical of formula 3), R .. and R, each represent a hydrogen or halogen atom, a nitro, carboxyl, ary-1, substituted aryl, alkyl or substituted alkyl radical and it also applies that when R ^ a Is hydrogen atom, R _{2 is} a hydrogen or halogen atom, a hydroxyl, nitro, carboxyl, optionally substituted aryl or optionally substituted alkyl radical, and 20988 S / 1209 η and m represent integers ^ 4Oh / ob IV. A carboxylated polymer with free carboxyl groups; V. a compound of the formula: 0 II R ₁ 0 - P - OM 0 y ^R 2 where mean: 1) R _{1 is} a radical of the formula ^CH 3 ~ ^ ^CH 2 ^ n ~ » ^{in which n is a number from 1 to 19} * then R _{2 is} a hydrogen atom or a radical of the formula CH ₃ -CCH ₂ - ^ ₇ with n ¹ - 1 to 19, where n is ¹ - η can be or different from η; 2) R. and R ₂ unsaturated hydrocarbon radicals or optionally substituted aryl radicals; 3) R _{1 is} the atoms of a polymeric structure, and R _{2 is} a hydrogen atom or a radical as defined for R ₂ under 1) and 2) and 4) M represents a hydrogen atom, an ammonium radical or an alkali metal cation VI, a polymer or copolymer with negative charges inducing negative charges extending over the polymer chains Substituents, as well VII. Mixtures of the listed compounds I to VI. 3. Process according to Claims 1 and 2, characterized in that the charge control means used is: 20988 K / 1209 I. sodium and potassium salts of substituted benzenesulfonic acids; Π. Polymers of the formula: -fr- CH CH- ^ COOH COOH in which Z is a radical of one of the following formulas (a) -CH ₂ - CH ₂ - (b) -CH »C -» a short-chain in the row The alkyl radical has 1 to 5 carbon atoms is; (C) -CH ₂ -CH- C ^ H.-R, where R is a halogen atom or a short-chain alkyl, hydroxyl
or is nitro radical; III. Polymers of the formula: -ECH ₂ C -ήτ COOH in which pure is hydrogen or a methyl radical; IV. Polymers of the formula: (COOH) _n 209885/1209 where mean: Z the atoms required to complete a polyester, polyamide or polycarbonate and η = 1, 2, 3 or 4; V. Polymers of the formula; Ό-c-S Il 0 with η = 1, 2, 3 or 4; VI. Polymers with both hydroxyl groups and aromatic, Residues containing carboxyl groups; VII. Polymers or copolymers with one extending over the polymer chains extending halogen, nitro and / or hydroxyl group substitutions; VIII. Alkyl phosphates with alkyl radicals having 1 to 5 carbon atoms and IX. Mixtures from I to. VIII. 4. Process according to Claims 1 to 3, characterized in that the surface of films and foils is modified. 5. The method according to claim 4, characterized in that the Surfaces of photographic substrates for the production of light-sensitive photographic recording materials modified. 209885/1209 6. The method according to claims 4 and 5, characterized in that the surfaces of photographic substrates made of cellulose esters, polyesters and polycarbonates with at least modified a layer located on the substrate. 7. Process according to Claims 5 and 6, characterized in that the surfaces of such photographic film supports modified, which has an adhesive or primer layer for improving the adhesion of the layer to be applied to the substrate photosensitive layer or layers, and / or a layer that is after application of the photosensitive layer or Layers forms a backing layer. 8. Process according to Claims 5 to 7, characterized in that the substrate made of cellulose acetate, cellulose acetate propionate or cellulose acetate butyrate is modified, 9, method according to claims 7 and 8, characterized in that the layer support is a customary adhesive or primer layer or have a gelatin-based backing layer. 10, method according to claims 8 and 9, characterized in that a layer support made of cellulose triacetate or cellulose acetate propionate, which is replaced by butyl sebacate, methoxyethyl phthalate and / or triphenyl phosphate is plasticized, is used. 11, method according to claim 9, characterized in that one Layer supports are used that have an adhesive or primer layer or backing layer based on gelatin-cellulose nitrate. 12, method according to claims 9 to 11, characterized in that the adhesive or primer layer or backing layer with 0.5 to 1.0 g / per 1.0 g of gelatin modified on a dry weight basis, 13, method according to claims 9 to 11, characterized in that the charge control agent in the form of a layer on the Adhesive or primer layer in concentrations from 0.2 to 7 of the "Charge Control Means 209885/1209 2 ■ * Plots micrograms / cm. 14. The method according to claims 6, 7 and 9, characterized in that a substrate made of polyethylene terephthalate is modified. 15. The method according to claim 14, characterized in that the Layer support has an adhesive or primer layer or backing layer made of unmodified (undoctored) gelatin. 16. The method according to claims 1 to 15, characterized in that the charge control means used is: peNitrösöphenol-Na-Salz; p-aminobenzoic acid; p-nitrobenzoic acid; 2,4,6-trinitrobenzoic acid; N-benzoate; p-nitrophenol; Picric acid; Trinitroresorcinol; p-nitrobenzenesulfonic acid; 3 * nitrophthalic acid; p-nitrocinnamic acid; Benzene dihydrogen phosphonate; p-nitrobenzenesulfonic acid Na salt; p-nitrophenylacetonitrile; p- ^ nitrophenylacetic acid; p-nitrophenoxyacetic acid; S'-nitrochalcone;2,6-dinitrothymol; 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, dibutylamine salt; 4-chloro-m * -toluenesulfonic acid; p-fluorobenzenesulfonic acid; p-toluenesulfonic acid (hereinafter referred to as pT.SS); p-chlorobenzenesulfonic acid, sodium salt; p-bromobenzenesulfonic acid, sodium salt; 2,5-dichlorobenzenesulfonic acid; p-hydroxybenzenesulfonic acid, sodium salt; o- (carboxymethoxy) benzoic acid; ρ-hydroxybenzoic acid; ρ-chlorphenyl acetic acid; ; 4,4'-biphenyl disulfonic acid; 2, S-dichlprsulfanilic acid, Na salt; Sulfosalicylic acid; 4-sulfophthalic acid, mono sodium salt; 2,2'-diphenic acid; Trimellitic acid; Benzenesulfonic acid (hereinafter referred to as B, S.S. designated); B, S, S., Didodecylamine salt; B.S.S ,, Dibutyl- .. amine salt; p-T, S, S ,, tridodecylamine salt; p-T, S.S., didodecylamine salt; p-T, S «S ,, tridodecylamine salt; p-T, S, S., didodecylamine salt; p-T.S.S., triethylamine salt; 4-sulfophthalic acid, dibtylamine salt; B, S.S ,, tridodecylamine salt; B, S.S ,, tridodecylamine salt; B «S, ~ S .., tributylamine salt; p-T, S.S ,, triethylamine salt; p-T, S.S., tributylamine salt; Pyromellitic acid; Terephthalic acid; 209885/1209 -χμ - 91 Phthalic acid; Me Hit acid; Citric acid; Salicylic acid; d-tartaric acid; Succinic acid; Oxalic acid; Malonic acid; Malic acid; Maleic acid; Adipic acid; Fumaric acid; Hydroquinone; Glutaric acid; 1-tartaric acid; 50-50 d-,! -Tartaric acid; Pyromellitic acid, mono-Na salt; 1,3-dicarboxymethyl-5 benzenesulfonic acid, sodium salt; Pyromellitic acid NhJ pH 4.3; Pyromellitic acid NH * pH = fi, 2; 5-sulfoisophthalic acid, Na salt; 5-sulfosalicylic acid; Trimellitic acid, Trimesic acid, compounds of the formulas: Me CONH (CH ₂ ) ₃ - N-Me ^ Me Me CONH- (CH ₂ ) ₃ -N -Me
■ Me Me " CONH- (CH ₂ ) ₃ -N Me Me OH ι, C ₉ Il ₁₇ -OP-OH
OH and OH 209 8ΒΊ / 120 9 Cellulose acetate phthalate; Cellulose hexahydrophthalate; Cellulose trimellitate; Polyvinyl chloride; Polyvinylidene chloride; Polychlorostyrenes; Polynitrostyrenes; Polyvinylphenols; Polyvinyl chlorobenzoate; Polyvinyl nitrobenzoate; Polyvinyl nitrophthalate and mixtures thereof. 17. The method according to claims 10 to 13, characterized in that sodium or potassium salts are used as the charge control agent of substituted benzenesulfonic acids or polyethylene pyromellitate used. 18. The method according to claims 1 to 17, characterized in, that in addition to a charge control agent, saponin used. 19. The method according to claim 7, characterized in that there is layer support for the production of photographic recording materials modified with at least one gelatin-silver halide emulsion layer. 20. Process according to Claims 1 to 3, characterized in that the surface of the top layer of a photographic recording material is provided with at least one gelatin-silver halide emulsion layer, on which the cover layer is located and / or the back layer of the recording material is modified. «'■ 21. The method according to claim 20, characterized in that one used as a charge control means: a Na or K salt of a substituted benzenesulfonic acid, polyethylene pyromellitate and / or a Compound of the formula: 209885/1209 CH ₂ - ^ - N 209885/1209