DE2128801A1 - Rapid reversal color photographic development process - Google Patents

Description

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DR. E. WIEGAND DIPUiNG. W. NOBODY? 1 ? R ft Γ) DR. M. KÖHLER DIPL-ING. C GERNHARDT Z I ^ O ö U I MONKS * HAMBUKG TELEPHONE, 55 54 7 * 8000 MÖNCHEN 15, TElEOTAMMEiICARPATENT. WALNUT ASSE 10

June 9, 1971

W. 40 537/71 - Ko / b

Fuji Photo Film Co., Ltd., Ashigara-Kamigun, Kanagawa (Japan).

Color photographic.es rapid reversal development process %

The invention is concerned with a rapid reversal development process for obtaining color photographic images with color films or color photographic images Papers within a very short period of time.

The color photographic light-sensitive materials to be treated by the process of the present invention are prepared by coating at least one light-sensitive emulsion layer containing a silver halide emulsion and a coupler on a support. For example, comprise such light- g photosensitive materials farbphotographisehe Single Bchlchtmaterialien which give colored line images and is used to reproduce, color photographic materials for drawings, clie two or three light-sensitive emulsion layers each having it own ^ indlichkeitstereichen a different coupler and different spectral, so.deß »Is obtained in three-color or single-color line images, mandatory materials for scientific recordings, for example for the registration of cscillograms, and light-sensitive materials

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Materials designed for industrial use.

For scientific research, for example Recording of oscillograms, or for photographic recordings in the industrial area used photosensitive materials it is necessary that they produce the images within a short period of time. It is also very cheap if one photographic light-sensitive material for reproducing drawings can be r-ash treated. To the Rapid treatment of such photosensitive materials is known a method in which a positive image is obtained directly by reversal development, and this is far cheaper than the usual method in which a positive image over a negative photosensitive one Material is obtained through two stages of image formation. Therefore, developing a rapid reversal development process yields for color photographic photosensitive materials, great practical advantages and is also not only for industrial Zv / corner, scientific Researches, drawings and educational audiovisual materials favorable but also for general color photographic photosensitive r-Ia.terif-.lien.

However, the commonly used color photographic reversal development process usually requires a treatment time · from 30 minutes to? u 1 hour, even the usual procedure with the shortest treatment Time from the well-known high-temperature repetitive development fortifications requires a treatment time of about 20 minutes, and it will continue to be a large one Volume of water required for washing and continuing, the stages of development are complicated. The usual ilnt

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development process is else complicated ones in the V /: In the conventional color reversal process such as black and ^T "ei Gent winding, so-called primary development, color development, a break and a Bleieharbeitsgang or bleach-fixing operation are steps applied inevitable and there are not only V / ash-, steps are required between the individual steps, but also often additional steps such as pre-hardening, post-baths and salt baths. As a result, the usual color reversal process usually requires more than 10 steps.

a These developments are therefore usually carried out in development laboratories with very good equipment and equipment.

The requirements of such a long development time, the cost of equipment and the methods of implementation the development stages limited the use of color photographic light-sensitive materials for those uses where rapid and simple development is required, for example Applications for drawings, industrial purposes, scientific Purposes, reproductions and dergj ..

On the other hand, an attempt to achieve images in a simple V / unternomir.en ice, and within a similar short period of time by use of the color photographic diffusion transfer process "This method has already but showing the error, that a magnification is not carried out so that a negative material and a iiildaufnahr / must be used itriiaterial, and therefore limited is ^one, the practical application of this test from dissenting points of view.

The object of the invention is a quick and simple color photograph. Onikehr development

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process for color photographic photosensitive Materials.

It has now become an economical and practical reverse development process for the above purposes found that reversal color photographic materials are developed within 3 minutes can, wherein no washing water or only a very small amount of washing water is required, and wherein the steps can be easily controlled and regulated.

According to the usual inverse development process, it is difficult, from various points of view, to shorten action time. First, since the usual procedure includes a large number of steps as stated above, and a limitation on the abbreviation Given the treatment time in each stage, the overall process may not be satisfactory in terms of the development time abbreviated v / earth and selbs ^ if the procedure could be shortened, the error that the procedure is complicated would not be overcome will.

To simplify the stages in the development, the omission of the washing stages can be considered drag, however, in such a case, the photographic properties of the images will deteriorate due to the contamination Each treatment solution is reduced during the treatments and therefore such an attempt can be made do not apply in practice. Also attempts to use a multi-purpose bath, such as an attempt for carrying out bleaching and fixing in one step by combining bleaching solution and fixing solution consider each other, however, the treatment solutions thus combined become unstable.

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Palls a stable composition for such a thing combined system is used, the coating speed is used decreased.

In order to easily and rapidly carry out a reversal color photographic process without these errors according to the invention applied the following improvement: To effectively simplify the process, the Washing steps are omitted and to prevent damage to the photographic properties of the images, which is caused in the case of omission of the washing steps, it is necessary to prevent a transfer of the treatment solution into the next treatment bath, which is caused by the photographic material or its support will prevent. For this purpose, a thin paper with a weight of less than 100 g / m 2 is used Water-non-absorbent resin-coated paper made by drawing a resin layer on a paper or obtained by impregnating a paper with a resin, or a plastic film as a support for the photographic light-sensitive material to be developed according to the invention is used. The application of this vehicle is especially in the stage following the primary development or the black and white development color photographic reversal process important. In other words, if a thick paper for an ordinary one color photographic paper is used and sufficient Water washing is not applied to the support between primary development and color development, The primary development solution makes the material of a black and white development in dex * color development stage accessible, the color density is reduced and color spots are formed. On the other hand, in the i-n case the

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use of a thin support or a water-non-absorbent support specified above The water wash step can be effectively eliminated from the process without these errors occurring.

The one to terminate the primary development in the case of the invention Procedure time required is usually about 10 seconds and is if it is long, no more than 30 seconds. One of the main reasons for the omission of the v / ash stage between the primary development stage and the primary development stage makes possible that the primary development stage can be carried out within a short period of time. This is because when the washing stage omitted, the bad influences in color development such as increase in color stain and decrease the color density, can be observed when the time for the primary development is lengthened.

The omission of the washing stage between the primary development stage and the color development stage brings not only the advantage of simplifying the process, but also the passing of a considerable increase in the speed of color development, since the swelling of the Emulsion layer is significantly limited by omitting the washing step. It is also believed that the state of the emulsion layer after the primary development treatment is in such a state that the color development is reduced and for induction. g suitable for color development. In any case, the omission of the water supply stage leads to unexpected problems Get benefits,

Another advantage of the invention lies in the point of view that the treatment can easily be carried out at high levels

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Temperatures can be run.

In general, the process involves reversal development baths different from color photographic films, each with different pH values and numerous Washing stages and therefore the emulsion layer becomes Swollen during treatment and tends to reticulate or be easily scratched. This one Tendencies occur more strongly when the temperature of the treatment is increased, it is impossible to increase the speed of the development process can only be increased by increasing the treatment temperature. "

Therefore, an additional step, the so-called pre-curing step, was used, in the case of the emulsion layer of the photographic light-sensitive material is hardened. By applying the pre-hardening stage however, the procedure becomes more complicated and also the treatment period for the development process becomes on Abbreviated at most about 20 minutes.

On the other hand, the omission of the washing stage according to the method according to the invention has the advantage that the Emulsion layer not by the high temperature treatment is greatly softened and therefore no pre-hardening stage is necessary because the emulsion layer has its necessary | Maintains hardness and thereby a very simple and very rapid development can be carried out.

When · a typical example of the muddled invention, the entire wet process is completed within 70 seconds at 45 ^C C. Treatment at such a high temperature cannot be practically carried out in the case of using even a single ash step because the strength of the emulsion layer is reduced and even if such treatment at high temperature is used

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In the case of applying a pre-hardening treatment, it takes 20 minutes to complete the whole process, as stated above. Thus, one of the advantages of the invention is that the development process can be carried out at high temperature and at high speed without using the precure step. According to the invention, therefore, a treatment temperature is usually higher than 30 ⁰ and preferably 40 G applied to 45 ⁰ C.

Even in a complicated package, that of the invention includes Procedure only the following-n six unit procedures:

1. Black and white development * £ 30 seconds

2. Post-development bath <£ 30 seconds

3. Color development 60 seconds.

4. Stop bath 30 seconds

5. Bleach stabilization <S0 seconds

6. Final bath 30 seconds

Since the second stage, i.e. the post-development bath at The above procedure is only necessary in one specific case, a procedure that is selected from the five Treatment stages consists, the most typical example of The invention. Furthermore, a five-stage procedure i.e. the above six-step process, from which the final treatment was omitted or the stop treatment has been omitted, can be used according to the invention.

As a further embodiment, a four-stage process, which is derived from the above six-stage process, advance the two stages of the second stage and the

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fourth stage or sixth stage have been omitted, consists, or a three-step process, which consists of the above six-step process, from which the second, fourth and sixth stage was omitted, can be used according to the invention.

In the first stage according to the invention, the black and white developing solution used contains a developing agent, such as Metol (IT-methyl-paminophenolsulfat), 1-phenyl-3-pyrazolidone, 'a pyrazolidone derivative or hydroquinone, a preservative such as ä sodium sulfite, an alkali such as sodium carbonate, borax or sodium hydroxide, an anti-fogging agent such as potassium bromide, potassium iodide or nitrobenzimidazole, and, if necessary, a solvent for the silver halide, a development accelerator and a surface active agent such as potassium thiocyanate, polyethylene glycol derivatives and sodium dodeeylbenzenes, respectively.

The primary developing solution has an ionic strength of at least 1.8 and the time required to complete primary development is less than 30 seconds, preferably about 3 seconds to 12 seconds, g

The second stage, i.e. the post-development bath, is ™ usually unnecessary and usually it is beneficial to leave the second stage v / eg and that in the first stage to feed treated photographic material directly to the third stage. However, sufficient if you wish To reproduce a less exposed part as an image is to use the post-development bath with a aqueous salt solution, for example a 5% aqueous Solution of sodium sulphate, effective for a short period of time.

ORIGINAL 109851/1712

The post-development bath specified above is fundamentally different from the V / äsohe. That is, the ionic strength of the post-development bath becomes set to a vvert higher than 0.8 so that the Swelling of the emulsion layer is controlled in a suitable manner during the post-treatment stage. The treatment time raua for the aftertreatment bath is 15 seconds or less.

The treatment bath for the third stage, i.e. the color developing solution, contains a color developing agent, for example N, IT-diethyl-p-phenylenediamine hydrochloride, p- (N-ethyl-N-hydroxyethylamino) aniline sulfate, 3-methyl-4- (N-ethyl-N-ß-methylsulfoaminoethylamino) aniline sesquisulfate or 3 methyl 4- (N-ethyl-N-hydroxyethylamino) aniline sulfate, a preservative such as hydroxylamine, or less than 10 g / l of sodium sulfite, an alkali such as sodium carbonate, sodium hydroxide or sodium tert-phosphate, a mist-forming agent, such as ethylenediamine, n-butylamine, sodium borohydride, potassium borohydride or aminoborane, and a solvent, such as benzyl alcohol or diethylene glycol.

The stop bath used in the above process is an aqueous solution with an acidic compound, such as sodium dihydrogen phosphate, peracetic acid and the like., further inorganic salts can be added to this in order to achieve a suitable salt strength and buffering capacity to surrender.

The bleach stabilizer contains an oxidizer for the developed silver and a ^% complexing agent for silver ions. Since the former oxidizes the developed silver to silver ions, and the latter

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converts the silver ion into a complex compound or a stable colorless compound, even if this colorless compound remains in the image in the colorless state, no disturbance for practical purposes.

Suitable oxidizing agents are a complex salt of trivalent iron and ethylenediaminetetraacetic acid, a perricyanide or potassium dichromate. Sodium thiosulphate or sodium thiocyanate are used as complexing agents for the iron-ethylenediaminetetraacetic acid-coraplex salt and sodium thiocyanate is used used for the other oxidizing agents.

The bleach stabilizer bath can be a salt with a buffering effect, for example sodium hydrogen phosphate contain. In addition, the use of a bleach stabilizing bath containing the iron-ethylenediaminetetraacetic acid complex salt contains, the fourth stage can be omitted.

The treatment solution for the final stage consists of an aqueous solution containing sodium sulfate, Natriurahydrogenphosphat, borax, and optionally sodium thiosulphate and has an effect for encryption g improving the quality of the image surface after loading 'treatment and the prevention of the formation of a tacky surface.

When exposed color photographic light-sensitive materials are subjected to the above series of treatments will see the speed of color photography urakehr development process many times over increased compared to the usual color photographic rapid reversal development process, the .desired

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positive image within a short period of time, at most within 3 minutes or within 1 minute, if "special favorable treatment conditions are chosen, obtained and furthermore the process is very simple.

The following are the "advantages of the invention not previously obtained in conventional processes were performed:

1). A stabilizing process for color photography can be applied to the inverse development method. So far, an inverse development process has been used a final y / ater wash required for a long period of time, but was within the scope of the invention a stabilizing process for reversal color photographic development in succession of numerous Investigations applied so that the final wash for a long period of time, which at the usual inverse development process becomes unnecessary. So far, the stabilization process has only been to very simple treatments either in black and white development or in color photographic Development applied, however, a simplification of the complicated color photographic was made within the scope of the invention Reversal development process is achieved and the stabilizing process is effective for reversal color development used,

2). The reversal color photographic development can be simplified will. A typical process of conventional reversal color photographic development consists of 10 up to H levels and is complicated and requires a long period of time to complete the entire levels, while according to the invention, the stages on 3 to 6 stages can be reduced *

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The minimally necessary baths in the process according to the invention are a black and white development bath, a color developing bath and a bleach stabilizing bath, i.e. using only these three baths For example, images satisfying practical purposes can be produced by the method of the present invention. To the Additional steps can still be applied to stabilize the process, however, by itself if such additional stages are used, the number of stages is 6 at most, which is far less than g the number of stages in the usual procedure and furthermore, each stage can be completed within a shorter period of time will,

3). The washing step between black and white development and color development can be omitted. In the usual reversal color photographic development, it is necessary to use sufficient water washing or a stop treatment after black and white development. On the other hand, as a result of the use of a photographic light-sensitive material having a support of low water adsorbability and completion of black and white development A within a very short period of time according to the method of the present invention, the reduction in color density and the formation of color stains are unexpectedly not observed even if the Color development is carried out immediately after the black and white development.

4), The method of the invention shows a particularly great effect when the method is applied to photosensitive Materials for drawings, scientific 'records and inductrie Zwecko is used and the-

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like combinations of the method of the invention and the specific photographic photosensitive Materials are one of the main features of the invention.

5). Although the inventive method is not successful on ordinary color photographic papers can be applied, the method according to the invention can be used on thin photographic films and other specific photosensitive materials, the supports which do not contain Absorb water, bssitasn, for drawings, records and the like without training in love and patches of color applied.

As a carrier for the photographic light-sensitive materials, which according to the inventive dye photographisahen Rapi & uaikohrv-ärfahrsn are developed, films or thin papers with wet water absorption properties are used used «As a carrier for photosensitive Materials for drawings are particularly thin paper or · a little water-absorbing or water-repellent paper. Possibly can also use transparent papers, with a polymer, like a polyolefin, paper or resin coated to prevent diffusion of a treatment solution = - Impregnated papers are preferred.

The various silver halide emulsions, emulsion layers, etc. can be used as photographic emulsions to be applied to the supports according to the invention . the different sensitivities are applied, for example, silver halide, silver iodine bromide, silver iodine bromide or silver-chloro-chlorobromide would be used as silver halide andts "^ '-' honestly sine photo-

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Graphic emulsion having a high specific sensitivity for the blue-sensitive emulsion layer and spectrally sensitized emulsions having low specific sensitivities for the green-sensitive emulsion layer and the red-sensitive emulsion layer are used, but if high sensitivity is required for the light-sensitive material, a silver halide emulsion, usually a silver iodobromide emulsion with such a high specific sensitivity as d for Kameraphoto-

graphics are used for each emulsion layer of the photosensitive material applied and there may be a suitable combination of spectral sensitization and the application of a yellow filter layer can be used.

As stated above, in terms of the layer structure, 1 to 3 silver halide emulsion layers can be used usually applied to the carrier and ,, how if necessary, intermediate layers and a * protective layer are applied. For example, a dichromatic one color photographic photosensitive Material prepared by applying a blue-sensitive emulsion containing a yellow coupler ™ to the support an intermediate layer, a green sensitive emulsion containing a magenta coupler and a cyan coupler, and a protective layer can be applied successively. The order of the layer structure of the light-sensitive material can be changed, as can the combination the coupler can be changed mutually. Of course can also use trichromatographic color photography light-sensitive materials with three oilber-

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halide emulsion layers, each different. Couplers contain and different spectral Sensitivity ranges "have to be developed by the method according to the invention.

The silver halide emulsions used in the context of the invention can chemically through a suitable combination of sulfur sensitization and reduction sensitization and gold awareness. Gelatin represents the usual binder for that Silver halide emulsions are, however, polyvinyl alcohol, polyvinyl acetate, albumin or highly hydrolyzed Cellulose derivatives are used or included.

Hardeners, anti-fogging agents, stabilizers, surfactants for drawing and Development accelerators such as are commonly used can be added to the silver halide emulsions will.

The following examples are provided for further explanation the invention.

example 1

A dichromatic color photographic material which can be formed by coating on a thin photographic Paper with a weight of 55 g / m for document reproduction a blue-sensitive silver iodobromide emulsion, which contains a magenta coupler, an intermediate layer made from a dispersion of a hydroquinone derivative in gelatin and an oilberchlorbromide emulsion containing a cyan coupler contains and was equipped with green sensitivity through dye sensitization, in this series

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Following had been prepared was printed by exposure and contact with a two-color line image on the light-sensitive photographic paper and then subjected to the following treatments at 40 ⁰ C:

Primary development 5 seconds

Color development 15 seconds

Stop treatment 10 seconds

Bleach stabilization 20 seconds d

The compositions of the treatment solutions used above were as follows:

Primary development solution :

Metol (N-methyl-p-aminophenol sulfate) 5 g

Hydroquinone 15 g

Sodium sulfite 80 g

Sodium carbonate · HgO 41 g

Potassium bromide 4 g

Sodium hydroxide 1 g

Sodium thiocyanate 1.5 g

, Water to 1 1 e

yarn development solution :

Sodium sulfite . 5g

4-Amino-3 ~ methyl ~: Kr-ethyl-N- (ß-hydroxyethyl) aniline sulfate . 10 g

Sodium tert-phosphate · 12HpO 100 g

Tri «(hydroxymethyl) nitromethane 3 g

Ethylenediamine (70 ^ ige aqueous solution) 11 ml

Sodium hydroxide 0.1g

"Water to 1

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Stop solution:

Sodium sulfite 40 g

ITodium dihydrogen phosphate · 2HpO 15 g

sodium sulfate 120 g

Water to 11

Bleach Stabilizing Solution:

Ferricyanide 70 g

Sodium dihydrogen phosphate ^ HoO 25 g

Disodium hydrogen phosphate 50 g

Sodium thiocyanate 1.00 g

Water to 11

As a result of the treatment for only 50 seconds, the reproduction of the two-color line image was obtained.

Example 2

In the method according to Example 1, the time for the bleach stabilization was extended to 4-0 beings and used as a solution for bleach stabilization the following composition:

Bleach Stabilizing Solution:

1: 1 complex salt of trivalent iron

and EDTA 36 g

Ammonium thiosulphate 100 g

Sodium sulfite '' 7 g

Potassium pyrosulfite 15 g

Sodium primary phosphate 20 g

Sodium carbonate · HpO 6 g

Water too

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A good image could be obtained by developing for 80 seconds.

' Example 3

When the stop treatment in the method of Example 2 was omitted, and the following treatment was carried out for 60 seconds at 40 ⁰ C, a good image was obtained line:

Primary development 5 seconds %

Parb development '15 seconds

Bleach stabilization 40 seconds

Example 4

In the procedure of Example 2, the following step was added to the bleach stabilizer bath treatment:

Stabilization at 40 ^° C. for 10 seconds

Composition for stabilization:

Sodium dihydrogen phosphate. 2H ₂ 0 50 gj |

Sodium sulfite 20 g

Water to 11

The addition of the StaMlisierstufe increased the stability of the colored image of the reproduced drawing and the physical properties of the same are improved.

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Example 5

A single-layer color photographic light-sensitive material for a line image was prepared by applying a fine-grain silver chlorobromide positive emulsion containing a cyanol rappler to a cellulose triacetate film and exposed to the following treatments to form a cyan color reproduction by development for 33 seconds, the entire process at 40 ^p C was executed:

Primary development 3 seconds

Color development 10 seconds

Bleach stabilization 10 seconds

The compositions of the treatment solutions used in the above process were as follows:

Primary development solution:

i-phenyl-3-pyrazolidone 1 g

Hydroquinone 15 g

Sodium sulfate 30 g

Sodium carbonate »HpO 30 g

Potassium bromide 2 g

Sodium hydroxide 2g

Potassium thiocyanate 1 g

VTascer to 11

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color development solution:

Sodium sulfate 5 g

methanesulfoamino ethyl aniline

sesquisulfate 8 g

Sodium Hydroxide 2.5 g

Sodium tertiary phosphate «12HpO 30 g

Ethylenediamine (70 ^c / olge aqueous solution). 5 ml sodium borohydride 0.07 g έ

V / ater to 11

Bleach stabilizer bath;
As in example 2.

Example 6

As a further embodiment of the procedure given in Example 5, the following five steps were used and a clear image was obtained. The entire steps were carried out at 40 ⁰ C:

Primary development 3 seconds

Color development 12 seconds

Stop treatment 5 seconds

Bleach stabilization. 15 seconds

Stabilization 10 seconds

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The compositions for the above treatments were as shown below. The primary development solution and the color developing solution

had the same composition as in Example 5

Stop solution;

Sodium bisulfite 15 g

Sodium sulfite 40 g

Sodium dihydrogen phosphate «2HpO 25 g

Sodium acetate 30 g

Water to 11

Bleach stabilizer solution;
As in example 1.

Stabilizing solution;

Sodium dihydrogen phosphate «2H ₂ 0 Beistdel 7 · 30th G Sodium thiosulfate 35 G Sodium sulfite 30th G Water too 1 1

The bleach stabilization stage was similar to Example 6 carried out for 20 seconds and the final treatment for 10 seconds with. ^ deni in the example 4 specified stabilizing bath carried out.

Claims (6)

Claims Process for the rapid development of an exposed color photographic reversal material, characterized in that that (1) the reversal color photographic material is developed in black and white for less than 30 seconds, wherein the material consists of a carrier with a coating at least one silver halide emulsion layer which contains a color coupler, the carrier _Λ either from (a) a paper weighing less ™ than 100 g / m, or (b) a synthetic resin coated Paper or (c) resin impregnated paper with low water absorption properties, or (d) consists of a resin film, (2) the material is color developed for less than 60 seconds, and (3) bleach stabilizes the material for less than 60 seconds is, with none in the treatment stages Water washing stage is applied. 2. The method according to claim 1, characterized in that a stop treatment is carried out between the black and white development and the color development. M. 3. The method according to claim 1 or 2, characterized in that a stabilization after the bleach stabilization is carried out. 4. The method according to claim 1 to 3, characterized in that daG dip black and white development during 3 to 12 seconds. 109851/1712 5. The method according to claim 1 to 4, characterized in that as Ge saintbehandlungs period in the Treatment stages are not used for more than 3 minutes. 6. The method according to claim 1 to 5, characterized in that! 3 the treatment stages at a higher temperature than 3O ^C C are carried out. 109851/1712