US3658573A

US3658573A - Support provided with antistatic layer

Info

Publication number: US3658573A
Authority: US
Inventors: Claude Guestaux; Jean Leaute; Claude Virey; Jacques Vial
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1969-04-08
Filing date: 1970-04-06
Publication date: 1972-04-25
Anticipated expiration: 1989-04-25
Also published as: CA945426A; BE748333A; DE2016593B2; GB1317907A; JPS5232572B1; DE2016593A1

Abstract

Compositions for coating onto polymeric surfaces such as photographic film supports to reduce static include alkali metal salts of alkylphosphoric acid esters, arylphosphoric acid esters or aralkylphosphoric acid esters. The alkyl chains of the phosphoric acid esters contain from about eight to 22 carbon atoms and the alkali metal has an atomic weight of at least 23, the preferred alkali metals being potassium, rubidium and cesium. The salts are applied to the polymeric surfaces from aqueous or organic solvent solutions which may contain a binder such as a polyvinyl acetal, cellulose esters and ethers, etc. The phosphoric acid salts have distinctive properties as antistatic agents compared to lower alkyl phosphate salts such as alkali metal amylphosphates; for example, they impart good static protection at low humidity and do not transfer to adjacent film surfaces so to interfere with coating of photographic emulsions thereon. They also function as film lubricants.

Description

United States Patent Guestaux et al.

[451 Apr. 25, 1972 [54] SUPPORT PROVIDED WITH ANTISTATIC LAYER [72] Inventors: Claude Guestaux; Jean Leaute; Claude Virey; Jacques Vial, all of Vincennes,

21 Appl. No.: 26,143

[30] Foreign Application Priority Data Apr. 8, 1969 France ..6910616 Dec. 23, 1969 France ..6944542 [52] U.S.Cl. ..ll7/76 P, 96/87 A, 117/92,

117/1388 F, 117/138.8 E, ll7/l38.8 UA,

1l7/l38.8 UF, 117/144, 117/145,117/168, 252/8.6

[51] Int. Cl. ..G03c 1/82, C09k 3/16 [58] Field ofSearch..... ..................96/87 A; 117/1395 CO, 76 P, 92, 138.8 B; 106/177; 252/8.6

2,384,053 9/1945 Thomas ..1l7/139.5 CQ

3,525,621 8/1970 Miller ..96/87 A X 3,341,343 9/1967 Beiswanger et al. ..106/177 FOREIGN PATENTS OR APPLICATIONS 912,334 12/1962 Great Britain ..96/87 A 1,089,923 10/1954 France ..96/87 A Primary Examiner-William D. Martin Assistant Examiner-Ralph Husack Attorney-Walter O. l-Iodsdon and Wendell H. McDowell ABSTRACT Compositions for coating onto polymeric surfaces such as photographic film supports to reduce static include alkali metal salts of alkylphosphoric acid esters, arylphosphoric acid esters or aralkylphosphoric acid esters. The alkyl chains of the phosphoric acid esters contain from about eight to 22 carbon atoms and the alkali metal has an atomic weight of at least 23, the preferred alkali metals being potassium, rubidium and cesium. The salts are applied to the polymeric surfaces from aqueous or organic solvent solutions which may contain a binder such as a polyvinyl acetal, cellulose esters and ethers, etc. The phosphoric acid salts have distinctive properties as antistatic agents compared to lower alkyl phosphate salts such as alkali metal amylphosphates; for example, they impart good static protection at low humidity and do not transfer to adjacent film surfaces so to interfere with coating of photographic emulsions thereon. They also function as film lubricants.

10 Claims, No Drawings SUPPORT PROVIDED WITH ANTISTATIC LAYER The present invention concerns antistatic compositions, usable in the preparation of antistatic layers, designed, in particular, for photographic and magnetic film products. In that which follows, the invention will generally be described by referring to photographic products, although it applies to all products involving the problems of electrostatic charges.

It is well known that numerous types of photographic film supports have a tendency to produce static electric charges during the winding or the unwinding of these films and that these electric charges do not dissipate easily, because the materials that are used as film supports are poor conductors of electricity. High potentials which are being created in this manner often discharge suddenly, in the course of manufacture or of use of the film by the user, which produces a flash of light and an undesirable recording of the discharge of static electricity on the photographic emulsion. In order to avoid this result, it was customary, in the prior art, to apply to the back of the film support, a conductive layer making it possible to facilitate the dissipation of static charges, thus making it possible to avoid the sudden charges and the light flashes which accompany them.

The antistatic layers usually consist of a binder wherein an organic or mineral organic conductive substance is dispersed, which makes it possible to render the surface of the support sufficiently conductive so as to make possible the flow of electrostatic charges. They are most often hygroscopic layers the effectiveness of which varies as a direct result of the degree of humidity in the air. Such antistatic layers are thus not suitable for low degrees of humidity because they are then no longer sufficiently conductive. These hygroscopic layers are also not suitable for very high degrees of humidity because they become sticky and hard to separate from the surface to which they adhere the effort that is necessary to separate two superimposed windings create, sometimes even higher charges than those which would appear without any antistatic layer.

In order to eliminate electrostatic phenomena, it was suggested in particular to use, as antistatic agents, mixtures such as described in French Pat. No. 1,089,923, which comprise two compounds, one of these compounds being selected from among the alkylphosphates of alkaline metals and alkaline metals, ammonium or amine cellulose sulfate salts or cellulose acetate sulfate salts, the other compound being a spreading agent selected from among the esters of higher fatty acids and polyalcohols. The alkyl groups of alkylphosphates consisted of lower alkyl groups, such as ethyl or amyl. There have also been described diester alkali or ammonium salts produced from orthophosphoric acid and lower aliphatic alcohols, such as described in French Pat. No. 1,282,354. There have also been described the ammonium or ethanolamine alkylsulfate and alkylphosphate salts, as described in French Pat. No. 1,435,826. Compound such as potassium amylphosphate and especially triethanolamine alkylphosphates have a good solubility in the usual organic solvents. However, when they are used on the photographic or cinematographic film supports, they are too sensitive to water and easily transfer to the opposite surface of the support with which they are in contact after winding in a roll and therefore cause a poor wettability of the photosensitive emulsion on this surface during its application. On the other hand, the organic salts, eg those of triethanolamine, have a damaging action on the photographic emulsions, such as a desensitization or fog-formation.

The present invention provides new antistatic compositions having no damaging action on the photosensitive layers of photographic and cinematographic films, and also usable for magnetic films, causing no adherence between the windings of the films and which are not deteriorated by heat or humidity and which are, for the most part, self-lubricating.

The antistatic compositions according to the invention, comprise as antistatic agent a salt of an alkali metal having an atomic weight at least equal to 23 of an organic monoor diester of phosphoric acid in an aqueous or organic medium, characterized in that the organic ester is derived from an alkylphosphoric acid the alkyl group of which contains of from about eight to 22 carbon atoms or from an alkylarylphosphoric acid, or an arylphosphoric acid containing a comparable number of carbon atoms. That is, when an aryl group is present as in phenylphosphate, the six-carbon atom phenyl group imparts the desired properties. Similarly, with an aralkyl group such as benzyl or phenylethyl, the carbon chain can contain less than eight carbon atoms. Moreover, the compositions may contain a binder.

The alkyl phosphoric acid esters of the invention containing eight to 22 carbon atoms in the alkyl group, straight or branch-chained, will be found to be generally superior, when they are used in antistatic layers, to similar esters, such as the ethyl or amyl phosphoric acid esters of the above patents. The esters of the invention show little tendency to transfer from the antistatic layer to adjacent surfaces such as a subbing layer on the opposite surface of the support on which they are coated and thus do not interfere with subsequent coating of a silver halide emulsion onto the subbing layer. In particular, the alkyl esters of 12, 14, 16 and 18 carbon atoms are exceptional in this respect in that they show no noticeable tendency to interfere with emulsion coating of the opposite surface of the support on which they are coated. The eight to ll and 19 to 22 carbon atom alkyl phosphoric acid esters, although useful, show some tendency to interfere with the emulsion coatings. The cetyl phosphate salts are exceptionally useful because of low tendency to transfer to the adjacent surfaces. Moreover, the cetyl esters when used in antistatic layers also exhibit excellent lubricating properties for the photographic films comparable to waxes such as Carnauba wax. The eight to 22 to carbon alkyl esters are also advantageous, compared to similar lower alkyl esters such as amyl phosphate, since they have higher solubility in organic solvents which allow dispersion of the esters together with waxes or synthetic polymers in organic solvent or aqueous organic solvent coating compositions for coating on all types of photographic film supports, as illustrated in the examples below. From the examples it will be seen that certain compositions, e.g., alkyl phosphate wax dispersions are very useful for coating film base such as linear polyester. Other coating systems containing, e.g., a mixture of alkyl phosphate and polymer such as Butvar are very useful for coating cellulose ester film bases.

It is unexpected that the esters having chain lengths of about eight to 22 carbon atoms should be so effective as antistatic agents. One skilled in the art knowing that the hydrophilic organic and inorganic compounds are usually the most effective antistatic agents would expect that after coating the antistatic layers from aqueous solution, the higher molecular weight aliphatic groups would orient at the air-water interface forming paraffin-like monolayers which would not-give antistatic properties, contrary to the facts.

The phosphoric acid esters that are preferred for preparing the salts according to the invention appear to correspond to the following formulas RO-P O and HO-P 0 HO V 7 7 ,H0/ wherein R represents a substituted or unsubstituted alkyl group, having eight to 22 carbon atoms. For example, R is the octyl, nonyl, decyl, undecylenic, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, etc. group. The R groups can be the same or different organic radicals.

R may also contain one or more substituted or unsubstituted benzene nuclei, joined or not joined directly to the phosphoric group, eg; phenyl, octylphenyl, etc.

The preparation of these acids produces a mixture of acids corresponding to the preceding formulas. One may use for the preparation of the salts of the present invention, the phosphoric acid monoor diesters alone or in a mixture.

The long alkyl chain or an aromatic radical reinforces the organophile character of the compounds, and thus conferring solubility in the usual solvents, decreases their sensitivity to water, and by minimizing transfer of the compounds to adjacent surfaces reduces the defects related to wettability of the surfaces by the emulsions. These compounds, especially in the case of those having long alkyl chains, display lubricating properties similar to those of the usual waxes. On the other hand, being alkaline salts, their properties bring them closer to soaps and they are dispersible in water and have a dispersive power toward certain substances.

When compared, e.g., to an amine salt, their antistatic power is increased by the presence of the alkali metal ion, their damaging action to the photosensitive emulsions is nil and their resistance to hydrolysis is increased.

One may use, according to the invention, as alkali metals, sodium, potassium, rubidium, as well as cesium, because for the same alkylphosphate, the effectiveness increases from lithium, for which it is practically nil, to the sodium, potassium, rubidium and cesium salts. in order to measure the surface resistivity, at 30 percent and 50 percent relative humidity, of the salts of lithium, sodium, potassium, rubidium and cesium of alkylphosphoric acids, one applies separately and without binder, e. g., the salts of Li, Na, Ki Rb and Cs of monooctylphosphoric acid to a cellulose triacetate support using a solution having l/ 100 mole of the salt per liter in a mixture of solvents containing 80 parts of methanol and 20 parts of 2- methoxyethanol. The results are indicated in the following table:

Salt Cation Surface resistivity in'Gn. crn/cm at 50% RH at 30% RH One sees that the surface resistivity depends on the relative humidity and that unexpectedly it decreases from lithium to potassium to then become fairly constant for rubidium and cesium salts.

With the use of potassium ion, the surface resistivities are practically constant, both at 50 percent and 30 percent relative humidity. The differences between the surface resistivities for 30 percent and 50 percent relative humidity are small for the potassium, cesium and rubidium. On the other hand, for sodium, this difference is very great since the surface resistivity for a 30 percent relative humidity reaches up to 6,000 GS). cm/cm, whereas it is only 1.10 GO. cm/cm for a 50 percen relative humidity.

From that which precedes, it appears that the salts which will produce the best conductive properties are, preferably, those of potassium, rubidium and cesium. On the other hand, the alkylphosphate salts in which the alkyl group contains of from 14 to 18 carbon atoms, generally give the most satisfactory combination of properties that are desired for forming film backings.

One may apply salts of alkylphosphoric acids or alkylaryl or arylphosphoric acids in an aqueous or organic medium, with or without binder. The solvents or dispersing agents usable according to the invention comprise the compounds which have, in particular, hydroxyl groups, such as water, alcohols, glycols, etc., such as methanol, ethanol, methyl monoether of glycol or Z-methoxyethanol, etc., or mixtures of these compounds. In the mixtures, the alcohols may be used in any proportion, but it is preferred to use mixtures containing, e.g., 80 percent of methanol and 20 percent of Z-methoxyethanol, although good results are obtained with other proportions. It is also possible to use mixtures of water and a alcohol, e.g., water and methanol, or other solvents, e.g., methylene chloride.

The use of a binder, although not indispensible, may prove in many cases beneficial. Among the usable binders, we may cite most of the cellulose derivatives: cellulose acetate, cellulose acetatebutyrate, cellulose ether phthalate, methylcellulose, hydroxyalkylmethylcellulose such as hydroxypropylmethylcellulose etc. Numerous vinyl derivatives are also usable such as acetals, e.g., polyvinyl butyrals such as the Butvar B 76" product sold in the U.S.A. by Schawinigan Resins Corp., suitable for applications in an organic medium, as well as polyvinyl alcohol and other polymers and copolymers soluble in an aqueous medium. Natural binders such as, e.g., gelatin, casein, agar-agar, waxes etc., may also be suitable.

On theother hand, due to the dispersing power of these antistatic compounds, one may consider the use, as a binder, of substances which have no mutual solvent. Thus, the compositions appear in the state of dispersions. As examples of such dispersions, one may indicate:

1. Aqueous dispersions of a natural or synthetic waxy substance, such as Carnauba wax, in which the antistatic compounds then play the part of dispersing agent. 2. Dispersions of these salts effected in the midst of an aqueous emulsion of synthetic polymer or copolymer, particularly of an acrylic ester, acrylonitrile, vinylidene chloride and of an unsaturated acid, e.g., a terpolymer of methyl acrylate, vinylidene chloride and itaconic acid or a terpolymer of acrylonitrile, vinylidene chloride and acrylic acid.

The products containing the salts of the invention in antistatic layers have particularly high conductive propertiesAs a result, a sizeable quantity of these salts is not necessary for obtaining an efficient protection, usually 2 to 200 mg/m suffice, which may be obtained from solutions containing of from 0.2 to 20 g per liter of antistatic compound by using coating means such as indicated hereinafter.

The quantities of binder that are used may vary. One may use proportions of a binder up to approximately 50 percent by weight with respect to the total weight of binder and salt of the phosphoric ester. One obtains particularly good results with approximately 30 percent by weight of binder with respect to the total weight of binder and salt.

The films according to the invention may have, as support, a film formed by one of the numerous customary film-forming substances. One may use, in particular, as supports, cellulose esters such as cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetobutyrate, linear polyesters such as ethylene glycol polyterephthalate, polycarbonates, copolyesters of terephthalate and ethyleneglycol isophthalate and of l,4-cyclohexane-dimethanol a polyolefin such as polyethylene or polypropylene polystyrene and a vinyl polymer such as a copolymer of vinyl acetate and vinyl chloride, a copolymer of vinyl chloride modified by maleic anhydride or a polymer of vinyl fluoride. A paper support coated with polyester or a polyolefin such as polyethylene is also useful.

The supports carrying the antistatic layers of the invention can be coated with well-known emulsion layers for black-andwhite or color photography, suitable subbing layers being employed to adhere the emulsion layers to the support. Ordinarily, the antistatic layer is coated on the surface of the film base opposite to the surface to be emulsion coated. However, the phosphoric acid ester can be coated under the emulsion layer. In the case of polymer-coated paper the esters are useful both for sizing the paper (as an internal antistat), prior to coating the polymer, or for coating the surface of the polymer-coated paper.

The coating processes include, in general, using a wetting cylinder immersed into the solution that is to be applied and films. In addition to the use of the antistatic compounds having a long alkyl chain or an aromatic radical chain having low sensitivity to water, when a binder is also used for adhering the compounds to the support the layers have a more permanent character than in the case of short-chain compounds per se of the above prior art.

On the other hand, certain of these layers may be removed in the course of treatments which photographic and cinematographic films may undergo. This is made possible, e.g., by using a binder that is soluble in an alkaline medium, such as an acidic or water-soluble polymer, or a binder that is capable of being submitted to chemical modifications in the course of treatment to render it soluble in water, acid or alkaline solutions.

The previously described phosphoric ester'compositions are of particular interest when they are used in the form of antistatic backing layers for photographic film supports; However, certain of these may be used as sub-layers of the emulsion. One may also use these antistatic layers as protective overlayers of the unexposed or developed emulsion. Certain other above-described compounds may likewise be incorporated in the surface layers of the photographic emulsion. Antistatic properties of the esters is also retained when they are placed in these layers.

The backings containing the long-chain phosphoric ester' compounds are self-lubricating. The friction coefficients, measured in contact with tungsten carbide are low, in therange of 0. l 5 for 20 g to 100 g, for example, of applied weight.

The surface resistivities are much below the resistivity of an untreated test sample. For example, with potassium octadecylphosphate in an organic medium (methanol and 2- methoxyethanol) applied on a cellulose triacetate support, the surface resistivities, measured for a relative humidity of50 percent and 30 percent, are equal to 9 G9. cm/cm and 270 G0,. cm/cm, respectively, compared to resistivities above 60,000 G9. cm/cm in the case of an untreated test sample.

The antistatic layers of the invention, as mentioned previ-' ously, may be used for photographic and cinematographic films. Another field for the application of antistatic layersof the invention is the magnetic recording, wherein one uses magnetic bands to the backing of which, in particular, one may apply an antistatic layer in order to remove the charges, due, in particular, to the friction of the bands in the various machines in which they are apt to be used.

The preparation of the antistatic salts, that are used according to the invention, may be effected, e.g., for the salts of alkylphosphoric acids, as follows.

Preparation of the alkylphosphoric acids.

One establishes a light circulation of dry air in a three-neck flask provided with a stirrer and introduces 3 moles of the selected alcohol, anhydrous, and melted if it is solid at room temperature. One heats and, without surpassing 95 C, one introduces, in small quantities, one mole of phosphoric anhydride. After the emission of heat has stopped, the reaction mixture is kept between 90 and 95 C for approximately 6 hours, until complete disappearance of the anhydride. Preparation of alkylphosphoric acid salts, in particular potassium salt.

In a flask provided with a stirrer, one introduces a sufficient amount of ethanol for dissolving the stoichiometric quantity of potassium hydroxide, in the form of pellets, necessary for the complete salt formation of the alkylphosphoric acid. The alcoholic solution is brought up to a temperature that is sulfcient for dissolving the acid, either solid or liquid, that one introduces into the flask in small quantities while stirring. After the complete introduction of the acid, the temperature of the mixture is kept at 70 C and the stirring for a period of 10 minutes.

If the obtained product is solid, it is cooled down to from to C and the resulting salt is filtered on a Buchner funnel. The residual ethanol is then removed by means of drying in an oven at a temperature of from 80 to 85 C. If the salt obtained is liquid, the alcohol is distilled under vacuum.

The following examples illustrate the invention. In these examples, the antistatic layers are applied to cellulose triacetate or ethyleneglycol polyterephthalate supports. However, it is possible to apply them to other supports such as those cited previously.

Except as indicated below (Example ll) the mixed esters prepared as above were used. In Example 11 the monooctyl ester had been isolated from the reaction mixture also containingthe dioctyl ester.

In these examples, the-surface resistivities are given in GO. cm/cm and the electrostatic fields in V/cm for endless-bands turning on a system of metallic rollers connected to the ground.

The Examples 1 to 14 relate to applications, effected without binder, in an organic medium as well as in an aqueous medium with different alkaline salts, to a cellulose triacetate support'(Examples l 'to ll) as well as on an ethyleneglycol polyterephthalate support (Examples 12 to 14).

EXAMPLE 1 A cellulosetriacetate film is. coated with a solution containing:

Potassium octadecylphosphate 0.4 g Methanol ml Z-methoxyethanol 20 ml After drying, the properties of the product are compared with those of an untreated test sample. The results are indicated in Table 1.

EXAMPLE 2 One applies to a cellulose triacetate support a coating solution comprising 0.4 g of potassium cetylphosphate, 80 ml of methanol and 20 ml of Z-methoxyethanol; The surface resistivities for 50 percent and 30 percent relative humidity are 4 GO. cm/cm and 230 GO. cm/cm, respectively.

EXAMPLE 3 The coating. solution contains 0.4 g of potassium tetradecylphosphate, 80 ml of methanol and 20 ml of 2- methoxy ethanol and it is applied to a cellulose triacetate support. The results obtained are given in Table I.

EXAMPLE 4- The coating solution contains 0.4 g of potassium dodecylphosphate and 100 ml of ethanol and it is applied to a cellulose triacetate support. The surface resistivities, measured for 50 percent and 30 percent relative humidity, are 1.1 G02 cm/cm and 45 G9. cm/cm, respectively.

EXAMPLES 5 and 6 One applies to cellulose triacetate supports, coating solutions containing, in'a solventmixture of 80ml of methanol and 20 ml of 2-methoxyethanol, 0.4 g of rubidium cetylphosphate for theexample 5, and 0.4 g of cesium cetylphosphate for the example 6.

EXAMPLES 7 and 8 In these two examples, the respective coatingsolutions are applied to triacetate supports. The coating solutions contain, the one, 0.4 g of rubidium octadecylphosphate, the other, 0.4 g of cesium octadecylphosphate, in 80 ml of methanol and 20 ml of 2-methoxyethanol.

EXAMPLE 9 One applies to a cellulose triacetate support, the following solution:

Potassium phenylphosphate 0.4 g Methanol ml 2-n1ethoxyethanol l0 ml EXAMPLE 10 One applies, in the above manner, to a cellulose triacetate support a solution similar to that of Example 9, but wherein the potassium phenylphosphate is replaced by'potassium octylphenylphosphate.

EXAMPLE 1 1 Potassium octadecylphosphate 0.25 g Low-viscosity cellulose ether phthalate 0.25 g Methanol 80 ml 2-methoxyethanol 20 ml The surface resistivities for 50 percent and 30 percent rela- .tive humidity are 35 GO. cm/cm and 460 G0. cm/cm, respectively. The electrostatic fields, measured for 50 percent and 30 percent relative humidity, are and 1,390 V/cm, respectively.

TABLE I.TESTS EFFEOTED WITHOUT BINDER Coeflicient of friction in contact Surface resistivity Electrostatic field with tungsten in G5}. cm.lcm. in V./cm. carbide under-- 'Inst number Support 50% Rn 30% Rn 50% R11 80% Ba 20 g. 100 g.

Untreated test sample- Cellulose trlacetate--. 60, 000 60, 000 +1, 320 +2, 040 0. 70 0. 62 1 9 270 0 +800 0. 12 0. 14 4 230 0 +740 0. 19 0. 14 1. 6 340 0 +660 0. 07 0. 06 1. 1 45 0 +56 0. 0. 13 0. 80 10 0 0 0. 17

EXAMPLE 12 The coating solution consists of 0.4 g potassium octadecylphosphate in l00 ml of water. It is applied to an ethyleneglycol polyterephthalate support. After drying, the surface resistivities and the electrical fields are measured for 30 percent and 50 percent relative humidity.

EXAMPLES l3 and 14 In these two Examples, the support is a polyester: ethyleneglycol polyterephthalate. The first coating solution contains 0.4 g of rubidium cetylphosphate, the second 0.4 g of cesium cetylphosphate in solution in 100 ml of water containing 0.08 g of saponlne as spreading agent.

In the following Examples, 15 to 26, one uses compositionscontaining a polymer binder soluble either in an organic medium or in an aqueous medium, which is applied to a cellulose triacetate support (Examples 15 to 20) or to a polyester support (Examples 21 to 26). The results obtained: surface resistivities, electrostatic fields, friction coefficients, are shown' in Table ll EXAMPLE 15 EXAMPLE l6 ln this example, the conductive layer that is applied is temporary and is completely removable with water after saponification in an alkaline bath.

One ,applies to cellulose triacetate support the following coating solution:

EXAMPLE 17 One applies to a cellulose triacetate support the following coating solution:

Potassium octadecylphosphate 0.25 g Product Butvar B 76 (Polyvinyl Butyral sold by Shawinigan Resins Corp.) 0.l g Methanol ml Z-methoxyethanol l5 ml EXAMPLE 18 One applies to a cellulose triacetate support a conductive layer from a coating solution containing: 0.1 g of the cellulose triacetate, 0.3 g of potassium cetylphosphate, 50 ml of dichloromethane, 46.5 ml of methanol and 3.5 ml of distilled water. The results that are obtained are indicated in Table ll.

EXAMPLE 19 One applies to a cellulose triacetate support a conductive layer from a coating solution containing 0.1 g of the product Butvar 8-76, 0.25 g of potassium cetylphosphate, 85 ml of methanol and 15 ml of 2-methoxyethanol. The surface resistivity electrostatic field and friction co-efficient are given in Table II.

EXAMPLE 20 One applies to a cellulose triacetate support the following composition:

Metltocel HG resin, I00

centipoises 0.2 g Potassium cetylphosphate 0.4 g Water l5 ml Melhylglycol 20 ml Methanol 65 ml EXAMPLE 21 The coating solution consists of 0.4 g potassium octadecylphosphate, 0.2 g of product Butvar 8-76, 80 ml of methanol and 20 ml Z-methoxy-ethanol. It is applied to a polyester (ethyleneglycol polyterephthalate) support. The results are given in Table II.

EXAMPLE 22 One applies to a polyester support the following composition:

TABLE II [Application in aqueous or organic solution with a binder] I Friction coeffieient in Surface resistivity Electrostatic field contact with G63. emJem. in V./om. tungsten carbide under Example Support Binder 50% Rn 30% RH 50% RH 30% Ba 100 g.

Triacetate Cellulose triacetate 34 700 +150 +400 0. 15 d CEP LV 35 460 0 +1390 0. 15 9 340 0 +430 0. 14 190 5500 +410 +1500 0. 16 12 550 +62 +376 0. l4 1. 2 6. 3 0 +254 0. 14 0. 36 6 0 79 0. 28 6. 2 l3 0 +550 0. 12 1600 0 +560 0. 15 100 7000 +245 +780 0. 17 2. 3 110 0 +020 0. 11 73 570 0 +600 0. 14

Methocel 90HG resin, I00

centipoises 02 g Potassium cetylphosphate 0.4 g Water I00 ml EXAMPLE 23 One applies to a polyester support the following composition:

Methocel 90I-IG resin, I00 centipoises 0.4 g Potassium cetylphosphate 0.4 g Water 100 ml EXAMPLE 24 One applies to a polyester support the following composition:

Methocel 90HG resin, I00 centipoises 0.4 g Potassium octadecylphosphate 0.43 Water I00 ml EXAMPLE 25 One applies to a polyester support the followingcomposition:

Methocel 90HG resin, I00 centipoises 0.2 5; Potassium octadecylphosphate 0.4 g Resorcinol 1.5. g Water 100 ml EXAMPLE 26 The ethylene glycol polyterephthalate film is coated with a composition obtained by mixing:

A polymer latex with a 15% content in methacrylate,

vinylidene chloride. itaconic acid (23- 5 2) 0.5 g Resorcinol 1.0 g Saponine 0.25g Wale? 98.25ml

To the surface of the coated and dried support, one applies the following antistatic composition:

Aqueous solution containing I()% of polyvinyl alcohol (acetvl content in the proximity of 2%) 5.0 g

In the following two examples 27 and 28, one uses gelatin as a binder (see results in Table Ill).

EXAMPLE 27 To the substrated surface of a cellulose triacetate support, one applies the followingcoating solution:

Gelatin 2 g Potassium cetylphosphate 2 3 Water ml The'solution is =keptat 35 C and vitisapplied ;by means of surface-tension coating followed by air knife" treatment under a-pressure of 4.5mm Hg. As in the preceding examples, the surface resistivities, the electrostatic fields, as wellas the frictioncoefiicient'are measured.

EXAMPLE 28 One operates as in Example 27, butithe layer is treated with an airknife under a pressure of 6mmHg.

TABLE III Frictlon co- Surface Electrostatic etficient in resistivity in field In contact with G9,. cm./c.m V./em. tungsten carbide under Example 50% RH 30% 50% RH '30%;Rn 100 g.

In thefollowing'Examples, the application of;the,conductive layer is effected in aqueousor dilute.alcoholicemulsion. The antistaticagent is incorporated with an aqueousdispersion of copolymers. A particularly advantageous composition comprisesa terpolymer of from approximately 10 to. l S percent by weightof alkyl acrylate, of from 8010 89 percent of vinylidene chloride andof from 1.0 to 4.0 percent of itaconic acid.

-e.g.,iCarnauba-wax-effectedwith the aid of; the alkaline salts of alkylphosphates (Examples 35 to 44).

11 7 EXAMPLE 29 triacetate support and it is dried for minutes at 1 15 C.

EXAMPLE 30 One operates as in Example 29, but potassium octadecylphosphate is used in the place of potassium cetylphosphate.

EXAMPLE 31 One prepares the following mixture containing:

1 liter of a latex containing 2 percent dry terpolymer comprising, by weight, 15 percent acrylonitrile, 83% vinylidene chloride and 2 percent acrylic acid.

l liter of an aqueous dispersion containing 2 percent of potassium cetylphosphate.

The mixture is applied to a cellulose triacetate support.

EXAMPLE 32 The following mixture is prepared containing:

' 1 liter of a latex containing 2 percent of dry polymer material comprising, by weight, 15 percent acrylonitrile, 83 per-- cent vinylidene chloride and 2 percent acrylic acid.

1 liter of an aqueous dispersion containing 2 percent potassium octadecylphosphate. The mixture is applied to a cellulose triacetate support.

EXAMPLES 33 and 34 One operates as in Examples 29 and 30, respectively, but the solution is applied to an ethyleneglycol polyterephthalate support.

TABLE IV {Compositions containing a latex 01 a torpolyrner and applied to a cellulose triacetate support] Measured at 50% RH Measured at 30% R Resistivity Field Resistivity Field Friction n G52, in in G51. in coefiicm./cm V./cm. cmJcm. V./cm. clent Ethyleneglycol polyterephthalate support EXAMPLE 35 With the aid of a stirrer, e.g., of the magneticbar type, one stirs a mixture consisting of 200 g of water at 60 C and 50 g of potassium octadecylphosphate, until a uniform dispersion is obtained. The temperature is then raised up to 90 C and the mixture is then poured into g of the fatty-grease type of Carnauba wax, kept at the melted state under stirring (e.g., with a paddle-type stirrer or a planetary-motion type stirrer).

The obtained dispersion is diluted with distilled water until one obtains a concentration of a 0.5 percent phosphoric acid derivative.

This preparation is applied according to well-known techniques (transfer cylinder, surface-tension coating, air knife) to a cellulose triacetatephotographic film support.

EXAMPLE 36 One applies, as previously, to a cellulose triacetate support a final dispersion containing 0.5 percent of phosphorous compound in a 50/50 mixture of water/ethanol, but modifying the salt/wax relation in the following manner:

Potassium octadecylphosphate 25 g Carnauba wax 6 g in the Examples 37 to 40, the type of alkylphosphoric acid used is varied. The compositions that are indicated are primary (concentrated) dispersions which one dilutes for use with a 50/50 mixture of water-ethanol until it contains no more than 0.02 percent of the phosphorous compound; one applies them to a cellulose triacetate support.

EXAMPLE 37 Potassium dodecylphosphate 12.5 g Carnauba wax 25 g Water 200 g EXAMPLE 38 Potassium tetradecyl phosphate 12.5 g Carnauba wax 25 3 Water 200 5 EXAMPLE 39 Potassium cetylphosphate 12.5 g Carnauba wax 25 g Water 200 g EXAMPLE 40 Potassium octadecylphosphate 12.5 g Camauba wax 25 g Water 200 g The values of surface resistivities of the electrostatic fields and of the friction coefficients are indicated in Table V.

In the above Examples, the ratio between the dispersing agent and the wax is 160% in example 35 400% in example 36 50% in examples 37 to 40,

but it is possible to have them vary within even greater limits. The maximum quantity of phosphoric derivative to be used with respect to the wax is limited only by the value of the friction coefficient that is desired, the minimum quantity being that which is indispensable for the preparation of the disper- Good results are obtained with antistatic emulsifier/wax ratios from 0.1 to 4.

Entirely comparable results may be obtained when an ethyleneglycol polyterephthalate support is used.

EXAMPLES 41 to 44 One operates as in Examples 37 to 40, respectively, but, the solution is applied to an ethyleneglycol polyterephthalate support.

The results of the measures are indicated in Table V.

Electrostatic fields Friction coclficlcnt Surface resistivity, in V/cm measured measured under a G53. cm./cm. at at charge 01-- Ex. 30% RH 50%RH 30% En 50% RH 20 g. 100 g.

Poly(ethyleneglycol terephthalate) support Friction coefficient measured under a Surface resistivity Electrostatic fields charge ol'- in G61. cm./cm. at inV./crn. measured 50% Rrr at 50% En 20 g. 100 g.

i TABLE v11 Surface resistivity Electrostatic Friction coelficients t in Ggg, cm./cm. ficlds in V/cm. unrler Tes s Number Supports 30% R}; 50% Rn 30% RH 50% Rn 20 g. 100 g.

1 {Astralon 100 43 +640 0. l 0. l4 Untreated control. 60, 000 60, 000 3.400 3,.l00 0.35 0.42 2 {Teslar 29 12 +450 0 0. 20 o. 17 Untreated control 60,000 60,000 4,800 4.000 0. 57 0. 52 3 {Paper pins polyethylene treated by corona discharge- 470 12 +160 0 v0. 20 0. l Untreated control. 60,000 60,000 800 710 0.19 0.20 Paper plus polyethylene treated by corolla discharge 400 24 310 "0 0. 0. 20 Untreated control 60,000 60.000 -l,060 350 0.52 0.50

EXAMPLE 45 The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be unone apphe? thefonowmg cetypliosphate coniposmon m 15 derstood that variations and modifications can be effected aqueous solution with Carnauba wax in a 4 to 1 ratio within the Spirit and scope of the invention Potassium cetylphosphate 0.4 g

Carnuuba wax 0.] 3 we claim: Distilled water 30 g 1. A polymeric photographic film support provided w th a Ethanol 19.28 g layer containing an antistatic agent consIstmg of a potassium, "Antarox co e36 (wetting agent sold by Genera rubidium or cesium salt of an alkylphosphoric acid ester, the Amlme Cmp) 8 alkyl group of which contains from about eight to 22 carbon atoms. to two supports 2. A polymeric photographic support according to claim 1 25 wherein the antistatic layer also containsa polymeric binder.

3. A polymeric photographic support according to claim 1 wherein the antistatic layer also contains a wax.

l. Diphenylopropane polycarbonate sold by Bayer, 2. Stretched polystyrene sold by Plax Corp. by means of surface tension coating followed by air knife treatment.

The following results were obtained 4. The product according to claim 1 wherein the support is a TABLE VI Surface resistivity Electrostatic fields Friction coefli- T t in Ggz..cm.lcm. in V./cm. cients under- 95 5 Number Supports RH 50% RH 30% R5 50% RH 20 g. 100 g.

1 {Polycarbonate 37 6. 7 +710 0 0. 20 0. 17 Untreated control- 60,000 60,000 +3.120 742 0.80 0.30 2 {Polystyrene 19 5. 5 +474 0 0. 17 0. 14 Untreated control. 60,000 60,000 -336 -292 0.68 0.64

EXAMPLE 46 linear polyester, polyolefin, polycarbonate, polystyrene, vinyl ol mer or co ol mer su ort, or a a er coated with said In the following example, one uses the aqueous disg g p y pp p p persion of potassium cetylphosphate and Carnauba wax in the 4 to 1 ratio; 5. The product according to claim 4 wherein both the anti- Gmms static agent and a wax are present in the antistatic layer.

P 322 5; gzi 3 i 6. The product according to claim 4 wherein both the antrstatic a ent and a 0i meric binder e res t in t- Distilled water 99. 28 g p y at p en the an l Antarox CO 43 ,,w :,u 9.421 50 statciaye" This dispersion is applied by means of the previously described methods to the following materials l. Astralon vinyl chloride copolymer modified with maleic anhydride, sold by Dynamit Aktiengesellschaft Vormals Al- 7. The product according to claim 1 wherein the support is a cellulose organic acid ester film support.

8. The product according to claim 1, wherein the support is a synthetic polyester film support.

fred Nobel & Co.

Teslar (vmyl Polyfluonde) Sold by Pom de 9. The product according to claim 1, wherein the support is Nemomsa paper coated with a polyolefin.

3. Paper for photographic use coated with a polyethylene layer Previously treated by f discharge; 6O 10. The product according to claim 1 wherein the alkyl 4. Paper for photographic use coated with a polyethylen group of the alkylphosphoric acid ester contains l2, l4, 16 or .layer, but which has not been submitted to corona discharge. 18 carbon atoms.

After treatment or" these various supports, the following results are obtained:

Claims

2. A polymeric photographic support according to claim 1 wherein the antistatic layer also contains a polymeric binder.
3. A polymeric photographic support according to claim 1 wherein the antistatic layer also contains a wax.
4. The product according to claim 1 wherein the support is a linear polyester, polyolefin, polycarbonate, polystyrene, vinyl polymer or copolymer support, or a paper coated with said polymers.
5. The product according to claim 4 wherein both the antistatic agent and a wax are present in the antistatic layer.
6. The product according to claim 4 wherein both the antistatic agent and a polymeric binder are present in the antistatic layer.
7. The product according to claim 1 wherein the support is a cellulose organic acid ester film support.
8. The product according to claim 1, wherein the support is a synthetic polyester film support.
9. The product according to claim 1, wherein the support is a paper coated with a polyolefin.
10. The product according to claim 1 wherein the alkyl group of the alkylphosphoric acid ester contains 12, 14, 16 or 18 carbon atoms.