DE2363654A1 - IMPROVED PHYSICAL PHOTOGRAPHIC DEVELOPER, CONTAINS A WATER-SOLUBLE SALT OF AN ALKENYLAMINE COMPOUND AS IONIC SURFACE-ACTIVE AGENT, AND USES THIS DEVELOPER - Google Patents

Description

Improved physical photographic developers containing a water-soluble salt of an alkenylamine compound as; ionic surfactant, and use

The present invention "relates to the field of physical photographic developer and uses of these developers.

Processes "in which" physical photographic developers " containing a solution of metal ions and a reducing agent for these metal ions have been used for many Years ago. In these processes, an image pattern is formed from seeds for physical development, for example, by exposing a photographic element containing a photosensitive layer which upon exposure Generates seeds for physical development. The photograph Element that sprouts the image for the physical

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Iisehe development is then carried out with a physical Developers brought into contact in those areas in which the germs for physical development the selective Catalyze the deposition of metal, create a metallic image.

Two types of physical development methods have been commercially successful. The first type is diffusion transfer physical development, which may more accurately be referred to as "physical solution development ^11, " in which a solvent is added to the developer to thereby dissolve and thereby dissolve the silver halide in the unexposed portions of a silver halide printing medium allow the silver ions to be used for imaging on suitable physical development nuclei These nuclei can either be in a special layer on the same sheet as the silver halide layer or on a special transfer sheet, as in the Polaroid In a second physical development process that has had some commercial success, the metal ion solution is applied to the exposed photographic element in a special bath, followed by a bath of reductant applied to the element.

However, there are currently no commercial photographic processes known to make use of a "unitary" physical developer who provides a solution of Contains metal ions and a photographic reducing agent for these metal ions. A significant reason for that the unified physical developer is not a commercial one Success was that of this physical Eat developer solution lacked consistency. Numerous Attempts have been made to address the instability of this physical Developer by adding ionic surfactants, anti-fogging agents and

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the like, to be overcome (see U.S. Patents 3,157,502 and 3,390,998, which are expressly referred to here). Also refer to the publication by Jonker et al. in Photographic Science and Engineering, Volume 13 (1969) * pages 38 to 44, refer to here When expressly referenced, reference is made to a preferred one as "stabilized physical photographic Developer "is discussed, uniform physical developer, which is a solution of ferrous ions, Ferric ions, silver ions, a complexing agent such as citric acid, and an ionic surfactant contains as a stabilizer for the physical developer. Preferably, the developer also contains a nonionic surfactant for solubilizing the ionic surfactant of the developer. By adjusting the concentrations of the various ingredients this physical developer has been achieved while maintaining a relatively stable physical developer relatively high development speeds achieved. Although the stability of the solution several days when the solution may not be needed, however, even this preferred physical developer degrades when it is continues to be used, depending on. of concentration and activity within hours or, at best, within of a few days. This lack of stability in use poses a particularly serious problem in attempting to use an automatic processing plant, since even with the use of a supplementary system of the developer path serious degradation problems must be completely replaced at very frequent intervals. This causes on G-round the increased Developer costs, the labor associated with changing the developer and cleaning the processing equipment and the loss of production caused by the off-time cause serious economic problems.

The invention claimed in IJSSN 258 769 attempts through these prior art problems

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Use of a unified physical developer lesser Activity or speed of development than was thought possible according to the state of the art to be overcome » "Such a developer is of course" more persistent in nature as a developer of greater activity »

The low activity developer ("lower, 4E") can be used because a "physical development activating material" ¹ such as an organic acid that complexes the ferric ion of the developer ₅ is present in the copying medium that the physical developer is actually locally activated at the point where development takes place in the copy medium A preferred physical development activating material is a complexing agent for the ferric ion of the physical developer.

In processes5 such as those relating to the manufacture of printing plates, However, it is often desirable to have a proportionate highly active developers available to help the

ο. large quantities of metal, for example 1 to 14 g / m, so can be deposited as quickly as possible. ”Hence, stabilized physical Entitfickler who, whether they are developers of low activity or high activity, have a inherently greater stability, desirable By the present invention, stabilized, photograph! see physical developers, the one have inherently improved stability and in particular have provided those developers who are suitable for the generation of metal image printing plates »The new physical developers are naturally so stable that a large Scope for variation in the activity of the developer and other photographic properties of the final copy, such as Gamma and cleanliness of the background area exist.

The present invention also provides a developer that has improved stability in use, and in particular

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In particular, a developer is provided who works in automatic processing systems together with a developer supplement system can be used over longer periods of time, such as several days, while achieving a uniform development.

The invention relates to a photographic physical developer, which preferably has an acidic pH, and an aqueous solution of a water-soluble silver salt which can be reduced to silver metal, a photographic iron (II) / iron (III ^ reducing agent for reducing the salt to metal and) contains at least one ionic surfactant for increasing the life of the developer and which is characterized in that at least one ronic surfactant is a water-soluble salt of an alkenylamine compound, which preferably has at least 8 carbon atoms in the alkenyl group. A preferred physical developer contains an additional, another type of ionic surfactant which is preferably a primary alkylamine compound having an alkyl group bonded to the nitrogen atom and at least 8 carbon atoms in the alkyl group, a preferred physical developer is a solc Her developer in which the reducing agent system is a solution of iron (II) ions and iron (III) ions. Preferably, the reducing agent system for reducing the silver ions to silver metal also contains a complex-forming _t . organic acid to bind the iron (III) ions complex. Preferably, a nonionic surfactant is also present in the developer. Improved methods of physical development include contacting a copy medium containing a catalytic seed that selectively catalyzes deposition of silver metal from a physical developer when contacted. aforementioned improved physical developers. In preferred processes, printing plates and photographic transparencies are made.

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A "salt of an alkenylamine" according to the invention dissolves in the aqueous physical developer described herein on. The salt is thus preferably water-soluble and preferably provides the reaction product of an alkenylamine an organic acid such as acetic acid. A "preferred salt is oleyl amino acetate.

The alkenylamine compound of the present invention is an amine which contains at least one alkenyl group which has at least 8 carbon atoms in its hydrocarbon chain. The term “alkenyl group” is intended to encompass hydrocarbon chains which contain one or more carbon double bonds, dhyc = οζ . Alkenylamine compounds useful in the present invention are preferably straight carbon amines such as oleylamine, palmitoleylamine and myristoleylamine.

That. The salt of an alkenyl amine is preferably present in an amount sufficient to extend the life of the developer by at least 50% compared to the life of the same Developer without the alkenylamine compound. If the developer's AE value is greater than about 100, the amine should preferably be present in an amount sufficient to at least extend the life of the developer "10 times the life of the same developer without the alkenylamine compound is extended.

The stabilized physical one according to the invention preferably contains Developer an additional ionic surfactant other than the water-soluble salt of an alkenylamine. Using this preferred physical developer resulted in higher gammas and a cleaner, more haze-free one Background in the finished exposed medium, especially in the production of printing plates, is preserved. Also was found that plating occurred to a lesser extent on the developer container in use. The preferred

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Additional surfactants are those disclosed in US Pat. No. 5,157,502, saturated ionic surfactants Middle. A preferred class of these "surfactants" is the class of primary alkyl amines which attach one to the nitrogen atom bonded alkyl group and at least 8 carbon atoms in the alkyl group. It is particularly preferred the water-soluble salt of a primary alkylamine, which under the trade name Armae 12D is known and a combination

of 90% by weight of C ₁₂ H ₂₅ NH ₂ -CH COOH and 9% by weight.

In addition, the physical developer of the present invention preferably added a material that helps increase the solubility of the ionic surfactant in the physical Developer. A nonionic surfactant is an example of such a material. One preferred class of nonionic surfactants is the class of the ethylene oxide condensate of an aliphatic alcohol, such as those under the trade names Lissapol N or Synthropol N known.

The activity of the developer or its ΔE value can be varied by methods belonging to the prior art, for example by changing the relative proportions of iron (II) ions to iron (III) ions and the like. Usually a Δ Ε value of at least about 100 is preferred. However, a Δ Ε value between about 100 and 400 is preferred for most photographic purposes. However, when a physical development activating material is used in the photographic print medium, it is often desirable that the physical developers used have .AE values less than 100. When a physical development activating material is used in the photographic copy medium, a jd'E value between about 60 and 100 is particularly preferred for the production of printing plates.

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In the physical developers used, this is reducible Metal ion usually silver, albeit the average A person skilled in the art is familiar with the fact that mercury ions and like »5 which can easily be achieved by the iron (II) / Let the iron (XII) reduction system reduce, likewise well working"

A particularly effective, uniform physical developer consists of silver ions5 from iron (II) ions and iron (III) ions as a reducing agent system for this; and preferably a material that preferably has a. Complex with the iron (IH) ions of the developer forms, e.g., "B ₀ is an organic. Acid. The iron (II) ions are of course special reducing agents. However, the ratio of iron (II) ions to iron (II I) ions helps to determine the activity or the ΔE value of the developer.

Organic acids suitable for use in the developer and 'as a. Activator for physical development suitable for incorporation in the light-sensitive layer, are dicarboxylic acids, v? Ie oxalic ₉ apple? Maleic, malonic or succinic acid, and hydroxycarboxylic acids, such as salicylic, tartaric, lactic, almond, glycolic and citric acids. The hydroxacarboxylic acids are particularly preferred as materials that activate physical development for incorporation in the sensitive layer the soluble salts of these acids, such as the alkali and alkaline earth as well as ammonium salts of these acids = The ammonium salts of citric acid, tartaric acid and lactic acid are on. Particularly preferred because of the particularly good results that can be achieved with them. Other complexing agents useful as physical development activators are complexing agents such as amino acids, e.g. B. glycine, amines, e.g. B. ethylenediamine, and ß-diketones, ζ. Β _β acetylacetone.

Because of the particularly desirable black image tones that are achieved, a combination of apple and malon

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Acid for Use In the physical developer of the present invention in an automatic processor for high speed development (about 30.5 meters per minute; 100 feet per minute) of photographic pilms. Also, the physical developer containing these acids, when used in such an automatic apparatus, appears to have improved stability and is less likely to be oxidized by oxygen in the air than when it contains other organic acids. Me Citric acid is the preferred organic acid in the physical developer of the present invention when the developer is used to make printing plates because an exceptionally high gamma is produced.

The physical developer of the present invention preferably has has an acidic pH. Preferably the pH is less than about 6, and most preferably less than about 3

The germs according to the invention for the catalytic or physical Development and preferably a metal such as silver, gold, mercury, platinum or palladium, a metal sulfide, such as silver sulfide, graphite or the like. In a silver halide copying medium the latent silver image forms in the silver shark ogenid grain in the emulsion upon exposure; through physical Development, the latent image is made visible. When a photosensitive material such as a metal oxide e.g. B. Titanium dioxide, zinc oxide or tin oxide, exposed and brought into contact with a solution of a reducible metal ion a visible or invisible, latent metal image is formed, which then by means of a uniform physical Developer can be reinforced, or it is also possible to apply the unified physical developer directly, without first using the metal ion bath.

The picture from catalytic germs can be:

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(i) the image formed upon exposure, e.g. the latent one Silver image in silver halide emulsions or the reversible,

■ latent 'image on a reversibly activatable photoconductor,

such as titanium dioxide;

(2) the irreversible image ₅ which is produced by bringing an exposed medium carrying a photoconductor into contact with a sensitizing metal ion, for example a solution of silver ions, which can lead to an invisible, irreversible image or a visible metal image;

(3) what is the latent ELsen (II) ion image _? which is generated by exposing an iron (III) sal-sensitized medium and then by sensitizing with silver ion solution to form a silver image,

(4) a conductive image or seed image produced by printing or Writing in accordance with the teaching of DT-OS 20 45 081.1 (US-SN 2440, filed January 12, 1970) ';

(5) .an image that is created by adding a metallic Physically adjoining the carrier;

(6) an image formed by diffusion transfer of metal ions according to the teaching of US Pat. No. 3,300,3O6 by means of an imagewise coated photopolymer layer over a seed layer, such as in USSN .697 9 ^ 8 (filed January 15, 1963)

is, is generated;

(7) the nucleation produced by exposing a previously veiled, photosensitive material, such as lead iodide or AspS, is produced, as described in the publication of Malinowski, "Photographic Science and Engineering," Volume 151 No. 3i May-June, to which reference is expressly made here; or

(8) the conventionally developed (mainly "Chemically" developed) image from a silver halide emulsion.

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A preferred photosensitive material contains a photoconductor such as silver halide or a photoconductor which when exposed to activating radiation is reversibly activated and enabled in the exposed areas a to cause a chemical reaction. By nature, the photoconductor is preferably finely divided, preferably a water-permeable one Binder is incorporated and is applied as a very thin, removable layer on the carrier, especially a superficial one roughened carrier, deposited in such a way, that the photoconductor at least partially soaks the roughened area of the carrier. This becomes easy for example accomplished by having a photoconductor, such as silver chloride, comparatively lower in a solvent-binder solution Viseosity deposited and then this mass is applied as a coating on the roughened carrier. You can Let the coating mass dry. Such a carrier with a Photoconductor binder coating preferably has a very high thin coating, which is solvent-permeable, so that a rapid processing in the preferred developer systems is made possible.

It is also understood that a catalytic nucleation is created by applying nuclei for physical development the metallic carrier can be produced. D; Les can be made by writing on the metallic carrier with, for example, a Graphite pencils or preferably by applying a seed layer in a binder coated with a layer which can be made opaque by light, and the following Exposure, in order to make the layer impermeable in exposed areas, take place. Germs can come from any Material that catalyzes the deposition of metal from the physical developer. Many such Substances belong to the state of the art, e.g. B. metal sulfide, finely divided Me tall particles, graphite and the like.

The preferred photosensitive media are those that

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Contain silver halide as a photosensitive material. Such Photosensitive media have been described more than adequately in the literature and are familiar to the person skilled in the art. Particularly preferred silver halide media are low in content Silver halide in the photosensitive layer; Particularly preferred are those that have a stoichiometric Excess of halogen ions, based on the amount of silver ions present in the photosensitive layer.

The so-called low silver thin photosensitive layer is a preferred embodiment of the invention, particularly together with metal substrates for the manufacture of printing plates, electrical components and the like. The silver halide used is that conventionally used in photography; it is produced in a conventional manner, ie by reaction in aqueous systems of soluble silver salts, such as silver nitrate or sulfate, and soluble alkali metal oxides, such as sodium chloride, sodium bromide or sodium iodide or corresponding potassium salts desired particle size in the range from only JO to 50 S units up to conventional particle sizes can be achieved. Preferred methods are those that favor fine particle sizes, usually less than 0.5 microns. For general reasons of expediency, such fine particle sizes are obtained by using systems with a high solids content, preferably with a total solids content of about 5 ° / ° (including the silver halide and binder weight) with a binder that is Ostwald ripening prevented, like polyvinyl alcohol, and by rapidly mixing the solution of soluble alkali halide with the solution of soluble silver salt for convenience usually at about room temperature.

In addition, the binder and catalytic nuclei or photosensitive material layer can be others as desired

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Substances are added in order to achieve special effects in this layer during or after exposure. For example the physical development activating substances described above, sensitizing dyes, thiourea, Tinting agents, mercury (II) salts or the like. Because of their known photographic effects, for example thiourea, so that the formation of black, photographic images is supported, and the sensitizing dyes, thus the spectral response of the photosensitive Layer is changed upon exposure.

The light-sensitive material can be any material, for example, US Pat is here expressly referred to the ¹ s 3380823 or 3623865 "from the" Lit era door, is known. In general, the preferred photoconductor Silver halide or compounds of a metal with a non-metallic element of Group VI of the Periodic Table of the Elements. Preferably these photoconductors are metal oxides or sulfides, such as titanium dioxide, zinc oxide, zinc sulfide, cadmium sulfide and cerium oxide, among others. Preferred oxides are titanium dioxide, zinc oxide, tin oxide and mixtures thereof.

The seeds for physical development or the photosensitive Material and the physical developer activating material in the selected binder are after any the prior art methods, for example by means of rollers, applied to the substrate in the desired thickness. After drying, the photographic media are ready for use. If desired, it can be used to protect the photographic. phischen emulsion a top coat can be applied. Naturally The emulsion may also contain substances commonly used in conjunction with the particular light-sensitive material become, like dye sensitizers, sensitizing Metal salts, e.g. B. silver and copper salts, photographic reducing agents and those materials used in photographic Emulsions are common.

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The photo exposure step performed is the same as it usually with the selected photosensitive material is carried out. Also the photo processing of the exposed Medium is the same as it is normally used.

The substrates for the media of the invention include all commonly used substrates such as paper, plastic and metal substrates. For example Cellulose acetate and polyalkylene terephthalate are used for clear films, while metals such as aluminum and Iron, as well as their alloys for the photographic manufacture of printing plates and printed electrical Components, for example of printed electrical circuits, capacitors and the like. As well as nameplates and Decorative metal plates can be used and are particularly suitable for this. The preferred carriers' for manufacture Printed panels that have been in operation for a long time are "grained" metal supports. Guide anodized aluminum beams to particularly desirable results.

Any desired metallic supports can be used for the preferred metallic supports suitable metallic or practically metallic base can be used, which is sufficiently strong and durable to be satisfactory to serve as a medium of reproduction. The carrier can be in any Ροπή, for example in pollen, Tape, roll, etc. are available. This foil can be made of any suitable metal or alloys of such metals, for example the hydrophilic metals such as chromium, winding, lead, stainless steel, magnesium or aluminum, or the oleophilic metals such as copper or zinc. Aluminum is desirable because of its physical and chemical properties as well as preferred because of its economy. The term "aluminum" is intended as used herein Meaning AltiminiumlegierÜngen, such as aluminum, the small amounts Contains manganese, copper or magnesium. A porous,

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Anodized surface is "special" for the aluminum support preferred. The anodized surface can be sealed by heating. The unlocked surface will however preferred because improved adhesion between the metal image and the aluminum support can be obtained. For printing plates, the. long in. Operation are, an alloy will be like an aluminum of the type 1100 is used., which causes ice formation withstands and has the strength required for such long use.

The preferred metallic support can be of any suitable thickness. However, thicknesses of about 0.1524 mm will be used (.006 inch) to Q.6J5 mm for use as printing plates preferred, and for printing plates that have been in long use, thicknesses of about 0.3048 to 0.381 mm are preferred.

The support and the metal forming the image can be selected so that there is good oleophilic-hydrophilic differentiation results in a lithographic process. Also can through special treatments or by applying the right one Substrate or image-forming metal this method for producing a plate are used in the so-called the aerographic method described in U.S. Patent 3,511,178 is useful.

Granular, metallic carriers, as described in BE-PS 787 828 are particularly preferred for the present invention. This carrier is able to create a bond with a metallic one produced by physical development Enter image and thus form a plate that can be used as a printing plate and preferably as a printing plate for the long-term operation can be used.

The thickness of the layer of catalytic seeds or photosensitive Material "capable of generating such nuclei", the insulating layer or the auxiliary adhesive layer,

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if any, will depend on the nature of the photosensitive material, the nature of the binder, if any, the amount of activating radiation applied, and other similar factors. However, in order to obtain an imaging medium that can be processed rapidly, it is preferred that the layer of physical development seeds or photosensitive material be relatively thin, preferably thinner than about 2 microns, and more preferably thinner than about 1 micron Most preferred are layers that are about 0.01 to about 0.5 microns thick or so thin that a completely coherent coating is unlikely to exist, but the thickness of these layers can vary Metal carrier embodiment, for example, the photosensitive coating or the coating of Eeitsen for physical development, apart from those subregions which are immersed in the roughened surface, can be scraped off. This coating thickness can be varied according to the desired effects. Most preferred, however, is a substrate in which this coating is thinner than A micron, in order to obtain kohäiejite metal images which are adhered to the support by the rapid processing which is most desirable.

In a "preferred embodiment, an internal diffusion transfer plate made by a layer of germs for physical development, such as Garey Lee-Silver, as Coating is applied to a substrate to a dry thickness of less than about 2 microns. This layer is in turn coated with a silver halide layer which is exposed and as disclosed in US Pat. No. 3,615-437, to which is expressly referred to here, can be developed, only that the physical development activating material according to the present invention of the plate is incorporated. Preferably this is done by physical solution development generated image then by means of the invention

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bulk, stabilized, uniform, physical developer instead of the electroplating baths of US Pat. No. 3,615,37 reinforced.

In use, the amount of binder can exceed the amount of catalytic nuclei or photosensitive material wide ranges vary. Preferably the approximate weight ratios of seeds or photosensitive material vary to binders from 1 to 6 to 6 to 1 and even more preferably from 1 to 1 to 1 to 3 "

To radiation sources used in the present invention Any of the conventional radiation means, which are useful for generating the initial latent image, belong together usually find use with the selected photosensitive material. So are actinic light, or x-rays Gamma rays are effective when photoconductors are used. Electron beams and rays of other similar particles can take the place of the usual forms of electromagnetic radiation can be used for imaging. These various activating agents are referred to by the term "activating Radiation ".

It may also be desirable to use the preferred silver halide emulsion, which contains excess halogen ions and which is a stabilized physical developer for development is used to incorporate a sulfur compound as a development initiator. A preferred compound is thiuram, such as tetramethylthiuram disulfide. This physical Development initiator works in such a way that he is goodness the formed metal deposit improved when exposed Silver halide plate is physically developed.

In a "preferred embodiment of the present invention, where it is desired to pass a metal printing plate To make use of a low activity developer,

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it has also proven desirable to have one layer ionic surfactants such as that disclosed in U.S. Patent 3,157,502, e.g. B. Armac 12D (ionic surfactant Kittel) and Synthrapol N (non-ionic surfactant) to add to the photographic element. ' The surface active agents can also be added to the physical development activator layer or the layer of the photosensitive material or the seeds for the physical Development can be added. It has been found that the presence of the ionic surfactant in enhancing metallic images of the photographic element Printing capacity leads by both the quality of the prints and the service life of the printing plate, in particular if the -metallic image of the plate with the unified physical Developing low activity is produced, improves v / ground.

In a preferred embodiment of the present invention, which comprises a photographic, stabilized, physical developer comprising a solution of silver ions, iron (II) ions, iron (III) ions, Armac 12D _? Synthrapol N and oleylamine, it has been found possible to improve the properties of the developer by simply changing the relative concentration of the three surfactants, i.e. of Armac 12D, Synthrapol N and oleylamine *. The Armac 12D tends to suppress background fogging in the final developed image and to increase the photographic gamma of the final print. The oleylamine, on the other hand, tends to produce a low gamma with a longer gray scale but to produce a haze in the background. Also, the oleylamine tends to produce pearlescent 5% points when a halftone image of 5% points is used as Printing plate is developed . Also, as mentioned earlier, the oleylamine gives the stabilized physical developer great stability. The Synthrapol Κ "on the other hand tends to make the ionic amines soluble

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to make, which ensures that the surface-active Agents in larger quantities can be present in the physical developer in order to extend the life of the developer to extend. These three surfactants have the following formulas:

Trade name or. . formula

ordinary urine

(Alamin 11) Oleylamine or Octadec-9-en-i-amine

(Armac 12D or

Alamin 4)

Dodecylamine 90 % C JSL _OC 1S (R _O 'CH ^ COOH

and ■ '

Tetradecylamine 9 % C. ^ I ^ gN ^ · CH ^ COOR

(Lissapol N or Synthropol N)

an ethylene oxide condensate of an aliphatic alcohol

A stabilized physical developer was produced by first adding the following developer solutions were set:

78.4 S. filled up 32.3 ε 80.0 ε 40.0 ε 1 1

_{5 5}

Tartaric acid
Citric acid ^ OH ₂ O. on

Armac 12D (Do decylaminac etat) variable concentration

Synthopol IT same weight concentration

like Armac 12D

H ₂ O made up to 1 1.

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Stabilizing 1min variable concentration

Acetic acid the same weight concentration

like that of the amine

Synthropol ΪΓ the same weight concentration

like that of the amine

H ₂ O made up to 1 1

The stabilized physical developer had the following composition:

. 250 ml of solution I.
50 ml solution II
6 ml JM AgEO ₇ '

Me silver concentrations were determined by titrating with ITodium thiocyanate solution certainly. The following Table I shows the determined silver ion concentration as a function of time the mixing of the developer. The initial concentration of a stable solution is 0.0588 molar. The developers were in Airtight, brown-colored bottles stored at ambient conditions (approx. 22.2 ° C). -

In the absence of any ionic surfactants in the physical developer formulation of Examples Λ to 13, the concentration of silver ions falls in a matter of minutes (a few minutes) to below 0.04-5 g / l '.

The silver ion concentration in a completely stable solution will of course remain constant at the initial value. So is the slower the speed, the more stable the physical developer Concentration drops.

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Table I.

Example of stabilizing surface concentrations (g / l)
active amine

1 ■ 7th Armac w 12D (90% dodecylamine ti 8th It acetate dd 9 Alamin 9% tetradeoylamine dd 10 Il acetate) dd 2 11 I! dd 15 (90% unsaturated 3 12th ti dd primary C.g amine 4th »» (Oleylarain and Lino 5 Il leylamine) 6th Alamin 9% saturated pri mares C o-amine I. '1% saturated pri ro märes G.g-amine • dd dd * l in *
CO 11 (oleylamine) OO
fO dd CD dd **>.
O dd OO
CD O

Time (hours) before the silver ion concentrations drop ^ are on: "" *

O, O5OM '

130

280

510

165

22nd 130 170 22nd 110 165 5 90 165 2 5 ■ 15th

730

300 720 1000 500 1100 1400 800 1500 > 3000 900 > 3000 > 3000 20th > 3000 > 3000 23 70 > 15OO 9 14th

K) CO CD CO CT)

A stabilized physical developer is produced, by first the solutions I and II are set as follows;

₂ * 6R ₂ Q 94.23 g

₅₃₂ O 38.82 g

Citric Acid · H ^ O 96.12 g

H ₂ O made up to 1 1

Stabilizing amine variable concentration

Acetic acid 1g

Synthropol Ή 1.2 g

H ₂ O. filled up to 1 1

The stabilized physical developer has the following composition:

Solution I. 220 ml solution II 40 ml 0.566N AgFO ₃ 70 ml

The initial silver ion concentration is before any Reaction takes place in stabilized physical developers of the above composition 0.120M.

The stability was as recorded in Examples 1-13 Measured manner »The results are summarized in Table II.

In these two examples, a polyester film base was

layer used, die'mit 1.5 g / m of a finely divided titanium dioxide was coated in a binder made of gelatin and polymethyl methacrylate.

The stabilized physical development approach had the the following composition: (ΔΕ = 88)

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²²⁵⁸ '236365A

Solution I.

Pe (KE ₄ ) ₂ (SO ₄ ) ₂ · 6H ₂ O. 128.10 g

Ee (HO ₃ ) ₅ -9H ₂ O 54.24 g

Malic acid 1.6.54 g

Malonic acid 19.60 g

H ₂ O made up to 1 1

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Table II

Example stabilizing surface no. active amine

14 myristoleylamine (impure)

15 palmitoleylamine (impure)

16 oleylamine (impure)

17 Alämin 26D (oleylamine and saturated amine)

18 oleylamine,

19 dodecylamine

20 tetradecylamine

21 hexadecylamine

Concentrations (g / 1) Time (hours) before the silver ίο

ion concentrations are reduced to:
0.1OM. 0.08M

0.79 <1: 168 o, 9O ■ 200 > 336 • 1.0 180 > 336 0.97 1 > 336 1.0, 500 > 500 0.75 40 50 0.80 1 8th . ' 0.90 <1 1.5 Ä

O CO OO IO CO

O OO CO O CO CD CO

Dodecylamine 0.1634 g

Oleylarain 0.2451 g

Acetic acid 0.4086 g

Synthropol F 0.4086 g

AgUO ₅ ■ 13.6 g

H ₂ O - made up to 1 1.

To prepare the developer, solutions I and II are mixed on an equal volume basis. The mixed developer is several honates without changing the silver concentration or activity stable.

The film was exposed on an EGG sensitometer to a step board for 10 "* seconds, contacted with an aqueous solution of 0.05 M AgNO- for 5 seconds, rinsed in HpO for 5 seconds, and after the physical developer 30 described above Developed for seconds at _{25-6 ° G, rinsed in H 2} O for 5 seconds, fixed in a normal silver halide fixer for 5 seconds, _{rinsed in H 2} O for 10 seconds, and in a 60 ° C for 10 seconds The result was an excellent, neutral, gray silver image.

The ELIm from Example 22 was / exposed and at 30.5 m / min. processed on an Itek Floxtffilm printer / processor. A 200 watt mercury vapor lamp was used as the exposure device. The exposed film was then Developed for 1 minute in the stabilized physical developer of Example 22 at 25.6 ° G, for 5 seconds in HpO rinsed in a normal silver halide fixer for 5 seconds fixed, rinsed in HpO for 10 seconds and 10 seconds Long dried in a 60.0 C hot air stream. It the result was a neutral gray image with Dmax = 1.8 and = 1.58.

A batch of this stabilized physical developer was used to process the film from Example 22 in the auto-

409826/08 90

automatic flow film processor for several months used, only silver ions and iron (II) ions were supplemented to the extent necessary to make a relative to maintain constant consumption of these ions in the developer.

The processing of this example with the modification that the oleylamine is omitted from the developer leads to rapid deterioration of the developer in the automatic Processing apparatus within a few hours with continuous use even when silver ions and Iron (II) ions were supplemented.

An anodized sheet of aluminum alloy grained with a brush (Alloy 1100) was coated with a fine-grain AgCl emulsion in polyvinyl alcohol. The emulsion had one mean particle size of 100 S and contained the .physical Development sensitizer tetramethylthiuram disulfide in an amount of 1mg / g AgCl. The plates were on a

Roller coater up to a silver coverage of -? 2

1 χ 10 "g / m and a«

0.03 micron coated.

—Ρ ρ

1 χ 1O ~ g / m and a dry thickness of about

Plates coated in this way were through a negative for 1 1/2 minutes long from a 625 watt quartz iodide source at a distance of 76.2 cm exposed and then J minutes in the below Developer developed:

Fe (NH ₄ ) ₂ (SO ^) ₂ * 6H ₂ O 78.4 g

Ee (KO ₅ ) ₃ • 9H ₂ O 52.3 S

Citric Acid ^ HpO 80.0 g

H ₂ O. filled up to 1 1

Alamin 4 1.6 g

Aliamine 11 0.8 g

Acetic acid 2.4 g

- 26 -

409826/0890

Synthropol N 0.75 g

H ₂ O made up to 1 1.

The stabilized physical developer is made by mixing from: . '

^: 125 ml of solution I.

25 ml solution II (ΔΕ = 127) 6 ml 3M AgWO,

manufactured.

Excellent metallic silver images were obtained showing the full range of halftone dots. In solid Image areas 3ag the image donating silver in an amount of 10 g / m. The plate was rinsed and treated with a varnish similar to that used for refurbishing Diazo plates 2-Hercaptobenzothiazole has been added is used. The plate was then treated with a gum arabic solution, as is conventionally done, and placed on a Brought to 66.04 em Harris Aurelia Press (26 "). There were Received 500,000 sharp, clear impressions. The stabilized physical developer allowed excellent stability its continuous use for several hours in an automatic processing machine with a supplement system that is responsible for maintaining a relatively stable concentration of silver ions and iron (II) ions.

- 27 -

409826/0890

Claims (1)

Claims Stabilized photographic physical developer, containing an aqueous solution of a water-soluble silver salt which is reducible to silver, a photographic one Reducing agent for the reduction of the above-mentioned silver salt to silver containing iron (II) ions and at least one ionic surfactant as a stabilizing agent to extend the life of the developer, at least one of the said ionic surfactants a water-soluble salt of a Alkenylamines having at least 8 carbon atoms in the alkenyl group. 2. Developer according to claim 1, characterized in that the water-soluble silver salt comprises silver nitrate. 5 · Developer according to claim 1, characterized in that the alkenylamine is a primary amine. 4. Developer according to one of claims Λ to 3 », characterized in that the salt of the alkenylamine is present in an amount sufficient to extend the life of the developer by at least 50 % , if it is used with the life of the same developer, which does not contain the salt of alkenylamine, however, compares. 5. Developer according to one of Claims 1 to 4, characterized in that that it additionally contains a primary alkylamine as an additional ionic surfactant, whose alkyl group has at least 8 carbon atoms contains. 6. Developer according to claim 5 »characterized in that he also has a non-ionic surfactant contains. - 28 - 409826/0890 7- developer according to one of claims 1 to 6, characterized in that that the AE value is at least 100 millivolts. 8. Developer according to one of claims 1 to 7i, characterized in that that the developer's Δ E-Vert is less than 100 millivolts. 9 · Developer according to one of claims 1 to 7 »characterized in that that the developer's AE value is between is about 100 and 400 millivolts. 10. developer according to one of claims 1 to 9, characterized in that it has an acidic pH value and
the photographic reducing agent iron (II) - and Iron (III) ions including an organic acid, which binds the iron (III) ions complex contains. 11. The developer according to claim 10, characterized in that the organic acid is at least one of the following
Acids are: citric, veinic, malonic and malic acid. 12. Developer according to one of claims 1 to 11, characterized in that that the alkenylamine is oleylamine. 15 · Developer according to claim 12, characterized in that the ionic surfactant alkylamine ^C i2 ^H 25 ^liH 2 * ^CH 3 ^{C00H and C} i4 ^H 2 ^qNH 2 ' ^CE 7p ^{00E is} 14. Photographic physical development process,
characterized in that a copy medium that
contains a catalytic seed image which is capable of physical evolution on said image
to catalyze selectively, brings into contact with a stabilized physical developer, which has an acidic pH and an aqueous solution of silver ions, - 29 - 40982 6/0890 a photographic iron (II) / iron (III) reduction agent to reduce these silver ions to silver metal and -at least one ionic surfactant as a stabilizing agent to increase the life of the Developer, wherein at least one of the ionic surfactants is a water-soluble salt of a Alkenylamine compound contains. 15 · The method according to claim 14, characterized in that the pH value of the physical developer is less than is about 3. 16. The method according to claim 14, characterized in that the salt of the alkenylamine is present in the physical developer in an amount sufficient to extend the life of the developer by at least 50 % when they are used with the life of the same physical Developer that does not contain the alkenylamine salt mentioned above is compared. 17 · The method according to any one of claims 14 to 16, characterized characterized in that another ionic surfactant is additionally present. 18. The method according to claim 17? characterized in that said additional ionic surfactant is a water-soluble salt of a primary alkylamine compound is. 19 · The method according to claim 18, characterized in that the developer is additionally a non-ionic surface-active Contains funds. 20. The method according to any one of claims 14 to 19 »thereby marked that the Λ Ε value of the developer is greater than 100. - 30 - A 0-9 826/0890 2258 21. The method according to any one of claims 14 to 19 »thereby characterized in that the ΔΕ value is less than 100. 22. The method according to any one of claims 14 to 21, characterized characterized in that the copy medium is a printing plate which consists of a catalytic nucleus, which is able to catalytically deposit silver. 23 · The method according to any one of claims 14 to 21, characterized characterized in that the copy medium is a permeable Is a carrier that consists of a catalytic nucleus that is able to catalytically deposit silver. -31.- 40982 6/0890