DE1597567B1 - Diffusion transfer process for the production of colored images - Google Patents

Description

1 2

The invention relates to a diffusion transfer "foreign" colors contaminated and the various Process for producing colored images in which colors are generally poorly saturated. This is Image-wise exposed color photographic record- especially the case with the red image colors, their tion material, consisting of a layer support so quality is often not satisfied, like at least two color-forming paints applied to it It is units that each consist of a silver halide ring and improve their color saturation emulsion splint and one immediately adjacent to it, therefore common, between the individual color-forming ones There are units in such recording materials in the form of a dye developer layer arranged in a beard and through water-insoluble, alkali-permeable intermediate layers, often also as barrier layers layers are separated from each other, of which min- io denotes to be arranged, which for example from Gedestin one can consist of a water-insoluble salt from latine.

a polyvalent metal cation and a water disadvantage in the known intermediate layers

soluble polymers with free carboxylate anions, however, that they have only limited effectiveness, stands or contains such, the intermediate d. i.e., the color contamination and the color saturation layer for the dye developer in aqueous alkaline 15 of the different spectral colors are not in shear solution is less permeable than the water-soluble extent is reduced or increased, as it is per se The polymer used to make up the layer would be desirable to produce high quality color images was treated with an alkaline working solution.

here the latent images in the exposed areas

of the silver halide emulsion layers, the 20 a recording dye developer for the diffusion transfer process Proposed fixing material in the exposed areas in which the dye is placed and the dye developer of the undeveloped developer through alkali permeable interlayers Districts are separated from one another by diffusion onto an image-receiving sheet, at least one being be transmitted. Interlayer made from a water-insoluble salt

It is known (see the USA patents 25 of a polyvalent metal and a water-soluble, 2,559,643, 2,647,049, 2,698,798, 2,774,668, 2,983,606 film-forming polymers with free carboxyl groups and 3,253,915, as well as British Patent 804,971. With EQKe one of the and French patent 1 313 767), for producing recording material, the occurrence creation of colored images after the dye of color impurities in the transferred BiI diffusion transfer process as dye developer 30 dem are reduced.

It has been shown, however, that in these recordings

In the molecule the chromophoric system of a dye is used as barrier layers and a remainder with silver halide developing interlayers tend to form part of the solubility contain. Recording materials with such dye developers in the underlying Like dye developers, there are generally 35 layers, especially the blue-green dye dew to prevent several photosensitive silver halide winder from getting into the image-receiving sheet sion layers that diffuse towards different areas. As a result, a decreased density becomes the visible spectrum are selectively sensitized. value A, ^ of the in the layer below before-The Dye developers are adjacent to the silver-bearing dye developer in the transferred one halide of each silver halide emulsion layer.

orderly. Their color is the color of the one in question. It is also known (see German Auslegeschrift

the silver halide emulsion layer recorded 1155 334), in the context of the silver salt diffusion over-light practically complementary. The exposed application process to use materials at Drawing material is developed by exposing one or both of the surfaces to which the treated with an alkaline solution. The coloring 45 transfer are in contact with each other Substance developers develop a latent image in the ne- one or more water-soluble metal alginates negative image areas and are at the same time exist or contain them. By using Development in these areas laid down, while in the metal alginates in the surfaces of the materiahen the unexposed areas the unchanged color should be the separation of recording material and Substance developers diffuse to the surface and are relieved by 50 image-receiving layer after transfer there to be in contact with the recording material.

Brought image receiving sheet to be transmitted and finally has already been proposed (cf.

on it a positive, multicolored picture (German patent 1291996), for the creation of blocking items, Layers in Photographic Materials Complex - Ideally, each individual dye developer should be compounds with trivalent chromium or aluminum to use the silver halide immediately adjacent to it as the central atom, develop, d. i.e., a cyan dye developer, an object of the invention is to provide diffusion over target only to specify the red-sensitive silver halide emulsion transfer process, in the case of which through the layer, a purple dye developer is only intended to prevent the occurrence of color impurities in the the images obtained in the green-sensitive silver halide emulsion layer 60 are greatly reduced and the coloring a yellow dye developer should only improve the blue saturation of the images, sensitive silver halide emulsion layer. if the recording material is a fusion transfer process for producing farbium a common "three-color" recording material for pictures, which is an imagewise exposed color photo. In fact, however, each dye develops a graphic recording material consisting of undesirably develop each silver halide, one layer support and at least two on top nidemulsionsschicht, which has the consequence that the individually applied color-forming units, each from nen colors in the transfer images by a silver halide emulsion layer and one to it

immediately adjacent dye developer layer and separated from each other by water-insoluble alkali permeable intermediate layers are at least one of which is composed of a water-insoluble salt of a polyvalent metal cation and a water-soluble polymer with free carboxylate anions or contains such, wherein the intermediate layer for the dye developer in aqueous-alkaline solution is less permeable than the water-soluble polymer used to build the layer with an alkaline working solution treated here, the latent images in the exposed areas of the silver halide emulsion layers developed, the dye developers in the exposed areas and the dye developers of the undeveloped areas are transferred to an image receiving sheet by diffusion, from and is characterized in that the treatment or development of the material in the presence of a organic, alkali-soluble complexing agent for the polyvalent metal.

The complexing agent can be present in the recording material itself. Can advantageously however, the complexing agent is also added to the alkaline working or developer solution or the Incorporate the image receiving layer.

If the complexing agent is used in the recording material, it has proven to be advantageous to apply the complexing agent in the form of a layer to the side of the color photographic material which

O C.

(CHM) _m O
CH i

(CHM) ₀
X

comprises the intermediate layer or layers.

The invention enables images to be obtained by the color diffusion transfer process are, which are compared to the images that can be produced by this process up to now due to reduced color impurities and have a significantly improved color saturation.

The complexing agents used according to the invention carry the ions of the polyvalent metal of the intermediate layer into a complex or a chelate and thereby make the intermediate layer for the one below Dye developer permeable after the dye developer has exposed the silver halide has developed in the emulsion layer immediately adjacent to it.

A wide variety of organic alkali-soluble substances are suitable for carrying out the process of the invention Complexing agents. Preferably used complexing agents are aminocarboxylic acids, oxyalkylamino acids, Sulfhydrylamino acids, aminosulfonic acids, aminophosphonic acids, oxycarboxylic acids or Ethylenediaminetetraacetic acid, d. H. acidic compounds. Derivatives can also be used in an advantageous manner those acids which form the complexing agents in the alkaline developer solutions used in the development of the color photographic recording material form or release, can be used.

It has proven to be particularly advantageous to use a compound of the general formula as a complexing agent

or (CHZ) _n

to use in which mean:

M and Z each represent a hydroxyl group or an alkoxy group of the formula

- OC - R

wherein R represents an alkyl radical or an aryl radical,

X is a hydrogen atom, a methoxy group, a group of the formula

O
- CH ₂ OCR ²

wherein R ^{2 represents} an alkyl radical or an aryl radical,

Y is a carboxy group, a carbamyl group or a group of the formula

.0

-COR ¹

wherein R ^{1 is} an alkyl radical,

A is a methoxy group, a carbamyl group,

a carboxy group, a group of the formula

O
- COR ¹

wherein R ^{1 represents} an alkyl radical or a group of the formula
~

-CH ₂ OCR ²

wherein R ^{2 is} an alkyl or an aryl radical

represents

m is an integer from 2 to 3,
η is an integer from 1 to 5 and
ο an integer from 0 to 2,

where at least one of the groups A, Y or Z is a carbamyl or an ester radical.

Typical advantageous complexing agents are those of the following formulas:

, P

C -

, y

C-OR ²

(CHOH) j, O (CHOH) p O (CHOCR) _g

CH ₂

O
C-OR ²

(CHOH) ₈

COR ²

CH

CH ₂ OH

C-NH ₂

(CHOH) ₂

CHoOH

CH ₂ OH

O C-OR ⁵

(CHOCR ³ ) ₂

CH ₂ OCR ³ O

O

and

(CHOCR ⁴ ^ O

CH

CH ₂ OCR ⁴

in which mean:

R ^{2 is} an alkyl radical,

R ³ and R ⁴ each represent an alkyl radical or an aryl radical,

R _{5 is} an alkyl radical or a hydrogen

atom,

ρ is an integer from 2 to 3 as well

q is an integer from 1 to 5.

P. 952 [1953]; J. Am. Chem. Soc, 78, p. 2825 [1956]; HeIv. Chim. Acta, 34, p. 2343; J. Am. Pharm. Assoc, 28, p. 364 [1949] and U.S. Patent 2,380,444). Special complexing agents which can be used according to the invention are listed in Table E below. Further particularly suitable complexing agents are z. B .:

l ^ -diaminocyclohexane-r ^ N'-tetraacetic acid, N-hydroxyethylethylenediaminetetraacetic acid, jÖ-mercaptoethyliminodiacetic acid, 2-sulfonanilinediacetic acid,

Adenosine triphosphate,

Glycolic acid,

Salicylic acid,

Ethylenediamine tetramethylene phosphonic acid, Ν, Ν-Dihydroxyäthyläthylendiammtetraessig-

acid and
N-methylthioethyliminodiacetic acid.

The preferred complexing agents are D-Galac-ίοη-μ-lactone, D-arabon-lactone, methyl-1-arabonate or methyl-D-gluconate peiita acetate is used.

The complexing agents can be used in various concentrations. In individual cases Most favorable concentration may depend on the number and type of interlayers that are present Amount of polyvalent metal ions, the type of complexing agent, the development time and further depend on the location of the recording material at which the complexing agent is arranged.

When using the complexing agent in the recording material, concentrations of about 25 to 150 mg complexing agent / 0.09 m ² layer are preferably used, while when using in an image receiving sheet, concentrations of about 50 to 200 mg complexing agent / 0.09 m ² image receiving sheet are preferably used. In alkaline working solutions, concentrations of about 0.1 to 5 percent by weight are preferably used.

The complexing agents can be mixed on the recording material and on the image receiving sheets can be applied with other components or in the form of special layers. So they can Complexing agent applied in an organic, hydrophilic colloid in the form of an aqueous layer will. Furthermore, the complexing agents can be used in solvents with a high boiling point, e.g. B. a Boiling point of over 175 ° C, dissolved and dispersed in the form of fine droplets in a hydrophilic colloid

If the substituents R, R 1, R ² , R ³ , A ⁴ and R ^{5 represent} alkyl radicals, these generally have 1 to 20, preferably 1 to 8 carbon atoms and are

For example, methyl, ethyl, isopropyl, butyl, 50 are gated, whereupon the resulting dispersion has heptyl, octyl, decyl, octadecyl or eicosyl radicals. can be applied to the carrier. If Z is a hydroxyl group, then R ^{1 is} preferably an alkyl radical having 1 to 2 carbon atoms. R ² is also preferably an alkyl radical

A wide variety of polyvalent metal salts and polymers can be used to produce the intermediate layers can be used with carboxylate anions. The intermediate layers can be obtained by that a solution or a water-soluble substrate, which the polyvalent metal in water-soluble Contains form, is applied over a layer of a polymer having free carboxyl groups,

with 1 to 2 carbon atoms. If the substituents represent aryl radicals, these exist, for example from phenyl, tolyl and naphthyl radicals, preferably Phenyl residues.

The complexing agents can by known amidation and esterification methods with saturated, 60 which in turn come beforehand via one of the Oxycarboxylic acids free of aldehyde residues, such as GIy- den layers were applied to the layer support.

This creates a thin layer of the water-insoluble metal salt. If necessary, can Solutions of the polyvalent metal are applied directly to silver halide emulsion layers when the binder for the silver halide is a polymer having carboxylate anions, which with the Metal ions form insoluble salts. Over or under

cerin, erythronic, arabonic, lyxonic, ribonic, xylon, gluconic, galactonic, mannonic, gulonic, tartaric, glucoguloheptonic acids and corresponding oxycarboxylic acids (cf. J. Am. Chem. Soc, 37, p. 345 [1915]; J. Am. Chem. Soc, 55, p. 2512 [1933]; J. Am. Chem. Soc, 62, p. 1074 [1940]; J. Am. Chem. Soc, 69, p. 915 [1947]; J. Org. Chem., 18,

7 8

Intermediate chloride can be applied to the water-insoluble salt layer in such an amount that

Layers of water-permeable compounds placed on a carrier area of 0.09 m ^2, about 5 to 100 mg

be ordered. Calcium chloride is not required.

The water-insoluble suitable alkali-permeable, water-insoluble salts are preferably used

Salts existing intermediate layers between the 5 in the intermediate layer or layers of the recording

the blue-green dye developer and the pure materials are z. B .:

color-forming zirconium gelatinate containing purple dye developer

the unit arranged to the purity and the thorium gelatinate

Saturation of the red pigment of the transferred 'calcium pectinate'

images formed by the dye developers on ver io calcium alginate '

improve. In a corresponding way, you can also use zirconium alginate,

between the yellow Farbstoffentw _lc Kler and Bleicarboxymethylcellulose,

manganese ginate containing the purple dye developer

color-forming unit and between the purple-chromalginate '

red dye developer and which _partially treats _{the blue-green 15 calcium of} ' _with p _o i yviny ialkohol

Dye developer containing unit arranged ester succinic acid

be to the color unity and color saturation of the over- polyacrylic acid calcium '

to improve carried images. Barium alginate,

For the production of a water-insoluble tin alginate

Intermediate layers of salt can contain the 20 magnesium alginate

various film-forming, alkali-permeable, water-strontium aleinate '

insoluble polymers, including their water- cobalt alginate '

soluble salts can be used. Characteristic Nickel Almnat '

contain suitable polymers, based on the weight of iron salsinate '

of the polymer, preferably about 5 to 60% free cadmium alginate

Carboxylate anions or, the equivalent amount of lead alginate and '

water soluble salts. Suitable polymers are e.g. E.g .: calcium salts of salicylic acid - formaldehyde con-

, .. _ _T ..,., _. . "" J. , j ,, .. -j. densation products, where appropriate also

(1) Natural proteins and mixtures of these salts derived therefrom are used Substances such as in particular gelatine and cheese; 30 can

(2) Naturally occurring polysaccharides with

high molecular weight with free carboxyl. The use has proven to be particularly advantageous

groups and their derivatives such as alginic acid, a recording material that contains a calcium pectic acid, Tragant acid, carboxymethylcellucium alginate layer between the color-forming Einlose and cellulose sulfate; 35 units from the red-sensitive and the green-sensitive

(3) Ungroup synthetic linear polymers with carboxyl borrowed gelatin silver halide emulsion layer, how they z. B. from the USA.-patent holds.

Writings 2,565,418, 3,062,674 and 3,007,901 so- for carrying out the method of the invention

as known from British patent specification 886 882, common known dye developers are suitable, are e.g. B. succinic acid residues containing poly 40 d. H. Compounds that are used both as silver halide

vinyl alcohol ^ maleic acid-styrene mixed polymer developer and also act as dye-forming agents. the

Sates, alkyl acrylate-acrylic acid copolymers, dye developers are characterized by the fact that they

Salicylic acid-formaldehyde resins, acidic poly- in colloidal layers, as in photographic ones

ester and acidic polyamides. Emulsions used hydrophilic organic

45 colloids at neutral pH proportionally

Polyvalent metals which are suitable for the formation of non-diffusing layers, however, are diffusing in the presence of alkaline, water-insoluble metal salts containing intermediate developer liquids. B. calcium, strontium, preferably those dye developers verBarium, magnesium, manganese, iron, chromium, nickel, applies, in which the chromophoric part is an azo-cobalt, lead, cadmium, tin, zirconium, thorium 5 ° or anthraquinone dye residue and the rest with and other polyvalent metals in the form of water-silver halide developer function a benzene, soluble salts applied, with the described, free z. B. represents a hydroquinone radical.
Polymers containing carboxylate anions. Suitable dye developers are, for. B. from the simultaneous crosslinking of the same water-insoluble, USA.-Patent 3,146,102, the Australian Paaber are able to form alkali permeable salts. 55 tentschrift 220 279, the German patent specification The amount of insoluble metal salt used in the intermediate layers 1 036 640, the British patents 804 971, can be very different and 804 973 to 804 975, the Belgian patent specification. It depends on the desired effect 554 935, the French patent 1168 292 and the nature of the multi-valued and Canadian patents 577 021 and term metal cations and / or the polymer with 60 579 038 known.

Carboxylate anions. Preferably, those for the preparation of the photographic recording quantities used that the water-insoluble salt preparation material are the dye developer withheld Interlayer used in aqueous-alkaline, preferably in the form of dispersions, Medium a permeability for dye developer which consists of finely divided droplets of solutions of the which is about that of a substantially 65 dye developer in high boiling or so-called Calcium alginate is equivalent to the existing layer, th crystalloidal solvents in hydrophilic, how it is obtained when one consists of essentially organic colloid binders. Such Borrowed sodium alginate layer calcium dispersions can be prepared by that

009546/314

9 10

the dye developers are used in high-boiling or with polyvinyl acetate, polystyrene, polyethylene terephthalate, practically immiscible organic liquids polyethylene, prolypropylene, paper, dissolved with polyethylene with boiling points above about 175 ⁰ C, coated paper and glass,
where appropriate, in order to facilitate the dissolving of the dye images from the developer in the high-boiling, water-insoluble solution 5 wrapped recording material, the usual means, in addition, an auxiliary solvent, known image receiving sheets can be used, ie either at least 25 ° C below the according to the invention, the boiling point of the high-boiling solvent used, the complexing agent, may be present in any layer of these images of the solvent or a water-insoluble receiving sheet. The image organic solvent is used. The dye-receiving layers for receiving the dye-removing agent can also be contained in binders or carriers for the dye-removing agents that are soluble in organic solvents, e.g. B. linear polyamides, proteins, such as Gelagesetzt, which also solve the dye developer. tine, polyvinylpyrrolidone, poly-4-vinylpyridine, poly-Finally, the dye developers can also use vinyl alcohol, polyvinyl salicylal, partially hydrolyzed by other methods in colloid binders, which are made of polyvinyl acetate, methyl cellulose, regenerated for photographic layers, dispersed cellulose, carboxymethyl cellulose, carboxymethyl cellulose be e.g. B. by grinding in a ball of ethyl cellulose and mixtures of these substances. The mill. Layers can be applied to a support of the type used for color photographic preparation of the recording material, in addition to the auxiliary developer compound. Bildempfangsdungen, z. B. colorless and practically insoluble in water, which release acidic substances and z. B. from borrowed hydroquinone derivatives, as they are known in the French US Pat. No. 2,584,030, verPatentschrift 1,313,086 are described. be turned.

Such auxiliary developer compounds can help the image-receiving sheet to be stripped cleanly Silver halide emulsion layers or optionally 25 from the recording material after transfer other layers, such as top layers, intermediate the dye developer image on the image receiving layers etc., can be added. To facilitate the layer, the image-receiving sheet can be used for the production of the color photographic on-surface with a non-diffusing hardness drawing material the known developing agents and a surface-active agent are hardened silver halide emulsions, of which positive 30 can be. For example, the image receiving layer can be made of Transfer images can be made using polyvinyl alcohol containing poly-4-vinyl. However, reverse emulsions, pyridine as a mordant with an oxyguar hardener such as solarized emulsions and emulsions, the solution used as a surface active agent e.g. B. Sodium latent images mainly inside the silver halo cetyl sulfate or sodium N-methyl-N-oleyl taurate entgenid grains form, are used as they are e.g. B. 35 holds, have been treated.

from U.S. Patent 2,592,250. If necessary, the color photographic on-off of such emulsions, negative transfer drawing material can also be produced with the image-receiving sheet and transfer images. form a whole. Suitable silver halides are silver chloride, SiI- in the immediate vicinity of the support, among the berbromide, silver bromoiodide, silver chloroiodide, SiI- emulsion layers and dye developer layers, berchlorobromoiodide and mixtures thereof. Arranged. In addition, suitable sensitizers for the silver halides can be on the support between the image-receiving sheet and the e.g. For example, the sulfoalkyl and carboxylalkylcarbocyanine layers overlying a so-called stripping dye of the type known from U.S. Patents 2,213,995 can be layered around image receiving sheets 2,481,698, 2,503,776 and 2,912,329. 45 easier to detach from the other layers. As a binder for these silver halide emulsions after the transfer of the dye developer has ended, the usual known organic hydroimages to the image-receiving sheet can be completed.
Phile colloids are used, especially gelatin For the development of an exposed Aufzeichtine and besides this z. B. polyvinyl alcohol and its processing material suitable alkaline working solutions water-soluble derivatives. 50 are generally strongly alkaline and have a pH of at least 12. In order to achieve this high alkali-different silver halide emulsion layer, the solutions contain e.g. B. Be alkali or in separate, but directly attached to the individual hydroxides, such as sodium hydroxide, or alkali carbon silver halide emulsion layers, such as sodium carbonate. The solutions can be adjoining layers. 55 but also volatile amines, e.g. B. diethylamine, ent- The photographic recording material contains, which have the advantage of evaporating from the produced holds at least two color-forming units with each images residue-free,
Because of a silver halide emulsion layer and the alkaline working solutions are developed in a camera next to the silver halide of this emulsion layer in a development process. The color-forming 60 uses and is used in breakable containers, so units are preferably so spectrally sensitive they can be thickeners such as. B. Hydroxyäthylbilisiert that they absorb light of a color that contain cellulose or carboxymethyl cellulose. Pre-practical the color of the dye developer in which the alkaline working solution is preferably complementary to the onium unit. compounds such as those in the U.S. Patent

For the production of the color photographic records 65 3 146 102 are described, added,

tion materials can have the most varied of trans- The color-forming units can be on the

Parent and opaque photographic supports arranged in a different order

Layer support, e.g. B. made of cellulose nitrate, cellulose acetate. With a "three-color material" it will

11 12

blue-green color image-forming unit expediently the 13 'can be formed in that one over the Layer support closest to the yellow color image layer 13 applies a layer 14, which a multi-forming The unit furthest from the substrate contains a divalent metal cation that is removed with the poly and the unit forming the purple colored image reacts with the carboxylate anions. Above the accordingly, between the blue-green color layer 14 there is a green-sensitive silver image and a halide emulsion layer 15 and an interposed thereover of the yellow color image forming unit. Selenium layer 16. Above layer 16 is a one

Preferably, the dye developers are in layer 17 containing yellow dye developer

a separate layer under each silver halide and over layer 17 a blue-sensitive emulsion layer of the color-forming units, the silver halide emulsion layer 18 borrowed to io, over which

the various emulsion layers are immediately followed by a top layer 19,

bordering, housed. The dye developers are shown in FIG. 2 shows a three-color recording medium

preferably selected so that their color corresponds to that of a water-insoluble salt

Color of the polyvalent metal cation in the associated silver halide and a polymer with

sion layer absorbed light practically grain 15 carboxylate anions existing intermediate layer between

is plementary. see the purple dye image and that

According to a particularly advantageous embodiment, the blue-green dye image and between that the yellow

form of the method of the invention becomes a recording dye image and that of the cyan dye image

ning material is used, the three unit forming one above the other.

Ordered color-forming units of red, green and 20 On the layer support 20 is a one

blue-sensitive gelatin silver halide emulsion blue-green dye developer and advantageous

contains layers, wherein the color-forming unit with way a complexing agent-containing layer 21

the blue-sensitive gelatin silver halide and above this a red-sensitive silver halide

sion layer furthest from the support emulsion layer 22. Above layer 22 is a

and the color-forming unit with the red-sensitive layer 23 containing polymer with carboxylate anions

Gelatin-silver halide emulsion layer arranged next to that. There is one above layer 23

Layer support is arranged and in which between the a purple dye developer and a water-

Units of alkali permeable, water-insoluble layers soluble salt from a polyvalent metal cation,

of calcium alginate are arranged and in which the with the polymer of the layer 23 to form

furthermore, the dye developer is a layer containing the color of the reacted in 30 of the intermediate layer 23 '

of the assigned gelatin-silver halide emulsion 24. Above the layer 24 there is a green emulsion

layer of light to be received essentially sensitive silver halide emulsion layer 25, and over

have complementary color and in the closing layer 25 there is a polymer with carb-

Lich between the support and the calcium oxylate anion-containing layer 26. Above the

alginate layer, which is between the one blue-green layer 26 is a yellow dye developer

Dye developer and one purple color and one water-soluble salt of a polyvalent

Material developer-containing layer is arranged, metal cation, which is with the polymer of layer 26

an organic, alkali-soluble complexing agent for reacts to form an intermediate layer 26 ',

Calcium ions applied in a concentration of about 25 to containing layer 27. Above the layer

150 mg complexing agent per 0.09 m ² layer support 40 27 there is a blue-sensitive silver halide

area is housed. emulsion layer 28, over which finally

In the drawing are in the F i g. 1 and 2 two a layer 29 is arranged.

Embodiments of a for carrying out the process The following examples are intended to illustrate the invention

illustrate in more detail suitable recording material according to the invention,
rials shown in section. 45

The in Fig. Example 1 recording material shown in FIG

shows between which the purple dye image forms- „ _Ύ,,,, ..,. . . ,

and the one that forms the blue-green dye image (use of the complexing agent in the recording

Unit of a polyvalent metal cation and nungsmatenal)

a polymer with carboxylate anions, 50 First, a recording material of the in

water-insoluble salt layer. The recording F i g. 1 structure shown in that

material has on a layer carrier 10 a conventional one having an adhesive layer

Layer 11 containing cyan dye developer. Cellulose acetate film supports successively

on, which were advantageously applied a complexing agent layers:
contains. On the layer 11 there is a red 55

sensitive silver halide emulsion layer 12 and layer No.

above a layer 13 made of a polymer with 1 blue-green dye developer layer (ent-carboxylate anions. Part of layer 13 consists of layer no. 11 of FIG. 1)
from a salt layer 13 ', with a salt from the A dispersion of metal cation polyvalent in Nn-butyl acetanilide and the polymer. The 60 dissolved 5,8-dihydroxy-1,4-bis [/? - hydroxy layer 13 'can e.g. B. by applying an aq quinonyl - α - methyl) äthylamino] - anthracite solution of the water-soluble salt of a polyether than blue-green dye developer in valuable metal can be produced on the layer 13, gelatin with a content of D-galactone with the polyvalent metal the polymer of γ-lactone as complexing agent, layer 13 was applied to the substrate with formation of the water-insoluble intermediate layer in such a way that layer 13 'reacts. Above the intermediate layer 13 'about 0.09 m ^{2 of} carrier surface 146 mg of dye is a layer 14 containing a purple dye developer, 221 mg of gelatin and 55 mg of the curler. The intermediate layer of complexing agent was omitted.

13 14

Send no. Shift no.

Red-sensitive emulsion layer (corresponding to 9 top layer (corresponding to layer No. 19 corresponding to layer no. 12 of FIG. 1) from Fig. 1)

A red-sensitized developable gel- A dispersion of the auxiliary developer 4'-Me-

tine silver bromide iodide negative emulsion layer ^{5 thylphenylhydroquinone in gelatin}

was applied to the blue-green dyes in this way to the emulsion-sensitive

Wrapping layer applied that applied to about layer that applied to about 0.09 m ²

0.09 m ^{2 support area} 219 mg silver and support area 10.5 mg auxiliary developer and

86 mg of gelatine were used. 32 mg of gelatin were omitted.

i °

Sodium alginate layer (corresponding to layer In Table A below, No. 13 of FIG. 1 described is designated as "Material A" recording material). On the red-sensitive silver halide emulsion layer, as "Material B" in Table A below, so much sodium algae was applied to the recording material that was ^{built up in the manner on about 0.09 m 2 of} carrier, but instead contained D-galactone 27 mg of sodium alginate were omitted. μ-lactone in the blue-green dye developer layer

D-arabonlactone at a concentration of 45 mg

Purple dye developer layer (corresponds _au fo O9 m ² support surface.

speaking of layer number 14 of FIG. 1) The recording material shown in Table A below as "Material C" - a dispersion of _{recording material drawn in Nn-butylacetanilide 20} - had the same dissolved 4 - isopropoxy - 2 - [p> - (ß - hydrochine structure, but contained in the cyan Farbstoffonyläthyl) phenylazo] -l-naphthol as a magenta developer layer methyl-l-arabonate in a Konzenioter dye developer iri gelatin concentration of 55 mg each about 0.09 m ² support surface, a content of calcium chloride was DER z _u comparative purposes another Aufzeichart prepared clot material to the Natriumalginatschicht 3 äufge- _25, which in the cyan Farbtrageri that at about 0.09 m ² support surface fabric developer layer contained no complexing agent. 64 mg of dye developer, 92.5 mg of gelatin This material was shown in Table A as a comparison and 18 mg of calcium chloride were omitted. The material 2 ”is designated. For comparison purposes, calcium chloride with the sodium sat _e j _n another recording material without Komplexalginat the adjacent layer under BiI- _3o formers, sodium alginate and calcium chloride hergedung a CalcmmalginatzwischenschichtlS provides'. The sodium alginate layer was replaced by one between layers 13 and 14 µm. Gelatin layer of 205mg gelatin per 0.09 m ^a _ _, .. ^ ,,. , Τ-, ·, replaced support surface. This recording material

Green-sensitive emulsion layer (· _η corresponds _{is the foi the Table A as} "comparison Mate Speaking layer no. 15 of F ι g. 1) _{35 rkl 1 ((hereinafter}

A green-sensitized developable _{The exposed} recording materials were

Gelatme silver _{bromoiodide negative emulsion dmch thin color} step wedge with density increments

was plotted in such a way to the layer # 4 _{yon Q3 in dnem} i _nth nsitätsskalensitometer exposed,

f ™. '",J" * T ™ ^ ^{0?. Tra} gerfl ^a che _{The exposed} samples _WUR d _s then to-103 mg accounted silver and 43 mg of gelatin. _{40 of a supply brin a a} i _kalisclien activator included-

Intermediate layer (corresponding to the layer of developer solution on the emulsion side and on no 16 von Fiel) developed from image receiving sheets.

On the shift no. 5 were ^ie from a loading _e £, Bildernpfangsblätter consisted of a

Layering mix as much gelatin and paper base with three coated on top

^ -Methylphenylhydroquinone applied, «layers of which a layer of polyvinyl alcohol

that on about 0.09 m ² carrier area 140 mg ^ ^{ο1 and} poly-4-vmylpyridm as a pickling agent and a

Gelatine and 10.5 mg ^ -Methylphenylhydro- ^da ™ ^te * arranged layer of a methyl

there was no quinone ■>? ■> * vmylather - maleic acid - copolymer.

There was one between these two layers

Yellow dye developer layer (ent- 5o layer made of polyvinyl alcohol.

speaking of layer number 17 of FIG. 1) ° i ^e image-receiving sheets were about A dispersion of 2 minutes dissolved in Ditetrahydrofurylädi- with the developed Aufzeichnungspat l-phenyl-3-Nn-hexylcarbox- materials left at 21 ⁰ C in contact, and then again vonamid-4- [p- (2'-5'-dihydroxyphenethyl) -phe- separated from each other.

nylazo] -5-pyrazolone as a yellow dye! - 55 The alkaline working solution consisted of one

Curlers in gelatin, was so highly viscous to the aqueous solution of 2.0 percent by weight

Intermediate layer no. 6 applied that on koser hydroxyethyl cellulose, 5.7 percent by weight

about 0.09 m ^{2 support area} 48 mg dye sodium hydroxide, 2.4 weight percent benzotriazole,

developer and 48 mg gelatine were omitted. ² A percent by weight of 1-benzyl-2-picolinium bromide and

6o 0.4 weight percent sodium thiosulfate pentahydrate.

! Blue-sensitive emulsion layer (corresponding to the reflection densities of the colored density levels transferred to the image-corresponding layer No. 18 of Fig. 1) One was measured out on layer no. 7.

windable gelatine - silver bromide iodide - Nega- In table A the determined for the color images are

tivemulsion, which are not compiled against blue 65th density values. From these values

If light was sensitized, applied in this way, there is an increased density value Dmax for the

that on about 0.09 m ^{2 of support area} 69 mg of blue-green dye (i.e. an improved color

Silver and 49.5 mg gelatine were omitted. Saturation of the cyan dye developer image)

and a reduced density degradation in the magenta image (i.e., the magenta dye developer image no longer showed the deficiency observed so far

Saturation) as a result of the use of the complexing agents in the under the blue-green dye developer layer lying layer.

Table A.

Recording material Blue green
dye density
Dmax Purple
dye density
D _m ax Yellow dye density
Dmax Purple dye
density drop Comparative material 1 ...
Comparative material 2 ...
Material A
Material B
Material C 1.51
1.30
1.59
1.60
1.68 1.91
2.05
2.03
2.02
1.99 1.95
1.85
1.90
1.87
1.85 0.61
0.08
0.19
0.26
0.32

Table A also shows that the calcium algmate-containing layer of comparative material 2 considerably reduces the magenta dye density drop, but leads to a decrease in the cyan dye density. The recording materials A, In contrast, B and C with a complexing agent in the blue-green dye developer layer show a Increase in cyan dye density. Furthermore, in the recording materials containing a complexing agent the decrease in the purple dye density compared to comparison material 1 is significantly less.

Example 2

(Use of the complexing agent in the alkaline working solution)

There were recording materials according to the preparation method described in Example 1 for Comparative Materials 1 and 2 were prepared; d. that is, it became a recording material without a calcium alginate barrier layer (Comparative material 1) and a recording material having such a barrier layer (Comparative material 2) produced.

Samples of the recording materials were exposed and developed as described in Example 1, however, with the exception that the alkaline working solution used is 1 percent by weight of that shown in Table 2 listed complexing agent contained.

Table B.

Recording material Addition to
Work solution Blue green
dye density
J ^ max Purple dye
density drop Comparative material 1
Comparative material 2
Comparative material 2
Comparative material 2
Comparative material 2 no
no
Ethylene diamine tetra
acetic acid
no
-Galacton-γ-lactone 1.52
0.63
1.18
0.90
1.38 0.53
0.03
0.22
0.07
0.28

From the data in Table B it can be seen that the complexing agents are advantageously in the alkaline Working solution can be applied to obtain high cyan dye densities while the magenta dye density drop is kept within acceptable limits.

Example 3

(Use of complexing agents
in the image receiving sheet)

Recording materials were produced as described in Example 1 for the production of comparison materials 1 and 2, ie a recording material without a calcium alginate intermediate layer (comparison material 1) and a recording material with such an intermediate layer (comparison material 2) were produced. Samples of the recording materials were exposed and developed as described in Example 1, with the exception, however, that the image-receiving sheet which was used for developing the comparative material 2, in the polyvinyl alcohol layer between the layer containing a mordant and the layer containing an acid releasing layer, tetrasodium ethylenediaminetetraacetic acid in contained such a concentration that 100 mg of tetrasodium ethylenediaminetetraacetic acid were accounted for on a carrier area of 0.09 m ^2. The results of the density measurements are given in Table C below.

009546/314

Table C.

Recording material Complexing agents
in the image receiving sheet Blue green
dye density
D _m ax Purple dye
density drop Comparative material 1
Comparative material 2
Comparative material 2 no
no
Tetrasodium salt
the ethylenediamine
tetraacetic acid 1.41
0.82
1.16 0.46
0.21
0.28

Table C shows the advantageous effect of the complexing agents in the transfer of Color developer images on an image-receiving sheet clearly.

Example 4

(Development of a recording material
with two intermediate layers)

A recording material of the type shown in FIG. 2 produced structure shown by on a a cellulose acetate film base having an adhesive layer is applied successively to the following layers became:

Shift no.

Shift no.

Cyan dye developer layer
speaking of layer # 21 of FIG. 2)
A dispersion of 5,8 - dihydroxy-1,4- bis - [(ß- hydroquinonyl - cc - methyl) - ethylamino] - anthraquinone dissolved in Nn-butylacetanilide as a blue-green dye developer in gelatin was applied to the substrate in such a way that about 0.09 m ^{2 of} carrier area, 146 mg of dye developer and 221 mg of gelatin were used. The coating compound used also contained D-galacton-γ-lactone as a complexing agent and 4'-methylphenylhydroquinone as an auxiliary developer in such concentrations that 60 mg of complexing agent and 10.5 mg of auxiliary developer were used ^{on approximately 0.09 m a carrier surface.}
Red-sensitive emulsion layer (corresponding to layer No. 22 of FIG. 2)
A red-sensitized, ausentwickelbare gelatin silver bromoiodide negative emulsion layer was coated so that 219 mg of silver and 86 mg of gelatin was accounted for about 0.09 m ^s bearing surface on the layer no. 1,. Sodium alginate layer (corresponding to layer no. 23 of Fig. 2)

Sufficient sodium alginate was applied to layer no. 2 that 27 mg of sodium ^{alginate were applied to approximately 0.09 m 2 of support surface.} Purple dye developer layer (corresponding to layer No. 24 of FIG. 2)
A dispersion of 4-isopropoxy-2- [p- (jö-hydroquinonylethyl) -phenylazo] -l-naphthol dissolved in Nn-butylacetanilide as a purple dye developer in gelatin with a content of calcium chloride was applied to the sodium alginate layer in such a way that about 0 , 09 m ^a carrier area 64 mg of dye developer, 74 mg of gelatine and 18 mg of calcium chloride were eliminated. The calcium chloride reacted with the sodium alginate in the adjacent one below

the layer with the formation of a calcium alginate intermediate layer, corresponding to the layer 23 'of FIG. 2.

Green-sensitive emulsion layer (corresponding to layer No. 25 of FIG. 2)

A green-sensitized, developable gelatin-silver broiodide negative emulsion was applied to layer no. 4 in such a way that 34 mg of gelatin and 103 mg of silver accounted for ^{about 0.09 m a support area.}

Sodium alginate layer (corresponding to layer no. 26 of Fig. 2)

So much sodium alginate was applied to the green-sensitive emulsion layer, that at about 0,09 m ² support surface 27 mg Na

trium alginate was omitted.

Yellow dye developer layer (corresponding to layer no. 27 of FIG. 2)

A dispersion of l-phenyl-3- (N-n-hexylcarb-

oxamido) -4- [p - (^ - hydroquinonylethyl) phenylazo] -5-pyrazolone as a yellow dye developer in gelatin containing calcium chloride was applied to the sodium alginate layer in this way applied that to about

0.09 m ^{2 of support area,} 40 mg of dye developer, 72 mg of gelatin and 18 mg of calcium chloride were used. The calcium chloride sat with the sodium alginate in the adjacent layer below under bil

formation of a calcium alginate salt intermediate layer26 ' between the yellow dye developer layer 27 and the sodium alginate layer 26 µm.

8 Blue-sensitive emulsion layer (corresp

according to layer no. 28 of Fig. 2)
A developable gelatin-silver bromoiodide emulsion with its own blue light sensitivity was applied to the yellow dye developer layer in such a way that approx

0.09 m ^{2 of support area,} 69 mg of silver and 40 mg of gelatin were used.

Top layer (corresponding to layer no.29

from F i g. 2)

A dispersion of the auxiliary developer 4'-Me-

ethylphenylhydroquinone in gelatin was applied to the blue-sensitive emulsion layer in such a way that 10.5 mg of auxiliary developer and 26 mg of gelatin were used ^{on about 0.09 m 2 of support surface.}

The recording material produced in the manner described is shown in the following table D

denoted by A. For comparison purposes, a corresponding recording material designated B was produced, the blue-green dye developer layer of which, however, did not contain any complexing agent, ie no D-galacton-γ-lactone. In addition, a recording material constructed like recording material B was produced, but instead of the sodium alginate layer between the green-sensitive silver halide emulsion layer and the yellow dye developer layer, it contained a gelatin layer which was applied to the green-sensitive silver halide emulsion layer in such a way that about 0.09 m ^{2 of support area} accounted for 140 mg of gelatin (Layer # 6) and in which there was no calcium chloride in the yellow dye developer layer (Layer # 7). This recording material is designated by C in Table D. Samples of the recording materials were then exposed and developed as described in Example 1, except that the image receiving sheets and the recording materials IV were left in contact for _{4 minutes.}

Table D shows the values of the magenta dye density drop and the yellow dye density drop caused by the yellow dye developer in the green-sensitive emulsion layer and the magenta dye developer in the red-sensitive emulsion layer. Density values for the cyan dye D _{max of} the dye images are also given.

Table D. Table E.

Complexing agent contained in the working solution

15th

25th

30th

on
drawing
material Blue green-
dye
density Purple-
dye-
density-
waste*) Yellow
dye-
density-
waste**) A.
B.
C. 1.40
1.00
1.80 0.07
0.07
0.11 0.43
0.42
0.80

35

40

*) This value is made up of: purple-red _{dye density i) maA:} minus density of the first exposure step at a density of 0.3 on the red scale.

**) This value is made up of the yellow dye density Dmax minus the density of the first exposure level at a density of 0.3 on the yellow scale.

Example 5

Several recording materials of the type designated as comparative material 2 in Example 1 were used The calcium alginate interlayers between the red-sensitive silver halide layer and the magenta color developer layer (see Fig. 1). The recording materials were exposed as in Example 1 b3sohrieb2n and developed, but with the alkaline working solution various listed in Table E. Complexing agents were added.

The results of the density measurements are shown in Table E as Δ D _max . This is the increase in the cyan dye density D _max that was achieved by using the complexing agents in the alkaline working solution. Unless otherwise stated, 1 percent by weight of complexing agents, based on the weight of the alkaline working solution, was used in each case. Unless otherwise stated, the development time was 2 minutes.

1. Gluconic acid (1 minute)

2. n-Propyl-D-gluconate pentaacetate

3. Methyl D-gluco-D-gulo-heptonate hexaacetate

4. D-gluconamide pentaacstate (1 minute) ...

5. Isopropyl D-gluconate pentaacetate

(1 minute)

6. Methyl glycolate D-gluconate pentaacetate ..

7. D-Gluco-D-gulo-heptonamide hexaacetate (1 minute)

8. Ethyl D-gluconate pentaacetate

9. Methyl D-gluconate pentaacetate

10. Gulon lactone

11. Sulphosalicylic acid, 2 percent by weight

(1 minute)

12. Gluconheptonic acid, 1.5 percent by weight (1 minute)

13. Sodium guanylate, 1.5 weight percent (1 minute)

14. Odenosine triphosphate sodium salt (1 minute)

15. Potassium hydrosaccharate (1 minute)

16. Dioxybenzenesulfonate disodium salt

(1 minute)

17. Methyl L-arabonate

18. Disodium anthranilic acid-N ^ '- diacetate

19. Pentasodium diethylenetriamine pentaacetate

20. glycolic acid

21. D, L-malic acid

22. tartaric acid

23. Citric acid

24. Sulphosalicylic acid

25. Aminosalicylic acid

26. Salicylic acid

27. Aminobarbituric acid-N, N'-diacetic acid

28. L-malic acid

29. D, L-mandelic acid

30.Methyl L-erythronate (1 minute)

31. D-lyxonamide

32.D-arabonamide (1 minute)

33. Methyl L-arabonate tetraacetate

34. D-Arabon-γ-lactone

35. D-gluconamide

36. Glucono-o-lactone

37. Methyl 2,4-3,5-dimethylene-D-gluconate ..

38. Methyl D-galactonate

39. D-galactono-y-lactone

40. Ethyl D-mannoate

41. D-gluco-D-gulo-heptoamid

42. D-Gluco-D-gulo-heptono-y-lactone

AD _n ,

0.35 0.22

0.28 0.40

0.26 0.32 0.36 0.74

0.37 0.71 0.51

0.87 0.86

0.58 0.37 0.65 0.71 0.34 0.17 1.11 1.02 0.46 0.77 0.93 0.83 0.58 0.28 0.34 0.52 0.13 0.39 0.87 0.45 1.04 1.04 0.37 0.71 0.78 0.75 0.43

As can be seen from Table E, the most varied of complexing agents are suitable for implementation of the method of the invention.

Claims (8)

Patent claims: 1. Diffusion transfer process for the production of colored images, in which an imagewise exposed, color photographic recording material, consisting of a layer support and at least two applied color-forming the units each consisting of a silver halide emulsion layer and a dye developer layer arranged immediately adjacent thereto and by water-insoluble alkali permeable Interlayers are separated from each other, of which at least one consists of a water-insoluble Salt made from a polyvalent metal cation and a water-soluble polymer with Free carboxylate anions consists or contains such, the intermediate layer for the color developer is less permeable in aqueous-alkaline solution than the water-soluble polymer, that was used to build up the layer, treated with an alkaline working solution, here developed the latent images in the exposed areas of the silver halide emulsion layers which Dye developers are set in the exposed areas and the dye developers are set in the undeveloped areas Districts are transferred to a picture receiving sheet by diffusion, thereby characterized by the treatment or development of the material in the presence an organic, alkali-soluble complexing agent for the polyvalent metal. 2. Diffusion transfer method according spoke 1, characterized in that as Complexing agents aminocarboxylic acids, oxyalkylamino acids, sulfhydrylamino acids, aminosulfonic acids, Aminophosphonic acids, oxycarboxylic acids or ethylenediaminetetraacetic acid are used. 3. Diffusion transfer method according to claim 1, characterized in that as Complexing agents Compounds of the general formula 35 40 45 used in which mean: M and Z each represent a hydroxyl group or an alkoxy group of the formula O
- OC- R wherein R represents an alkyl radical or an aryl radical, X is a hydrogen atom, a methoxy group, a group of the formula 55 60 - CH ₂ OCR ² wherein R ^{2 represents} an alkyl radical or an aryl radical, Y is a carboxy group, a carbamyl group or a group of the formula -COR ¹ wherein R ^{1 represents} an alkyl radical, A a methoxy group, a carbamyl group, a carboxy group, a group of the formula - COR ¹ wherein R ^{1 represents} an alkyl radical, or a group of the formula .0 - CH ₂ OCR ² wherein R ^{2 represents} an alkyl or an aryl radical, m is an integer from 2 to 3, η is an integer from 1 to 5 and 0 is an integer from 0 to 2, where at least one of the groups A, Y or Z is a carbamyl or an ester radical. 4. diffusion transfer method according to claim 1, characterized in that as Complexing agents D-galacton-y-lactone, D-arabonlactone, Methyl 1-arabonate or methyl D-gluconate pentaacetate used. 5. diffusion transfer method according to claim 1, characterized in that the Complexing agent added to the alkaline working or developer solution or to the image receiving layer incorporated. 6. diffusion transfer method according to claim 1, characterized in that the Complexing agent in the form of a layer on the side of the color photographic recording material applies, which has the intermediate layer or intermediate layers. 7. diffusion transfer method according to claim 1, characterized in that a recording material is used, which has a calcium alginate layer between the color-forming Red-sensitive and green-sensitive gelatin-silver halide emulsion layer units contains. 8. diffusion transfer method according to claim 1, characterized in that a recording material is used, the three superposed color-forming units of red-, green- and blue-sensitive gelatin-silver halide emulsion layers contains, wherein the color-forming unit with the blue-sensitive gelatin-silver halide emulsion layer furthest away from the substrate and the color-forming one Unit with the red-sensitive gelatin-silver halide emulsion layer next to the support is arranged and in which alkali permeable, water-insoluble layers between the units are arranged from calcium alginate and in which the dye developer continues to be one of the Color of the gelatin silver halide genide emulsion layer of light to be absorbed essentially have complementary color and finally between the support and the calcium alginate layer, which is between the one blue-green dye developer and one pur- purple dye developer-containing layer is arranged, an organic, alkali-soluble complexing agent for calcium ions is housed ^{in a concentration of about 25 to 150 mg complexing agent per 0.09 m 2 of substrate surface.} 1 sheet of drawings 009 546/314