DE1106601B - Methods and means for the physical development of photographic images - Google Patents

Description

BiBiJOTHSK DSS GERMAN

PATtfH'AföTES

The invention relates to a method for Production of photographic images through a stabilized, purely physical and physical development Developers to carry out this procedure.

Under "purely physical development" is meant the intensification of a weak photographic one Metal nucleation, which in many cases cannot even be perceived with the eye, results in an image of the desired optical density understood, with a water-soluble reducible metal compound from the beginning is present and wherein that resulting from reduction by means of a photographic reducing agent Image metal at least for the most part from the metal ions of the mentioned metal compound or originates from complex anions containing the metal.

The "purely physical development" becomes what is known as the chemical development differentiated, be which a developer solution is used, which at least initially not a dissolved one Compound of the noble metal and in which the figurative metal resulting from reduction exclusively originates from metal ions, which are already present in the crystal lattice of a metal compound which cannot be dissolved in water which is contained in the photographic material before processing. These chemical development can, under certain circumstances, be accompanied by a certain development, the is due to the dissolution of the image-forming metal compound in the developer.

A "pbtographic reducing agent" is understood here to mean a compound which is in solution able to reduce the mentioned metal ions or complex anions containing the metal to metal and their effects; in the physical developer under the conditions otherwise prevailing therein due to the presence of a photographic metal seed image, it is accelerated that a sufficiently selective metal deposit on it Metal nucleation result.

One can distinguish three large groups of photographic developer substances:

1. The group of organic compounds with two OH groups. In addition to hydroquinone, these include ζ. Β. Breecatechin, pyrogallol, gallic acid, and ascorbic acid.

2. The group of organic compounds which have an O Η group and an optionally substituted one Amino groups included. These include o-md p-aminophenol, p-methylaminophenol sulfate (»Metol«) and p-hydroxyphenylglyein, which is inter the name »Kodurol« is in trade.

for physical development

photographic images

Applicant:

NV Philips' Gloeilampenfabrieken,
Eindhoven (Netherlands)

Representative: Dipl.-Ing. H. Zoepke, patent attorney,
Munich 5, Erhardtstr. 11

Claimed priority:
Netherlands 11 October 1958

Hendrik Jonker, Cornells Johannes Dippel

and Arian Molenaar, Eindhoven (Netherlands),

have been named as inventors

3. The group of organic compounds which contain two amino groups, one of which is optionally monosubstituted, the other optionally mono- or disubstituted. These include o- and p-phenylenediamine and Ν, Ν-diethyl-p-phenylenediamine.
There are also some other photographic reducing agents, such as l-phenyl-3-pyrazo-iidone ("phenidone") and various inorganic photographic reducing agents, such as ferrous, titanium and vanadium ions, which are usually in the form of complex compounds, e.g. B. the ferro-oxalate complex can be used.

In purely physical developers, combined with photographic reducing agents, only Metal ions and complex metal ions of metals that are more noble than copper are used. A multiple physical developer used is e.g. B. a solution of silver nitrate in water, the hydroquinone, Metol or p-phenylenediamine is added. Furthermore, such a developer will be multiple Still other substances are added to extend the service life or to regulate the speed of development serve, e.g. B. organic acids, buffer mixtures or substances that interact with the noble metal salt react to form complex anions.

However, the purely physical development has so far still had disadvantages, those of its general use

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have stood in the way of photographic technology. The physical developers are in fact In contrast to the chemical developers, unstable systems because between the noble metal compound and the reducing agent, apart from the heterogeneous reaction on the metal nucleus, which intensifies this a homogeneous reaction can still take place in the solution, which then leads to spontaneous formation of metal nuclei in the solution and in the photographic material outside the growing nucleus leads. In addition, a spontaneous, catalyzed Reduction take place, which also gives rise to an undesirable loss of metal. If such Once metal nuclei have arisen spontaneously, their growth competes with the growth of the through the exposure to light resulting from the metal nucleation. Naturally, this spontaneous nucleation also takes place when the physical developer is not in use, and this has the consequence that these developers perish relatively quickly with metal deposition and that the vessels used in the process get dirty considerably. So they are uneconomical to use. The spontaneous formation of Germs in the photographic material outside of the growing germ pattern resulting from exposure can cause undesirable fogging of the final photographic image. The spontaneous one Decomposition in the physical developer usually takes place in a period of time that is not very long is longer than the time it takes for the metal seed image to develop into a photographic metal image of the desired optical density is necessary.

It is known that in certain cases it is possible to extend the life of a purely physical developer, e.g. By lowering the temperature, by dilution, by decreasing the p _H -value or by the addition of the oxidation product of the reducing agent as used. However, this is accompanied by an extension of the development time, which makes these processes usable only in certain cases or in connection with additional measures for the technology. Such a measure is z. B. increasing the temperature of photographic material which has been provided with an amount of such a developer sufficient for image formation. Developers treated in this way have in certain cases been called "stabilized"developers; however, they are not stabilized within the meaning of the invention, according to which the spontaneous metal deposition is likewise considerably reduced, but without the development rate being significantly delayed as a result. The first-mentioned type of extension of the service life is hereinafter referred to as "inactivation" and the developers concerned are referred to as "inactivated developers". If, on the other hand, attempts are made, as is often desired, to shorten the development time in purely physical development, e.g. For example, by increasing the temperature, higher by applying concentrations of the reactive components or by increasing the p _H -value, it always comes at the expense of the life of the developer, while the veil opportunities increase significantly, sometimes to such an extent that the selectivity of the Metal deposition on the photographic metal seed image is lost to a substantial extent.

The disadvantages associated with the purely physical development have had the consequence that one in the photographic process based on the photosensitivity of halogen silver the preferred chemical development. But there are cases in which chemical development is not possible and thus a physical development is the only way of enhancing the photographic Metal nucleation because the metal that forms the image is not yet like the chemical Development in the form of an insoluble compound is present at the location of the image. Even in those Cases in which chemical evolution in itself is possible is physical evolution sometimes desired with regard to the quality of the image, e.g. B. in connection with it achievable high resolution.

The invention makes it possible to overcome the disadvantages mentioned and to extend the life of the developer to significantly prolong the spontaneous loss of metal and the consequent pollution and to combat unwanted fogging and thus also the waste of chemical To keep substances within reasonable limits without having these beneficial technical effects be accompanied by significant inactivation, d. H.

without an undesirable drop in speed, with which the photognphic metal nucleation grows occurs. It's mi: help of the procedure According to the invention, it is even possible to strengthen the photographic nucleus image was previously associated with an inadmissibly strong veil to carry out in this way, leave the result fully meets the requirements of praxii.

The method according to the invention, in which a photographic material is used, the one Contains photosensitive compound which is converted into a light reaction product by exposure to light, which can either be physically developed as such or physically developed in a secondary reaction Forming windable metal nuclei consists in the fact that a purely physical developer is used one or more suitable ionic surface-active substances as development stabilizers are added so that its service life is extended by at least half. In practice During the process it even happens that the life of a stabilized developer is up to 10000 times is as long as that of the corresponding non-stabilized developer (see Example X).

The method according to the invention is based on the different behavior of the development stabilizers in physical development, if on the one hand it is a question of the spontaneously formed metal nuclei in the developing liquid nd, on the other hand, around the metal seed in the photographic material acts. Such a selectivity is, of course, required for the deadening stabilizers to work well essential. It is extremely surprising that the ionic surface-active substances mentioned The growth of spontaneously formed glues can, under certain circumstances, be significantly delayed without that Enhancing the photographic metal nucleation in the layer in a manner which is practical matters.

The procedure after the birth can thus be carried out with all photographic materials in which there is direct exposure to light or a physically developable metal nucleation can be formed indirectly. This includes above all those photographic materials which form a light-sensitive compound

hold whose light reaction product is already a physically developable photographic Represents metal nucleation, e.g. B. the materials that contain halogen silver as a photosensitive compound. This also includes all photographic materials that contain a light-sensitive compound contain, the light reaction product of which is not physically developable as such, but in a secondary reaction converted into a physically developable photographic metal seed image can be. This secondary reaction exists when the light reaction product is a metal compound, in the triggering of metal nuclei from this metal compound, as it is, for. B. in the photographic process is the case in which the photosensitivity of the so-called Eder solution, as described in J. Plotnikow, "Allgemeine Photochemie", 2nd edition, 1936, pp. 640 to 644, use is made and the light reaction product consists of mercurochloride. There are also many photosensitive compounds known whose light reaction product in a secondary reaction in the presence of moisture with mercury ions or with silver ions with the formation of physically developable mercury or Silver germs can react. Such photosensitive compounds as aromatic diazonium compounds, Diazosulfonates, and diazocyanides, and inorganic complex compounds, are used in has been used in a wide variety of methods for producing photographic images.

Surfactants, d. H. Substances that are adsorbed at the interface between two phases are in usually organic compounds with amphipathic properties; their molecule or ion contains one or more hydrophilic and one or more hydrophobic groups which are directly or via z. B. an ester, ether or amide group are linked together. The hydrophobic groups are e.g. B. aliphatic Carbon chains with 8 to 18 carbon atoms with a very low affinity for water in the In contrast to the hydrophilic groups, which have a great affinity for water; one speaks of the latter hence sometimes from solubilizing or polar groups. This can e.g. B. sulfonate or Be pyridinium groups.

The surface-active substances can be chemically divided into two classes:

a) The ionic surface-active substances whose hydrophilic group carries the charge and which therefore occur in the form of an anion, a cation or a "zwitterion". One speaks then from anionic, cationic or amphoteric surfactants.

b) The non-ionic surfactants, the hydrophilic group of which is non-ionizable.

When the invention came about it was show that a favorable technical effect in the sense already described only when using more surface active. Substances of the first mentioned category can be achieved. The non-ionic surface-active Substances are therefore useless as development stabilizers. The useful development stabilizers essentially belong to the classes the cation-active and the amphoteric micelle-forming and to the class of cation-active macromolecular surface-active substances.

Chemical developers also sometimes use certain surface-active substances, z. B. surface-active quaternary ammonium compounds. These can be the development various types of photographic emulsions in developers of a particular composition accelerate significantly. This effect already occurs when you put the exposed material in front of the Development during a short time z. B. in a 0.2% solution of laurylpyridinium p-toluenesulfonate bathes. The problem for which the invention in physical development a

ίο creates a solution lies in chemical development but not before, and the effect mentioned is therefore of an entirely different kind.

As noted, the composition of physical developers can vary widely; they can have an acidic, neutral or alkaline reaction, and they can contain various noble metal compounds, photographic reducing agents of various kinds and a variety of auxiliaries. It is therefore obvious that the choice of ionic surface-active compounds with which the developer is to be stabilized cannot be arbitrary. There are e.g. B. ionic surface-active compounds which in some way form a precipitate with one of the constituents of the physical developer so that they are not useful. One reason for a less good efficacy may be the developer in question, the small dissociation of the surfactant at the _pH value.

The following sample can be used to determine whether a certain ionic surface-active substance used therein as a stabilizer under the conditions prevailing in a physical developer is useful.

With the help of a sensitometer wedge, similar photographic metal nuclei are displayed on two Sheets of one of the above photographic materials prepared. One develops in covered Development trays one of these foils in a developer, in which the surface active to be tested is Substance is located (A) and the other in the corresponding developer, from which this surface-active Substance is omitted (B). Develop the two foils for as long as necessary is to achieve a predominantly neutral gray wedge copy in developer B. If the service life of developer B is so short that it will develop into a single neutral gray copy not allowed, development is terminated when the developer has been worked out. After completion The development of the first two slides is brought about in certain time intervals, the size of which is natural can be changed according to the life of the developer, a few more new nucleation films similar to the first in the two developers. This will approximate the life of the both developers, d. H. the time lapse between the time the two developers put together and the times at which their developmental capacity is practically completely exhausted, established. This sample has at most a semi-quantitative character because of the spontaneous nucleation is naturally not exactly reproducible in non-stabilized developers. To incorrect Avoiding conclusions that might result from the fluctuations mentioned is considered to be Criterion of effectiveness that the life of developer A compared to that of developer B must be extended by at least half.

Care must be taken with this sample.

that the total amount of image metal required for image construction in all in one and the same Developer bath developed wedge copies is consumed not more than 10% of the original potential Metal supply of this bath is.

It is not possible to limit the effective concentration range of the developer stabilizers to specify. Most of the commercially available surfactants are technical products, which usually consist of a mixture of homologues with the same hydrophilic group; they are therefore not clearly defined chemically. These technical products are, moreover, as a rule can be used very well without further purification, provided they are not undesirable in the physical developer Reactions, e.g. B. Precipitation, enter. When the invention came about it was however, when starting out from pure, well-defined compounds, the number of carbon atoms of the hydrophobic group has an influence on the lower limit of effectiveness. So was z. B. for a certain physical developer found that this limit for octylamine acetate at one concentration of about 0.1 mol / l, for decylamine acetate at a concentration of 0.03 mol / l and at Dodecylamine acetate is at a concentration of 0.003 mol / l. This speaks in favor of the view that the .Stabilisierung something with micelle formation in the solution by the ions of the surface-active Substance is related, because the micelle-forming surface-active substances occur above a certain concentration, the so-called critical micelle concentration, micelles. In the Literature has used the abbreviation »c. m. c. «naturalized. These micelles exist from groupings with colloidal dimensions, their hydrophobic molecular parts in certain Way are directed, among other things as a result of an orientation of the hydrophilic parts. Another one The argument for this view is the fact that the lower limit of effectiveness of these developer stabilizers Can be influenced to some extent in the same way by using neutral electrolysis in the developer is like the c. m. c. Incidentally, the situation is again not such that the lower limit of effectiveness with the c. m. c. coincides exactly in this solution. It is more likely that the »Micelle formation« on and around the spontaneous metal nuclei is responsible for the stabilizing effect is. So

The stabilizing effect decreases as the concentration of the surface-active substance increases in certain cases, then peaks and finally disappears completely. With the latter is then often accompanied by flocculation of the surface-active substance; in this case the Efficacy often decreases in magnitude when the flocculated surfactant by means of another ionic surface-active substance of the same charge type or by means of a nonionic surfactant is made soluble. In other cases, however, it could not Decrease in effectiveness noted with increasing surfactant concentration will. It is not yet clear how all of these appearances are to be interpreted. On the basis of the previously described photographic sample it is possible in all cases to find the most effective one Determine the concentration of the surfactant.

When the invention came about, microelectrophoretic measurements on germinating Physical developers reveal that the developer stabilizers reduce the electrophoretic charge affect the spontaneously forming metal nuclei. Without the presence of stabilizers results that these germs are more or less clearly negatively or positively charged, while also cases occur in which germs with the two signs of charge are found in one and the same developer will. So is z. B. in a smren metol-citric acid-silver nitrate developer the electrophoretic charge of the spontaneous silver nuclei is clearly negative, but in a correspondingly acidic one ρ - phenylenediamine - citric acid - silver; nitrate - developer predominantly positive. In the same alkaline developers where sodium sulfide is used as a complexing agent acts, the charge is negative in the two cases mentioned. De charge of Mercury nuclei formed spontaneously in a hydroquinone - nitric acid - menkuronitrate developer but again clearly positive.

The above-mentioned influence on the charge of the spontaneously formed metal nuclei by the developer stabilizers consists in a strong positive or negative charge and charge reversal, depending on the cation-active or anion-active stabilizer can be used and depending on the spontaneously generated germs have a charge in the corresponding non-stabilized developer that is equal to or opposite to that the effective surfactant ion is. Conversely, there is a clear stabilizing effect is present if it is such an influence on the electrophoretic behavior of late titanium formed Germs in physical developers act through ionic surface-active substances.

It goes without saying that influencing the charge of the germs, with which, as already '' was noted, probably a micelle formation by the surface-active ions around the metal nuclei goes hand in hand, for the growth of these germs must have consequences. A strong positive charge the germ will inhibit an approach of positive metal ions, while a strong negative charge the transfer of electrons to the nuclei and the approach of negative complex metal ions can prevent. In certain "all" one can therefore use a surface-active ion of the one, in other cases with a solcbn of the other type of charge, but often with ions of both types, bring about a stabilizing effect of a physical developer. The one described above However, a photographic sample always gives an answer to the question of whether a certain stabilizer is in a specific developer is effective

Nevertheless, it remains surprising that the photographic metal seed image does not work in the same way how the spontaneously formed germ is influenced, in other words that no appreciable decrease the speed of development occurs. Obviously the situation is that in the photographic Material no micele formation occurs and micelles formed outside of this material also cannot enter into it.

In the above-mentioned mikrolektrophoreti examination it is the rule that if the developer stabilizer is chosen so that the charge of the surface-active ion is opposite for electrophoretic leaching of the germs, which spontaneously in the corresponding] physical development

winder are formed, from which the stabilizer is omitted, and if then the stabilizer in an amount is dosed, which is able to generate spontaneous metal nuclei, which unequivocally determines the charge of the surfactant ion possess effective stabilization of the physical developer is secured, provided that the stabilizer does not react with one of the components of the developer, z. B. by precipitation, becomes ineffective.

When using physical developers containing a soluble silver compound, in a non-stabilized developer often spontaneously formed silver nuclei, the predominantly negative Have charge. According to the rule mentioned above, it is therefore possible to use a suitable cationic surface-active Provide a good stabilizing effect on the substance. But with these substances an effect, albeit usually somewhat less, can also be achieved when in the non-stabilized Solution will spontaneously form silver nuclei with a predominantly positive charge.

Anion-active and amphoteric polymer, macromolecular surface-active substances have in the Usually an insignificant effect as a developer stabilizer; on the other hand, the cation-active polymers are surfactants, especially when using a physical developer with a soluble silver compound, extremely useful.

If an acidic silver developer is used, a particularly favorable one is achieved technical effect in terms of stabilization with the help of compounds from the following classes of cationic substances:

a) Salts of primary alkylamines whose hydrophobic alkyl radical has at least 8 carbon atoms possesses, or mixtures of these compounds;

b) Compounds whose basic, hydrophilic, nitrogen-containing group indirectly via a Amide group is linked to the hydrophobic group;

c) Compounds whose basic, hydrophilic, nitrogen-containing group is part of a Forms morpholine ring system;

d) Compounds whose basic, hydrophilic, nitrogen-containing group is part of a heterocyclic Five-membered rings.

If acidic silver developers are used, alkylarylsulfonates derived from diphenyl derived, excellent stabilizing properties.

When using alkaline reacting silver developers have compounds from the following Classes of cation-active substances have a particularly favorable stabilizing effect:

a) Compounds whose basic, hydrophilic, nitrogen-containing group is part of a pyridine ring system forms;

b) Salts of primary alkylamines whose hydrophobic alkyl radical has at least 8 carbon atoms possesses, or mixtures of these compounds;

c) Compounds, their basic, hydrophilic, nitrogen-containing group via an ether bridge is linked to the hydrophobic group.

In the case of the last-mentioned type of silver developers, compounds of the following can also be used Use classes of anion-active substances as developer stabilizers:

a) salts of half-esters from aliphatic alcohols and sulfuric acid;

b) alkylarylsulfonates.

The already known method for coloring physical development with the help of developers, which contain a soluble silver compound, wherein

ίο a dye image with a silver image in places is achieved, gives the same favorable results when using stabilizers according to the invention. When selecting the surface-active substance, the acidic or alkaline reaction of the relevant developer must be taken into account.

In physical developers containing a soluble mercury compound, the use results anion-active stabilizers usually give the best results. But if these developers react alkaline, one can also with cation-active compounds a favorable stabilizing effect bring about, in particular with substances that contain a basic, hydrophilic, nitrogen Have a group which forms part of a pyridine ring system.

A very special stabilizing effect can be achieved in physical developers that Contain soluble silver or mercury compounds and which react acidic when used as a reducing agent Hydroquinone or a derivative thereof and, as a stabilizer, an alkylarylsulfonate derived from diphenyl used.

Physical gold developers can best be found with the help of the same ones derived from diphenyl Stabilize alkyl aryl sulfonates.

As mentioned earlier, a surfactant can sometimes have a considerably smaller stabilizing effect than expected because they are among those prevalent in the physical developer Conditions is flocculated or has too low a solubility. In this case it can the effectiveness of the substance can be increased considerably by solubilization. This can be done with the help of another ionic surface-active substance of the same charge type or with the aid of a non-ionic Surfactant done.

From the German patent specification 810 109 a method for the production of existing metal is already Images in photographic material through the purely physical development of photographic metal nuclei known, in which the photographic material in the form of a stack of sheets in one possibly inactivated physical developer developed, which is no more than about three times the Contains a sufficient amount of metal salt for image build-up. In that according to the invention Stabilizers used in the developers give much nicer results, a lesser one Haze and less contamination of the leaves by finely distributed loosely deposited on them Metal.

In connection with measures already known from German patent specification 867 053 which the pure physical development is applied in a continuous process imparts the invention gives the developer properties that make him even more attractive for practical use do.

You can carry out the development process so that the developing liquid from two

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separate, inherently stable stock solutions is continuously fed. The invention is included successfully applicable by adding a development stabilizer to at least one of these Solutions so that better results are achieved and work is more economical.

The invention makes it possible if you are in a certain stabilized and optionally Inactivated amount of developing liquid several times in succession a certain amount of photographic Material physically developed so that this fluid can be regenerated as needed by the addition of a metal salt or an aqueous solution optionally provided with a stabilizer same. The developer can naturally also be regenerated continuously.

The continuous process known from German patent specification 809279, in which the photographic material an inactivated amount of developer which is at least sufficient for image formation can be absorbed and the development can be carried out essentially outside of this supply through Application of the invention can be considerably improved, since with the help of stabilizers it is possible to compose stock solutions which have a much longer shelf life are than the corresponding, non-stabilized solutions and still have an appropriate development effect exhibit.

The invention is explained in more detail below on the basis of a number of exemplary embodiments.

Examples

The formulas of the surface-active substances mentioned in the examples are at the end of the table given in the description.

A surface saponified cellulose acetate film was photosensitized by 2 minutes long soaking with a 0.15 mol o-methoxy-benzenediazosulfonic acid Sodium and 0.1 mole cadmium lactate per liter containing aqueous solution and subsequent scraping and drying. A piece of this film was made using a mercury lamp exposed behind a sensitometer wedge and then with a 0.005 mol of mercuronitrate and 0.01 mol of nitric acid Treated per liter containing aqueous solution, whereby a mercury nucleation formed became (the so-called »germ film«). After nucleation, the film was soaked in distilled water flushed. A strip of the germ film was washed for 10 minutes with a fresh solution of 0.5 g Metol, Physically developed 2 g citric acid and 0.2 g silver nitrate in 100 g distilled water. It it was found that the silver nuclei which formed spontaneously in this solution had a negative electrophoretic effect Have charge. Another strip of the same nucleation film was observed during the same Duration developed in a fresh solution, which in addition to the mentioned ingredients per liter still Contained 0.02 g of the cationic substance "Sapamin KW"; this is the methyl sulfate of monostearylamido-ethylenetrimethylamine (Formula I). It was found electrophoretically that the spontaneously forming nuclei in this solution were very clear were positively charged. At certain intervals, which in this case were about 30 minutes new strips of the nucleation film were introduced into the two developing solutions and held in them for 10 minutes long developed. This continued until the evolving power of the two solutions came in handy was completely exhausted, taking care that no more than about 10% of the total at the beginning of the sample as silver salt in the unwinders for the image build-up was used. In the case of the stabilized developer solution, the ineffectiveness occurred after a time which was three times as long (the "stabilizing factor") than that in which the developing solution was without stabilizer became ineffective. A development delay could occur with this and the following Examples of stabilized physical developers - unless expressly stated otherwise - at all cannot be determined.

Instead of the photosensitive material mentioned, this and the corresponding Examples below also use similar materials that have been regenerated by soaking a Cellulose film or a superficially saponified cellulose ester film with solutions of other aromatic substances Diazosulfonates, such as. B. p-methoxy or p-ethoxy-benzenediazosulfonic acid sodium, chloro-2-methyl-4-benzenediazosulfonic acid Sodium-1 and dimethoxy-3,4-benzenediazosulfonic acid sodium-1, or with solutions of other light-sensitive compounds were obtained from which one or more of the following molecules or Ions are split off:

CN-; CNS-; NO ₂ -; SO ₃ =; SO ₂ ; S ₂ O ₃ =; NH ₃ ; Pyridine; Thiourea or its derivatives.

II

A portion of a nucleation film produced in the manner described in Example I was left for 5 minutes long in a freshly prepared, 0.036 mole hydroquinone, 0.1 mole nitric acid and 0.005 mole mercuronitrate physically developed per liter containing aqueous solution. On electrophotographic Ways it was found that the mercury nuclei which form spontaneously in this solution are positively charged was. Another piece of the same foil was freshly prepared in one for just as long Solution developed which also contains 0.2 percent by weight of the anion-active substance »Aresklene-400« (Formula II), that is dibutyl-o-phenylphenol sodium disulfonate, contained. The spontaneous germs in this solution were clearly negatively charged. Part of a of the first similar nucleation film, which 2 hours after the preparation of the developing solution without surfactant was introduced therein, was practically no longer reinforced. With the die On the other hand, developers containing surface-active substance were still able to use strips of such nucleation films to neutral black in 50-hour-old solutions with a development time of 5 minutes Images are amplified.

III

Superficially saponified cellulose acetate film was made photosensitive by holding for 2 minutes Soak in a 2 percent by weight solution of 2.7 sodium anthraquinone disulfonic acid and then Skimming and drying. After

The silver nuclei were formed by treating the films with an aqueous solution containing 0.01 mol of silver nitrate and 0.2 mol of an acetic acid / sodium acetate buffer mixture (Ph ⁼ 6) per liter of 6 g of exposure of films of this material using a mercury lamp. After this nucleation

the slides were rinsed in distilled water for 10 seconds.

The physical developers used were:

a) An aqueous solution containing 0.027 moles of p-phenylenediamine, Contained 0.028 moles of silver nitrate and 0.95 moles of anhydrous sodium sulfite per liter, and

b) such a solution that also contains 0.02 percent by weight of "Fixanol-C" (formula III), that is cetylpyridinium halide, contained.

The development time was always 30 minutes.

A microelectrophoretic test showed that the charge formed spontaneously in solution a Silver nuclei was negative, while the charge of the spontaneous nuclei in solution b was clearly positive was. The life of developer b was 50 times that of developer a.

Instead of the above-mentioned photosensitive material, this and the corresponding The following examples also use similar materials obtained by soaking at least superficially made hydrophilic films with solutions of other photosensitive compounds goods whose light reaction product is able to deposit metallic silver from solutions of silver salts, such as B. various known naphthoquinone and anthrachmone compounds and certain known thiazine, azine and oxazine dyes.

IV

Surface-saponified cellulose triacetate film was made photosensitive by holding for 2 minutes Soaking in an aqueous solution containing 0.4 mol of hydroxy -1 - diazo - 2 - methyl - 6 - benzenesulfonic acid - 4, Contained 0.05 mol of mercuron nitrate and 0.1 mol of nitric acid per liter. After drying and exposure behind a sensitometer wedge by means of a mercury lamp, the film was for a short time in rinsed with distilled water, creating a mercury nucleation. Parts of this way The resulting nucleation film was physically in the freshly prepared solutions below for 10 minutes developed:

a) 0.5 g Metol, 2 g citric acid and 0.2 g silver nitrate per 100 g distilled water;

b) solution a + 0.02 percent by weight "amine-220" nitrate (formula V); this is hydroxyethyl-1-heptadecenyl-2-imidazolinium nitrate; ^ ₀

c) solution a + 0.02 percent by weight "amine-0" acetate (formula IV); this is just like that Amine-220, a compound whose basic, hydrophilic, nitrogen-containing group has a Forms part of an imidazole ring system;

d) Solution a + 0.02 percent by weight »SapaminA« (Formula VI); this is a compound whose basic, hydrophilic, nitrogen-containing group is linked to the hydrophobic group via an amide group;

e) solution a + 0.04 percent by weight of the acetate of "Ethoduomen T / 13" (Formula VII); This is a ditertiary diamine;

f) solution a + 0.2 percent by weight "Desogen" (formula VIII); this is a quaternary ammonium compound.

When the sample was repeated in the same developing solutions, it was found that solutions b to f have an IV2 to 3 times longer service life than that Had solution a.

Instead of the above-mentioned sensitizing solution, you can also use a solution that varies 100 g water 3 g hydroxy-l-diazonium-2-naphthalenesulfonic acid-4, Contains 2 g citric acid and 4 g silver nitrate. With germination films of this material will be achieved very similar results.

A surface saponified cellulose triacetate sheet was made photosensitive by holding for 2 minutes Soaking in an aqueous solution containing 0.07 mol of sodium p-methoxy-benzenediazosulfonate per liter and 0.07 moles of cadmium lactate, followed by drying. After a sensitometer exposure a mercury lamp was used to treat with an aqueous solution for 2 seconds, which contained 0.005 mol of mercuron nitrate and 0.01 mol of nitric acid per liter, whereby the mercury nucleation was formed. This was followed by rinsing in distilled water for 10 seconds.

Part of the nucleation film obtained in this way was placed in a freshly prepared, 2 percent by weight pyrogallol, 2 percent by weight citric acid and 0.2 percent by weight silver nitrate containing aqueous solution physically developed. Another part of the same germ film was developed at the same time and for just as long in a solution prepared in the same way, the also 0.2 percent by weight of the macromolecular, cation-active ones quaternized with methyl sulfate Substance polyvinyl imidazole (formula IX) contained.

With further strips of the nucleation films described in paragraph 1 of this example, the described Development samples repeated at 15 minute intervals until the development force of the Development solutions was practically exhausted. It was found that the stabilized with polyvinylimidazole Developer had a life 3 times longer than the unstabilized developer.

When using developing liquids that contain 0.5 percent by weight Metol instead of pyrogallol or 0.2 percent by weight Ν, Ν-dimethyl-p-phenylenediamine-4-nitrate included, but otherwise composed in the same way as indicated above are, very similar extensions of the lifespan of the developers in question result from the mentioned polymeric surfactant.

VI

A strip of the nucleation film obtained in the manner described in Example V was used for 5 minutes long physically developed in an aqueous solution containing 0.05 mol of ferrous sulfate, 0.005 mol Ferric nitrate, 0.14 moles of citric acid and 0.006 moles of silver nitrate. Three other strips of the same The nucleation films were simultaneously and for the same length of time in correspondingly composed solutions which also contained 0.02 percent by weight of

a) "Armacl2D" (Formula X);

b) "Aerosol C 61" (American Cyanamid Company, New York [USA]), an ethanolated alkyl guanidine compound;

c) "Deodorant G 271" (formula XI), a compound whose basic, hydrophilic, nitrogen-containing Group forms part of a morpholine ring system;

d) the nitrate of "amine-S" (formula V), a compound whose basic, hydrophilic, nitrogen containing group forms part of an imidazole ring system.

The life of each of the developing solutions was determined in the manner set forth in the description of the invention. It turned out that as a result of the addition of the four mentioned cationic substances stabilization with one factor between about 2 and 15 occurred.

When working in an analogous manner with developing solutions containing 0.02 percent by weight of phenyl-1-pyrazolidone-3 ("Phenidon"), 2 percent by weight citric acid and 0.02 percent by weight silver nitrate contained, one of the four mentioned cation-active substances was stabilized with an intermediate factor lying around 2 and 10 brought about.

VII

20th

The stabilizing effect of the cation-active substances (always used in concentrations of 0.02 percent by weight) "Sapamin KW" (formula I; see also Example I) and "Deodorant G271" (formula XI; see also Example VI) was ₂ solutions of the following compositions tested:

a) 2 percent by weight hydroquinone, 2 percent by weight citric acid and 0.2 percent by weight Silver nitrate (development time: 15 minutes);

b) 2 percent by weight pyrogallol, 2 percent by weight citric acid and 0.2 percent by weight silver nitrate (Development time: 5 minutes);

c) 2 percent by weight catechol, 0.5 percent by weight citric acid and 0.2 percent by weight Silver nitrate (development time: 20 minutes);

d) 0.25 percent by weight o-aminophenol, 2 percent by weight Citric acid and 0.2 percent by weight silver nitrate (development time: 15 minutes);

e) 0.125 percent by weight p-aminophenol, 1 percent by weight Citric acid and 0.05 percent by weight silver nitrate (development time: 10 minutes) ;

f) 0.06 percent by weight of N-p-hydroxyphenyl-glycine (»Kodurol«), 2 percent by weight citric acid and 0.05 percent by weight silver nitrate (development time: 7 minutes);

g) 0.21 percent by weight Ν, Ν-diethyl-p-phenylenediamine nitrate, 2 percent by weight citric acid and 0.2 percent by weight silver nitrate (development time: 7 minutes).

Seed film made in the manner described in Example I were used. The lifespan of the stabilized or non-stabilized developers was limited to that in the description specified way determined. The determined factor of the extension of the service life was IV2 to 3.

VIII

The stabilizing effect of the cation-active substances:

a) "Alamac26D" is a mixture of oleyl, Palmityl and stearylamine acetate, and

b) "Deodorant G 271" (Formula XI), used in concentrations of 0.02 percent by weight,

was in a physical developing liquid

35

40

^4S

55

60 tested, which contained 0.25 g ascorbic acid, 2 g citric acid and 0.06 g silver nitrate in each 100 g of water. In 10 minutes, germ film that z. B. were prepared in the manner described in Example I, developed into practically neutral gray images.

The cation-active substance a extended the life of this developer by a factor of 6 and the Substance b by a factor of 2.

IX

Filter paper was sensitized, exposed to light, and a mercury seed image was then placed on the im Example I formed in the manner described.

A strip with the seed image was physically developed for 10 minutes in a freshly prepared aqueous solution containing 0.1 percent by weight Metol, 0.42 percent by weight citric acid and 0.05 percent by weight Contained silver nitrate. Other strips with similar germ patterns were in for just as long developed in the same way composite solutions, which also add 0.02 percent by weight "Sapamin KW" (Formula I) and "Deodorant G251" (Formula XII) contained. With intervals of two and a half hours strips with the first similar nucleation patterns became simultaneously in the stabilized and the unstabilized Development solutions developed. The life of the developer due to the addition of the Stabilizers was lengthened by a factor of 2 to 3.

Instead of nucleation patterns in filter paper, similar results could also be obtained in one-sided sensitized, white, wood-free lithographic paper can be used.

On the photosensitive material and following the nucleation procedure described in Example III The resulting nucleation films were used to test the stabilization of an alkaline physical development solution of the following composition:

0.38 percent by weight »genochrome« (this is the ρ-Ν, Ν-diethylaminoaniline sulfite complex [cf. Werner Schultze: "Farbenphotographie und Farbenfilm", 1953, pp. 49 and 50]), 6.2 percent by weight anhydrous Sodium sulfite and 0.5 weight percent silver nitrate in distilled water. It got the effect the following additives of cationic substances tested:

a) 0.014 percent by weight »FixanolC« (formula III), a compound whose basic, hydrophilic, Nitrogen containing group forms part of a pyridine ring system;

b) 0.014 percent by weight »Armac 12D« (Formula X), a primary dodecylamine acetate;

c) 0.014 percent by weight "Hyamin 10X" (Formula XIII), a compound whose basic, hydrophilic, Nitrogen-containing group indirectly via an ether bridge with the hydrophobic Group is connected.

The test method used was reproduced in detail in the general part of the description. The development time was always 2 minutes.

It was found that the solution containing no surfactants was already after a few minutes had lost their power to develop. When arriving

17 18

The use of substance a was the lifespan of e) the phenyl-1-pyrazolidone-3 developer from co-developer about 1 hour, when using sub-game VI with 0.02 percent by weight of the top punch b about 250 hours, when using the sub-surfactant;

punch c about 5 hours. When using a, _{f) the} o-phenylenediamine developer was

a slight development delay was found. 5 _sa mm composition: 0.2 percent by weight o-phenylene

XI diamine nitrate, 2 percent by weight citric acid,

,,. _TT . ,, j ι · η · ■ ι ν j 0.2 percent by weight of silver nitrate and 0.02 ge

^ ¹ * S ¹ ? ^der f ^C V ^{m B} f ^1S P ^{iel X} ^ applied weight percent Aresklene-400 (development time

Germination foils, using an alkaline y minutes ¹ ) ·

physical developer, which is 0.014 mol io 'per liter

Hydroquinone, 0.95 mol of anhydrous sodium sulfite S) the diethyl - ρ - phenylenediamine developer from

and contained 0.0146 moles of silver nitrate (Development Example VII, g with 0.02 percent by weight of the

time 8 minutes), the stabilizing We surface-active substance;

Additions of 0.014 percent by weight follow _{h) the Ferr0} developer from Example VI, likewise

of surface-active substances tested: 15 _{with 002} percent by weight of surface-active substances

a) cetylpyridinium bromide; Substance;

b) "Armacl2D" (Formula X); The lifespan of this developer was two to four

c) "Aerosol C 61" (see Example VI). ^ach ^ ^a l ^{so 1} ^ as that of the corresponding non-

ao stabilized developer. The development of germinal

The lifespan of the developing solutions with foils in these developers was free of fog,

these fabrics were 3, 100 and 2 times as long as those during development in the non-stabilized ones

Lifetime of the developing liquid without stabilizing developers sometimes with disturbing fogging

sator. went along.

XII ²⁵ XIV

A strip of one prepared according to Example I for the following alkaline physical The nucleation film was left in a fresh developing solution for 7 minutes as the stabilizing compound was used aqueous solution developed, tested the kung of several anionactive substances that lead to the 0.06 percent by weight of N-p-hydroxyphenylglycine 30 classes of salts of sulfuric acid half-esters ali - (»Kodurol«), 2 percent by weight citric acid and phatic alcohols and the alkylarylsulfonates ge-0.05 Containing weight percent silver nitrate. Same-heard:

early three other strips of the same seed - _{a) the alkaline} hydroquinone developer from the

bildfohe also for 7 minutes in the same _g -j -sq. Developing solutions composed in a manner 35

winds, which also contains 0.02 percent by weight ^b ) ^the alkaline p-methylaminophenol sulfate

held by (Metol) developers of the composition:

a) "Areskap-100" (Formula XIV); this is mono-metol ... 0.014 mol / l

sodium butylphenylphenolsulfonic acid; Sodium sulfite anhydrous .... 0.95 mol / l

UN αϊ m / -π-, V _1n a- ■, u *, i ⁴ ° silver nitrate 0.0146 mol / l

b) "Aresket-300" (Formula XV); this is monobutyl development time 8 minutes

sodium diphenylsulfonate;

.__, ",", ". . . ". c) the alkaline ρ-Ν, Ν-diethylamino-aniline sulnt-

c) "Aresklene-400" (Formula II, see also Example II). (»Genochrome«) - developer of the composition

By repeating the above samples:

with strips of new germ "genochrome" similar to the first 0.0157 mol / l

Photo films after the course of 15, 30, 60 and 120 Mi- anhydrous sodium sulfite 0, 95 mol / 1

utes it was found that this anion silver nitrate 0.0295 mol / l

active substances had a stabilizing effect, development time 2 minutes

that of extending the service life by a factor of 4 50

is equivalent to. The following surfactants were used:
XIII

1. 0.014 percent by weight »Lissapol C« (form

The effectiveness as a development stabilizer of mel XVI) in developers a, b and c. Stable

"Aresklene-400" (Formula II) was used for the foliation factor: 4 to 10; low number of acidic physical developers

^CT tested · 2. 0.14 percent by weight »Areskap-100« (For-

". _ _TT mel XIV, see also example XII) in the developer a.

a) the ascorbic acid developer from Example VIII Stabilization factor:> 2 with 0.02 percent by weight of the surfactant

Substance; 3. 0.14 percent by weight »Aresket-300« (Formula XV,

_1S '. . _iTrTT see also example XII)) in the developer a. Stable

b) the o-aminophenol developer from Example VII, d sierun ° "sf aktor ·> 2 · with 0.2 percent by weight of the surfactant

Substance · 4. 0.14 percent by weight »Aresklene-400« (Formula II,

₆ see also example II) in developers a and b;

c) the p-aminophenol developer from ^{Example VIe 5} 0.014 percent by weight of "Aresklene-400" in the 0.2 percent by weight of the surface-active curler c. Stabilization factor: 5 to 20;
Substance; ₅ _ ^ _{014 weight percent} »Nekal BX«, an alkyl

d) the Metol developer from example I with 0.02 aryl sulfonate, in developers a and b. Stable weight percent the surfactant; 70 sizing factor: 3 to 8.

20th

In the latter case, if instead of “Nekal BX” one of the alkylarylsulfonates “Invadin N” or “Perminal BX «was used, there were also very satisfactory stabilizing effects.

XV

With the aid of nucleation films which had been obtained in the manner described in Example III, for an acidic and an alkaline color-forming physical developer are still being examined to what extent the life of these developers is extended by the use of ionic surface-active substances can be.

The compositions and development times of the developers concerned were as follows:

a) 0.2 percent by weight ρ-Ν, Ν-dimethyl-amino-

amiline nitrate,

2 percent by weight citric acid, 0.2 percent by weight silver nitrate and 0.8 percent by weight of a-naphthol (color-forming

Component) in distilled water. Development time: IV2 minutes;

b) The "genochrome" developer from Example X, the 0.11 percent by weight phenyl-1-methyl-3-pyrazolon-5 was added as a color-forming ingredient. Development time: 6 minutes.

In the case of developer a, the following cation-active substances had the stabilizing effect mentioned:

35 0.02 percent by weight “Armac 12 D” (formula X), stabilization factor: 20;

0.02 percent by weight of "SapaminKW" (Formula I), Stabilization factor: 5;

0.02 percent by weight of the nitrate of "Amine-S" (Formula V), stabilization factor: 5;

In developer b, the effects achieved with some cationic and anionic compounds were as follows:

a) acidic hydroquinone developer: see Example II;

b) Acid Metol Developer:

p-methylaminophenol sulfate

(Metol) 0.012 mol / l

Nitric acid 0.1 mol / l

Mercuronitrate 0.005 mol / 1

Development time 5 minutes

c) acidic Ν, Ν-dimethyl-p-phenylenediamine developer:

Ν, Ν-dimethyl-p-phenylene-

diamine nitrate 0.01 mol / l

Lactic acid 0.02 mol / l

Mercuronitrate 0.001 mol / l

Development time 3 minutes

d) alkaline hydroquinone developer:

Hydroquinone 0.03 mol / l

Anhydrous sodium sulfite 0.45 mol / l

Mercury bromide 0.0145 mol / l

Development time 10 minutes

e) alkaline Metol developer: p-methylaminophenol sulfate

(Metol) 0.03 mol / l

Sodium sulfite anhydrous .... 0.45 mol / l

Mercury bromide 0.0145 mol / l

Development time 10 minutes

f) alkaline Ν, Ν-dimethyl-p-phenylenediamine developer:

N, N-dimethyl-p-phenylene-

diamine nitrate 0.004 mol / l

Potassium rhodanide 0.008 mol / l

Borax 0.05 mol / l

Mercury bromide 0.0017 mol / l

Development time 1 1/2 minutes

The table below shows the lifespan extensions of various processing solutions indicated by the addition of the listed anion-active substances.

45

55

0.014 percent by weight "Armac 12 D" (Formula X), stabilization factor: 250;

0.014 percent by weight cetylpyridinium chloride (formula III), where X = Cl), stabilizing 5 <> factor: 250;

0.014 percent by weight »Hyamin 10 X (formula XIII), stabilization factor: 20;

0.014 percent by weight "Lissapol C" (formula XVI), stabilization factor:> 2;

0.014 percent by weight "Aresklene-400" (formula II), stabilization factor:> 2;

0.014 percent by weight "Invadin N" (see Example XIV), stabilization factor:> 2.

XVI

In a similar manner and using the same 6g of seed film as in the previous example for some acidic and alkaline mercury developers tested the stabilizing effect of several anion-active substances. Compositions of developing solutions without stabilizers:

Anion-active substances Conc
tration of
anion-active
substance
in the Ent
winding
solution
Weight
percent Used
Development
■ development
solution “Stabilize
factor « "Lissapol-C" J
(Formula XVI) j
"Aresklene-400"
(Formula II)
"Perminal-BX". 0.02
0.02
0.02
0.2
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02 a
b
f
b
C.
d
e
f
a
b
C.
d
e
f 50
2
5
10
20th
100
6th
4th
250
10
10
40
4th
2

XVII

With regard to the stabilizing effect of cationic substances in alkaline mercury

Some more results are mentioned below. They were achieved with development solutions which, apart from the surface-active substance, were composed as follows:

a) the alkaline hydroquinone developer of Example XVI, d;

b) the alkaline Metol developer from the example XVI, e;

c) the alkaline Ν, Ν-dimethyl-p-phenylenediamine developer:
Ν, Ν-dimethyl-p-phenylene-

diamine 0.025 mol / l

Potassium rhodanide 0.046 mol / l

Borax 0.05 mol / l

Mercury bromide 0.0097 mol / l

Development time 2 minutes

b) acidic pyrogallol developer from Example VII, b;

c) acid catechol developer from Example VII, c.

"Aresklene-400" (Formula II) was used as a stabilizer

Cation-active
substance Conc
tration of
cation-active
substance
in the development
winding
solution
Weight
percent Used
Ent
winding
solution “Stabilize
factor « "Armac 12 D"
(Formula X) 0.02 b 6th Cetylpyridinium
bromide
(Formula III) 0.02 a > 12 where X = Br 0.02 b > 8 "Hyamin 10 X"
(Formula XIII) 0.02 C. 2 "Aerosol C 61"
(Example VI) 0.02 C. 3 "Deodorant
G 271 "
(Formula XI) 0.02 C. 2 Nitrate from
"Amin-S"
(Formula IV) 0.02 a 3 “Quater
nary S «*) 0.02 C. 2

used. developer "Stabilization factor" Concentration of
Aresklene-400
in the developer
to a
a 8th
> 100 0.02
0.2 b
b 6th
> 100 _ις 0.02
0.2 C.
C. 4th
about 100 0.02
0.2

XIX

*) "Quaternary S" is a quaternary imidazolinium chloride, derived from amine-S (formula IV) with a molecular weight of 455 ..

For these tests, a photosensitive material obtained by superficially saponified cellulose acetate film was soaked for 2 minutes in a solution, each 100 g distilled water contained 5 g of mercury chloride, 5 g of ferric ammonium oxalate and 2.5 g of ammonium oxalate.

XVIII

Acid developing solutions of the "hydroquinone" type were used, whereby the alkylarylsulfonates, which derivatives of diphenyls resulted in very special concentration-dependent effects, such as can be seen from a comparison of the results below and those from Example II on the one hand those of Examples XII and XIII on the other hand.

Developer:

a) acidic hydroquinone developer from Example VII, a;

The nucleation films produced in the manner described in Example I were rinsed in distilled water for 1 minute with an aqueous solution containing 0.8 mol / l ammonia treated and rinsed again in distilled water. Then the physical development took place For 8 minutes in solutions each containing 100 g of distilled water:

a) 0.33 g potassium gold chloride,
1.3 g of oxalic acid.

b) like a) with also

0.2 g "Aresklene-400" (Formula II).

The life of developer b) was at least twice as long as that of developer a).

XX

A strip of one on the one described in Example I.

Well-prepared nucleation film became physically in a freshly prepared solution for 10 minutes which contained 0.5 g metol, 2 g citric acid and 0.2 g syllable paritate per 100 g of distilled water. Another strip of the same nucleation film was developed in such a solution, as well still 0.02 percent by weight »Alamac26D« (Example VIII, a) and 0.02 percent by weight »Sapamin KW« (Formula I) included. "Alamac26D" resulted in flocculation when it was solely due to the aforementioned Metol-Citric Acid-Silver Nitrate Developer was added. This cation-active substance was made soluble by the likewise cation-active "Sapamin KW". the The stabilizing effect was expressed by extending the life of the developer by a factor of 40. "Sapamin KW" alone only resulted in an extension by a factor of 3, while »Alamac 26 D« had no effect when flocculated.

XXI

In the following tests, nucleation films were used, which were produced by exposing a specially manufactured for electron microscopy by Gevaert, Antwerp (Belgium) Films "Scientia 14 B 50" were achieved with a silver halide emulsion. According to the physical development The films were in a 5 weight percent sodium thiosulfate and 0.5 weight percent Sodium hydroxide-containing aqueous solution fixed and rinsed on it.

Formula trade name
(registered trademark)

company

"C ₁₈ H ₃₇ C-NC ₂ H ₄ N (CHa) _8" OH

⁺ (SO ₄ CH ₃ ) -

) n - C ₁₆ H ₃₃ )

(C ₄ Ho) ₂

OH

(SO ₃ Na) ₂

(X = Cl or Br)

CH ₃ - (CH ₂ ) ^ -C

y N-CH ₂

^ N-CH,

for amine O: η = 16; Mol. Wt. = for amine S: η = 16; Mol. Wt. =

R is a low molecular weight substituent

, N-CH,

ENT,

N-CH ₂ CH ₂ -CH ₂ OH

[C ₁₇ H ₃₃ CO-NHC ₂ H ₄ N (C ₂ Hs) _2] CH ₃ COOH ·

r xj

, CH ₂ -CH ₂ -CH ₂ -N (CH ₂ -Ch ₂ OH) ₂

XH ₂ -CH ₂ OH sapamin KW

Areskiene 400

Fixanol C

Amine O
Amine S.

Amine 220 nitrate

Sapamin A

Ethoduomeen T 13

Ciba, Basel (Switzerland)

Monsanto Chem. Co., St. Louis (U.S.A.)

unknown

Alrose Chem. Co., Cranston (U.S.A.)

Union Carbide and Carbon Corp., New York (U.S.A.)

Ciba,

Basel, Switzerland)

Armor and Co., Chicago, 111. (U.S.A .;

formula H
CH ₃ - C ₆ H ₄ - C - (CH _{2) 10} - CH ₃
N (CH ₃ ) ₃ (SO ₄ CH ₃ ) - f
(SU ₄ C ₂ H ₅ )
(R = C ₁₆ H ₃₃ , C ₁₈ H ₃₁ , C ₁₈ H ₃₃ , C ₁₈ H ₃₅ , C ₁₈ H ₃₇
or an alkyl radical having 20 to 24 carbon atoms (SO ₄ C ₂ H ₅ ) - er H ₂ O Trade name
(registered trademark) company VIII HH
• · · y ^ . VvXIg Ks "* VvXl2 · · ·
NN
/ \ / \
HC CH HC CH
Il Il Il Il ⁺ Γ CH ₃ CH ₃ CH ₃
III Desogen Geigy,
Basel, Switzerland) IX ! I Il Il Il
ΤΤΓ Ν ΤΤΓ N II
(CH ₃ J ₃ C - CH ₂ - C - C ₆ H ₃ -
CH ₃ Polyvinylimidazole Baden aniline and soda factories,
Ludwigshafen (Germany) 90% [C ₁₂ H ₂₅ - NH ₂ ] CH ₃ COOH
9% [C ₁₄ H ₂₉ -NH ₂ ] CH ₃ COOH
1% [C ₁₈ H ₃₇ - NH ₂ ] CH ₃ COOH -0- X -CH ₂ - CH ₂ - Ν - CH ₂ - ζ \
CH ₃ Armac 12 D Armor and Co.,
Chicago, IU. (UNITED STATES) XI Deodorant G 271 Atlas Powder Co.,
Wilmington, Del. (UNITED STATES) XII Deodorant G 251 Atlas Powder Co.,
Wilmington, Del. (UNITED STATES) XIII
S. R CH ₂ - CH ₂
C ₂ H ₅ CH ₂ • -CH ₂ Hyamine 10X Röhm and Haas,
Darmstadt (Germany) C ₁₆ H ₃₃ CH ₂ - CH ₂ \ / \
NO
C ₂ H ₅ CH ₂ - CH ₂

formula O <_ C ₄ H ₉ IT + he Trade name
(registered trademark) company o-c OH
SO ₃ Na XIV CH ₃ (CH ₂ ) ₇ -C =
H
or
CH ₃ (CH ₂ ) ₇ - CH V ₁ (C ₄ H,
/ [SO ₃ Na R is a low molecular weight substituent; η = 16 Areskap 100 Monsanto Chem. Co.,
St. Louis (USA) XV H
₂ -CH- (CH ₂ ) ₇ -CH ₂ OH -CH ₂ ) _n -OH
R is an alkylated phenol radical; η stands for any number Aresket 300 Monsanto Chem. Co.,
St. Louis (USA) XVI SO ₃ Na Lissapol C Imp. Chem. Ind.,
London (England) 0 Na ⁺ "O ₃ SL. , -C-OC ₅ H ₁₁ Na + -O ₃ SI ^ ₇ Uc-OC ₅ H ₁₁
Ii
0 XVII Often
R ₁ and R ₂ are alkyl radicals, e.g. B. butyl or amyl substituents Invadin N Ciba,
Basel, Switzerland) XVIII ^R \ ₊ 1
^ N-CH ₂ Perminal BX Imp. Chem. Ind.,
London (England) ^C \
^ 2 ^ ( XIX --H ₂ Quaternary S. Alrose Chem. Co.,
Cranston (USA) CH ₃ - (CH ₂ ) "- XX Lissapol N Imp. Chem. Ind.,
London (England) R- (O-CH ₂ - / '

The Metol Citric Acid Silver Nitrate Developer was tried of the previous example with 0.02 percent by weight »Armac 12 D« (formula X) to stabilize. However, flocculation occurred in the developing liquid. This flocculation left avoid each other by adding 0.02 percent by weight of the 25% solution of "Lissapol-N", which as such had no stabilizing effect. The combination of the two Substances, on the other hand, had a stabilizing effect with a factor of 10.

XXII

A strip of seed film prepared in the manner described in Example I was left for 5 minutes long developed in a freshly prepared aqueous solution containing 0.06 percent by weight of N-p-hydroxyphenylglycine, Contained 2 percent by weight citric acid and 0.1 percent by weight silver nitrate. Two more Strips of the same nucleation film were simultaneously in such fresh solutions, also for 5 minutes developed, which also added 0.098 percent by weight of pure dodecylamine acetate or 0.098 percent by weight neat dodecylamine acetate and 0.087 weight percent neat decylamine acetate. These substances had been purified by converting the free, unpurified amines under reduced pressure into distilled in an apparatus with high separability and then the calculated amount of acetic acid was added to the constant boiling fraction. After 10, 20, 40, 80 and 160 minutes the above-mentioned development tests were repeated in the same solutions as above. In the Solution, which only contained pure dodecylamine acetate as surface-active substance, occurred after 10 to 30 minutes flocculation on. The stabilizing effect in this solution was quite small and not reproducible; namely, it was dependent on the time in which the flocculation essentially subsided had performed. In the solution, which contained both dodecyl and decylamine acetate, after a few Flocculation was still on for hours, and the stabilizing effect factor was greater than 10 during Decylamine, if it is the only surface-active substance in the concentration given above in the developing solution was present, had no noticeable effect on the stabilization.

XXIII

A strip of a seed film prepared in the manner described in Example III was physically developed in the freshly prepared, unstabilized alkaline hydroquinone developing solution of Example XI. Another strip of the same nucleation film was developed in the corresponding stabilized developing solution containing 0.014 percent by weight of the amphoteric compound N-lauryl- (aminosulfo) - /? - aminobutyric acid of the formula CH ₃ -CH (CH ₂ -COOH) -NH ( CH ₂ ) ₁₂ -NH - SO ₃ Na ("Desil"). After every 15 minutes, other strips of the nucleation film were developed in the two developing solutions. The stabilization factor was about 5 under the conditions described.

Claims (18)

Claims 1. A process for the production of photographic images on light-sensitive material which has a Contains photosensitive compound which is converted into a light reaction product by exposure to light which is either physically developable as such or in a secondary reaction Physically developable metal nuclei can form, the metal nucleation through pure physical development is enhanced, characterized in that the physical Development solution one or more ionic surface-active substances suitable for this purpose are added as development stabilizers, so that their service life by at least half is extended. 2. The method according to claim 1, characterized in that the charge of the surface-active Ions of the development stabilizer used opposite to the electrophoretic charge is the metal nuclei that spontaneously formed in the physical developing solution used from which the stabilizer has been omitted, and that this development stabilizer in an unequivocally reversed charge of the germ in question is added. 3. The method according to any one of claims 1 and 2, wherein the physical developing liquid contains a water-soluble silver compound, characterized in that a stabilizer cation-active substance is used. 4. The method according to claim 3, characterized in that that as a stabilizer, a polymeric macromolecular cation-active substance, in particular Polyvinylimidazole is used. 5. The method of claim 3, wherein the physical developing liquid is acidic, characterized in that the stabilizer used belongs to one of the following classes heard of connections: a) Salts of primary alkylamines whose hydrophobic alkyl radical has at least 8 carbon atoms possesses, or mixtures of these compounds; b) Compounds whose basic, hydrophilic, nitrogen-containing group indirectly via an amide group is linked to the hydrophobic group; c) Compounds whose basic, hydrophilic, nitrogen-containing group is part of a Forms morpholine ring system; d) Compounds whose basic, hydrophilic, nitrogen-containing group is part of a five-membered heterocyclic rings. 6. The method of claim 1, wherein the physical development liquid is an in Contains water-soluble silver compound and reacts acidic, characterized in that as Stabilizer an alkyl aryl sulfonate derived from diphenyl is used. 7. The method of claim 3, wherein the physical developing liquid is alkaline reacts, characterized in that the stabilizer used is one of the following Classes of connections include: a) Compounds whose basic, hydrophilic, nitrogen-containing group is part of a Forms pyridine ring system; b) Salts of primary alkylamines whose hydrophobic alkyl radical has at least 8 carbon atoms possesses, or mixtures of these compounds; c) Compounds whose basic, hydrophilic, nitrogen-containing group has a Ether bridge is connected to the hydrophobic group. 8. The method of claim 1, wherein the physical development liquid is an in Contains water-soluble silver compound and has an alkaline reaction, characterized in that the stabilizer used belongs to one of the following classes of anionic substances: Salts of half-esters from aliphatic alcohols and sulfuric acid and alkylarylsulfonates. 9. The method according to any one of claims 3 to 8, characterized in that the used physical developer is a color developer. 10. The method of any one of claims 1 and 2, wherein the physical development liquid is a soluble mercury compound contains, characterized in that an anion-active compound is used as a stabilizer will. 11. The method of claim 1, wherein the physical developing liquid is soluble Contains mercury compound and has an alkaline reaction, characterized in that as a stabilizer a cation-active compound is used which belongs to the class of compounds whose basic, hydrophilic, nitrogen-containing group is part of a pyridine ring system forms. 12. The method according to any one of claims 6 and 10, wherein the physical developing liquid reacts acidically and as a reducing agent Hydroquinone or a derivative thereof, characterized in that a stabilizer alkyl aryl sulfonate derived from diphenyl is added to the physical developing liquid will. 13. The method according to any one of claims 1 and 2, wherein the physical developing liquid contains a soluble gold compound, characterized in that a stabilizer alkyl aryl sulfonate derived from diphenyl is used. 14. The method according to any one of the preceding claims, characterized in that a Insufficiently soluble ionic surface-active substance by means of another ionic substance the same type of charge or is made solvable by means of a non-ionic substance. 15. The method according to any one of the preceding claims, wherein the photographic material in the form of a stack of sheets in an optionally inactivated developing liquid is developed that is no more than about three times that which is sufficient for the image construction Contains amount of metal salt, characterized in that the developing solution contains a stabilizer is added. 16. The method according to any one of claims 1 to 3, wherein thereby continuously developed that the developing liquid is in the form of two separate, inherently stable solutions is fed continuously, characterized in that at least one of these solutions a development stabilizer is added. 17. The method according to any one of claims 1 to 14, characterized in that the photographic material used at least one sufficient for the image build-up with Amount of developing liquid provided with stabilizer and optionally inactivated can be taken from a supply and the development takes place essentially outside of this supply leaves. 18. Physical development fluid for performing the method according to one of the preceding claims, characterized in that it is a developer stabilizer contains ionic stabilizing surfactant. Considered publications:
German patent specification No. 552 434. © 109 580/369 '5.61