CH630732A5 - PHOTOGRAPHIC LIGHT-SENSITIVE SILVER HALOGENIDE MATERIAL WITH AT LEAST ONE DYE-CONTAINING REAR LAYER. - Google Patents

Description

The object of the present invention is to provide photographic silver halide materials with at least one dye-containing layer (filter or antihalo layer) 35 in which the dyes have sufficient absorption and are bound diffusion-resistant and likewise do not diffuse the mordants and with hydrophilic colloids, in particular Gelatin and latices are well tolerated and give no precipitations. 40

It has now been found that when the binders present in the colored layers are crosslinked with special hardening agents, an excellent pickling effect can be obtained on the acidic dyes present in this layer and, at the same time, good compatibility with the latices present in these layers can be achieved.

The present invention relates to a photographic light-sensitive silver halide material which contains at least one photographic silver halide emulsion layer and at least one 50 colored, silver halide-free layer on a photographic support, characterized in that this layer (1) contains at least one water-soluble organic dye containing acid groups, one with one

(2) Crosslinking agent which has 2 or 3 reactive groups capable of reacting with the binder and at least one tertiary amino group which may be part of the reactive groups

(3) colloidal binder and

(4) contains a water-insoluble polymer 60.

The present invention furthermore relates to a process for the preparation of photographic light-sensitive silver halide material, characterized in that at least one casting solution is applied to the photographic support

(1) at least one water-soluble organic dye containing acidic groups,

(2) a curing agent which has 2 or 3 reactive groups capable of reacting with the binder and at least one tertiary amino group which may be part of the reactive groups,

(3) a crosslinkable, water soluble colloidal binder and

(4) contains a water-insoluble polymer.

Particularly suitable dyes are those which are readily water-soluble, have a high molar extinction coefficient and can be removed from the material as completely as possible in the usual photographic processing processes, in particular by decolorization. Furthermore, the dyes should be photographically inert, i.e. H. they should not adversely affect the photographic layers, which z. B. can manifest itself in a reduction in sensitivity or in increased fog. Furthermore, the dyes must be easy to pickle, otherwise the dye will not remain fixed in the colored layer and then z. B. the reproducibility of the colors (color balance between blue, green and red) can be disturbed. Particularly suitable dyes belong to the classes of oxonol, styryl and triphenylmethane dyes, those with one or more sulfonic and / or carboxylic acid groups being preferred.

The oxonols are anionic polymethine dyes which have the following grouping:

The last two carbon atoms at the end of the poly-methine chain are part of a heterocycle. This heterocycle can e.g. B. a pyrazolone, a hydroxypyridone, a pyrazolidinedione (3,5) or a barbituric or thiobarbituric acid ring.

Dyes of this type are e.g. B. from British Patent 506,385, U.S. Patents 3,247,127, 3,379,533 and 3,653,905, British Patents

1 278 621 and 1 466 836 and the German Offenlegungsschrift

2,711,450 are known.

Suitable styryl dyes are e.g. B. those containing an indole core (US Pat. No. 3,652,283), as well as further styryl dyes as are known from US Pat. Nos. 2,298,733, 2,622,082 and 3,884,487 and German Offenlegungsschrift 2,517,143.

Triphenylmethane dyes are e.g. B. from British patents 790023 and 1 025 567, German patents 1 038 395 and 1 447 792 and US patents 1 912 792.2 147 112.2 150 695.3 018 177 and 3 382 074 are known.

In order to obtain a good antihalation and, if appropriate, filter action in the entire sensitivity range of the photographic emulsions used, the dyes are generally used in the form of mixtures. Usually, a yellow, a purple and a blue-green dye are mixed, it being possible for the densities obtained in the layer to be the same or different in the different regions.

Compounds which contain two or more groups which can react with the colloidal binder under customary conditions are generally referred to as hardening agents because they give the binder layers greater mechanical strength. A number of different types of hardening agents are known to the person skilled in the art. Within the scope of the present invention, Här

630 732

4th

described for colloidal binders which lead to a mechanical solidification of the binders and which also give the crosslinked (hardened) binder layers of a photographic light-sensitive silver halide material a mordant effect on the acidic dyes present in these layers.

Suitable hardeners are those which, in addition to good solubility in water, have a good hardening action in the pH range from 4 to 7, since the likewise desired pickling action can practically only be achieved at pH values below 7.

Hardening agents of this type are e.g. B. known from the following patents: French patents 871 377, 1 196 359 and 1 270 785; U.S. Patents 2,615,889, 3,102, 112, 408, 198,3,490,911 and 3,977,881, and German Offenlegungsschrift 2,514,425.

Particularly suitable curing agents correspond to the formula r,

A — R3 — N-

A — R;

N

/ ch2-

-ch,

\

or

CH;

r,

-cii2

NO.

/ 6

N

A - Rj ~ c - R £ - A1

r4

wherein Ri alkyl having 1 to 5 carbon atoms, optionally substituted with aryl, alkoxy, acylamino, sulfonylamino, aryloxy, cyano or dialkylamino, aryl, optionally substituted with alkyl, alkoxy, acylamino, sulfonylamino, halogen, hydroxy, cyano or dialkylamino, cycloalkyl , -R2A1 or -R3A, R2 and R3 are alkylene of 1 to 6 carbon atoms, R4 is hydrogen, alkyl of 1 to 6 carbon atoms or aryl, Rs and Re are aryl of 1 to 6 carbon atoms, -R2A1 or -R3A or Rs and Re together with the nitrogen atom to which they are attached form a 5- or 6-membered heterocyclic ring which may contain further heteroatoms, and A and Ai represent the methanesulfonic acid group, epoxy groups, the vinylsulfonyl group, the aldehyde group or groups of aldehyde-bisulfite adducts, acetal or anil groups or the N-acryloyl urea, N- (β-chloropropionyl) urea or aziridinyl group.

The substituent Ri is alkyl having 1 to 5 carbon atoms, where alkyl can be both straight-chain and branched, such as. B. methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, tert-butyl, n-amyl, iso-amyl and tert-amyl. Aryl, especially phenyl, alkoxy, e.g. B. with 1 to 4 carbon atoms (methoxy, ethoxy, propoxy or butoxy), acylamino, in particular with 2 to 5 carbon atoms in the acyl part and preferably acetylamino (CH3CONH-), sulfonylamino (-SO2NH2), aryloxy, especially phenoxy, cyano or dialkylamino in question come in which alkyl may contain 1 to 4 carbon atoms, such as. B. dimethyl, diethyl, dipropyl or dibutylamino or dialkylamino radicals with two different alkyl radicals on the nitrogen atom; Ri is also aryl, in particular phenyl, the substituents on the arylrin being alkyl (C1-C4), alkoxy (C1-C4), acylamino having 2 to 5 carbon atoms in the acyl part, 5 preferably acetylamino, sulfonylamino (-SO2NH2), halogen, such as fluorine , Chlorine or bromine, hydroxy, cyano or dialkylamino z. B. with 1 to 4 carbon atoms per alkyl radical: are; Ri is also cycloalkyl with 4 to 10 carbon atoms, preferably cyclopentyl and cyclohexyl; Ri also represents the groupings -R2A and -R3A, where R2 and R3 are straight-chain or branched alkylene with up to 6 carbon atoms, e.g. B. -CH2- or - (CH2) e- and corresponding isomeric groups. The meanings for A and Ai are given below.

15 The substituent R4 is hydrogen, alkyl having 1 to 6 carbon atoms, where straight-chain and branched alkyl radicals come into question, and aryl, especially phenyl, which may optionally be substituted, for. B. with alkyl (C1-C4).

The substituents Rs and Re can be identical or different from one another and are alkyl having 1 to 6 carbon atoms, where the alkyl radicals can be straight-chain or branched. Furthermore, Rs and Re have the meaning -R2A1 or -R3A or together with the nitrogen atom to which they are attached they form a 5- or 6-membered optionally further -25 heteroatoms, such as, for. B. nitrogen, oxygen or sulfur containing heterocyclic ring. The saturated rings such as. B. piperidine, piperazine, pyrrolidine, morpholine or thiomorpholine.

The symbols A and Ai represent the reactive groups 30 of the curing agents. The methanesulfonic acid group (CH3SO3-), epoxy groups, in particular 1,2-ethyleneoxy or 1,2-propyleneoxy groups, the vinylsulfonyl group (CH2 = CHS02-), the aldehyde group are suitable or groups of aldehyde derivatives such as aldehyde bisulfite adducts, acetal

^ OR .R

(~ HC ^ 0R) or anil groups (-N = C ^);

R

furthermore the N-acryloylurea-40 (CH2 = CHCONHCONH-), the N- (ß-chloropropionyl) urea (CI-CH2CH2CONHCONH-) and the aziridinyl group

(-c:

45

'n

Preference is now given to curing agents of the formulas (1), (2) and (3) in which R 1 is alkyl having 1 to 5 carbon atoms or phenyl, R 2 and R 3 are alkylene having 1 to 4 carbon atoms, R 4 50 is hydrogen, alkyl is 1 to 4 Is carbon atoms or phenyl, Rs and Re are alkyl having 1 to 4 carbon atoms, -R2A1 or -R3A1 or Rs and Re together with the nitrogen atom to which they are attached are a 5- or 6-membered, optionally oxygen, sulfur or other Form nitrogen-containing heterocyclic ring and A and Ai are the methanesulfonic acid group, epoxy group, the vinylsulfonyl group, the aldehyde group or groups of aldehyde bisulfite adducts which are N-acryloylurea or N- (β-chloropropionyl) urea group.

60 The hardening agents of the formula are particularly valuable

[C1CH2CH2C0NHC0NH (CH2) 312 x, wherein

65 X -N- or -n 'N- and R-, alkyl-r \ / 7 y

(5)

R-

5

630 732

having 1 to 5 carbon atoms or phenyl and of the formula

[CH2 = CHCONHCONH (CH2) 3] 2X

where X is -N- or -N ^ N-

R7 (6)

and R7 is alkyl of 1 to 5 carbon atoms or phenyl.

Examples of preferred colloidal binders are gelatin, gelatin derivatives, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol or mixtures thereof.

Gelatin is particularly suitable as a layer-forming colloidal binder. Gelatin can be obtained by various methods. It is usually produced by alkaline or acidic degradation of skin or bone collagen, gelatins having different properties being obtained depending on the type of production. So z. B. the isoelectric point is significantly influenced by the type of degradation. It has been shown that gelatins with an isoelectric point above 7, which generally occur in the case of acidic degradation, are particularly suitable according to the invention, since they themselves have a certain pickling effect.

In addition, low isoelectric point gelatins and other hydrophilic colloids crosslinkable with the curing agent can also be used. Combinations of gelatins with different isoelectric points or of gelatin with other hydrophilic colloids can also be used.

The gelatin can be partially or completely replaced by a so-called gelatin derivative, which can be obtained by reacting or modifying the functional amino, imino, hydroxyl or car-boxy groups in the gelatin molecule with a reactive compound, or by a graft gelatin compound, as is the case with grafting another polymer chain can be obtained on the gelatin molecule.

Suitable examples of compounds that can be used to prepare the gelatin derivatives are e.g. B. iso-cyanates, acid chlorides and acid anhydrides (U.S. Patent 2,614,928), vinyl sulfones (U.S. Patent 3,132,945,3,186,846) and polyalkylene oxides (U.S. Patent 3,322,553).

A variety of polymers or copolymers can be used for grafting onto gelatin, such as. B. polymers and copolymers of vinyl monomers, such as acrylic acid, methacrylic acid or their derivatives, for. B. esters, amides or nitriles or styrene.

The water-insoluble polymers used as component (4), which in the form of very small particles, (latices) z. B. as a rule for the purpose according to the invention on average less than 1 (im, preferably less than 0.5 (im) are generally prepared by emulsion polymerization of suitable, in particular of ethylenically unsaturated, monomers. The polymers used according to the invention are said to have no or only have a low swelling in water and have a refractive index that comes as close as possible to that of dried gelatin, and should also be easy to manufacture and inexpensive.

Such homopolymers and copolymers are known from the large number of publications, e.g. B. from German Offenlegungsschriften 2 040 875.2 048 455.2 218 218.2219 004.2 329 142,

2,357,853.2,421,859.2,423,826 and 2,515,379, French Patents 1,234,458 and 1,364,027, British Patents 1,053,043.1,348,815 and 1,399,484 and U.S. Patents 2,376,005, 2 852 386.2 865 753.3 488 708,

3,508,925 and 3,867,152.

Preferred polymers are those which are derived from vinyl, acrylic, diene or styrene compounds or mixtures of these compounds, in particular from acrylic or methacrylic acid and their salts, esters and amides, from polybasic, unsaturated acids having 3 to 6 carbon atoms, from Acrylonitrile, of vinyl esters with 2 to 12 carbon atoms in the acyl radical, of vinyl halides, of butadiene or substituted butadienes or of styrene and substituted styrenes or mixtures of these monomers.

To produce the homo- and copolymers, acrylic and methacrylic acid can be used as free acids or as z. B. alkali or alkaline earth metal salts, in particular as sodium, potassium, magnesium, calcium or strontium salts. As esters of these acids, alkyl esters with 1 to 12 carbon atoms, for example the methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, tert-butyl, pentyl, hexyl, octyl -, 2-ethylhexyl, decyl or dodecyl ester can be used. Furthermore, esters of unsaturated alcohols, such as allyl (meth) acrylate, hydroxyalkyl esters with 2 to 10 carbon atoms, in particular 2-hydroxyethyl (meth) acrylate and alkoxyalkyl esters with 2 to 10 carbon atoms each in the alkyl and alkoxy part, in particular 2-ethoxyethyl (meth) acrylate.

In addition to acrylic and methacrylamide, the N-substituted or N, N-disubstituted (meth) acrylamides are suitable as amides.

In addition to alkyl with z. B. 1 to 10 carbon atoms also hydroxy alkyl with 1 to 10 carbon atoms possible.

The polybasic unsaturated acids with 3 to 6 carbon atoms which are suitable for the preparation of the water-insoluble homo- and copolymers are, for example, maleic, fumaric, itaconic, mesaconic, citraconic, methylene malonic or aconitic acid.

Acrylonitrile can also be used as a monomer. Other suitable monomers are vinyl esters with 2 to 12 carbon atoms in the acyl part, for example vinyl acetate, vinyl propionate, vinyl butyrate or vinyl laurate, vinyl halides, such as vinyl fluoride, vinyl chloride, vinylidene fluoride or vinylidene chloride, butadiene, substituted butadienes, such as, for example, 2,3-dimethyl l, 3-butadiene, 2-methyl-l, 3-butadiene (isoprene) or 2-chloro-l, 3-butadiene (chloroprene), styrene or substituted styrenes such as methylstyrene, dimethylstyrene, ethylstyrene, chlorostyrene, 2,4 -Dichlorostyrene, 2,5-dichlorostyrene and divinylbenzene, also a-methylstyrene.

Particularly suitable polymers of component (4) are derived from acrylic or methacrylic acid, their alkyl esters with 1 to 10 carbon atoms, their hydroxyalkyl esters with 2 to 6 carbon atoms, from acrylonitrile, from vinyl esters with 2 to 5 carbon atoms in the acyl part of vinyl chloride and vinylidene chloride , Butadiene, styrene or mixtures of these monomers.

Homo- or copolymers of acrylic and methacrylic acid, their alkyl esters with 1 to 8 carbon atoms, vinyl acetate, styrene or isoprene are particularly preferred.

These polymers are generally prepared by the known methods of emulsion polymerization at temperatures of, for. B. 20 to 100 ° C, in the presence of radical-forming polymerization catalysts (persulfates, azo compounds) and optionally under pressure. The polymerization generally gives a latex with a solids content of 20 to 55 percent by weight.

The photographic material according to the invention is produced by known methods by applying the various layers to a suitable support material.

The casting solutions used for the production of the colored layers (filter layers or anti-halo layers on the front and back of the carrier material) contain

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

630 732 6

Most preferably 2-80 mg / l of any water-soluble solution present are cyan-forming couplers in the red-sensitive dye containing acidic groups, 0.1-10 g / l of hardening silver halide emulsion layer, magenta-forming couplers, 30-100 g / 1 of the colloidal binder, 6-40 g / 1 of the water-insoluble polymer in the green-sensitive silver halide emulsion layer and optionally further and yellow-forming couplers in the blue-sensitive silver halo usual components. s gene emulsion layer included. If necessary, you can

However, the amount of dye in the colored layers can change these combinations.

depending on the desired absorption density in the range of 10 mg. The photographic photosensitive

up to 2 g per m2. The ratio of crosslinked colloidal silver halide materials after exposure of the binder to water-insoluble polymer can be about 1:10 according to the customary processing methods and can be up to 1: 1. The thickness of the colored layers is in general. For the production of color images, for example the negative general can be about 1 μm, but it can also be a smaller or larger positive method, the color reversal method or a method for producing direct positive images.

The colored filter or antihalation layers in the invented material can prevent glass plates and films made of photographic materials according to the invention. The polymers, such as polyalkyl (meth) acrylates, polystyrene, are outstandingly suitable as support materials for the inventive photographic materials Halation and the formation of light polyvinyl chloride, polycarbonates, polyesters, e.g. B. Polyethy. They do not cause any harmful effects, such as lenterephthalate, polyamides or semisynthetic polymers, desensitization, damage to the latent images, increases such as cellulose acetate, cellulose nitrate or cellulose acetate butane or the veil in the photographic emulsion counters, coated papers and other transparent and opaque layers. with which "they are contacted. The possible in the carrier. 20 colored layers of existing dyes or dye

The colored layers according to the present invention are very well fixed by the pickling action of the inventive coating, in addition to the dyes mentioned, other wetted binders. On the other hand, known dyes or pigments can be included, provided that these do not adversely affect the behavior of the layers during processing of the exposed material. remove easily and quickly, e.g. B. by detaching or reduc-

Other additives can e.g. B. antistatic, matting agent 25 tive decolorization, so that these materials can also be used for rapid or surface-active aids. work (development) processes are suitable.

The colored filter or antihalo layers can consist of one or more layers in the following examples. Components (1) to (4) for the production of backing layers

The composition of each layer e.g. B. regarding the nature of the photosensitive photographic according to the invention and the amount of dyes, binder and water-30 material used:

Insoluble polymer and other additives can be strong. Parts are parts by weight and percentages are

vary. Likewise, the thickness of the layers can be different.

be. Some of these layers can be colorless. For example, the colored layer can be formed as a back layer, which is either directly on the carrier under 35

one or a plurality of further layers or component (1) (dyes)

the most distant layer from the support, i. H. the extreme

Be shift. If there are three or more layers, yellow:

the colored layers can also be present between the other 1. 1- (p-sulfophenyl) -3-methyl-4- (isopropylbenzylidene) pyrazo layers. 40 Hn-5-one

The colored backing layer is preferably applied directly to the back of the backing material and a methinoxonol 2. bis- [1 - (p-sulfophenyl) -3-methyl-pyrazolin-5-one (4)] - mono

Top layer, which can be colorless, colored or matt, 3.4 - [(3-ethyl-2 (3H) -benzoxazolylidene) -ethylidene] -3-methyl-1-can then be applied to this backing layer. The pho- (p-sulfophenyl) pyrazolin-5-one tographic silver halide emulsions for use with 45 4.2- (2,4-disulfobenzylidene) -2,3-dihydrobenzo (b) -thiophen-3-one for the preparation of the photographic 5 according to the invention Bis- [l- (m-sulfophenyl) -3-methyl-pyrazolin-5-one (4)> mono materials can be prepared by various known methinoxonol processes, so that the properties suitable for the use of the photographic materials are different Orange:

surrender. 50 6. l- (p-sulfophenyl) -3-methyl-4- (p-dimethylaminobenzylide) -

For example, the methods and methods as described, for example, in pyrazolin-5-one in C.E.K. Mees & T.H. James, The Theory of the Photo- 7. l- (2-Chloro-5-sulfophenyl) -3-methyl-4- (p-dimethylaminoben-graphic Process, 3rd Edition, MacMillan Co., New York (1966) cyliden ) -pyrazolin-5-one or in P. Glafkides, Chimie Photographique, 2nd edition, Photo-cinema Paul Mon tel, Paris (1957) 55 Magenta:

the. 8. C.I. Acid violet 19 (CI. = Color Index)

The suitable silver halides are e.g. B. Silver chloride, Sil- 9. Bis {l- (p-carboxyphenyl) -3-methyl-pyrazolin-5-one- (4)] - tri-beryl chloride bromide, silver bromide, silver iodide bromide, Silberjomethinoxonol didchloridbromid, whereby the halogen content is not limited to 10. bis- [In-butyl-3-carboxymethyl-hexahydro-2,4,6-trioxo-pyri-ist. 60 midin- (5)] - trimethinoxonol

The colored filter or antihalation layers can be found in 11. bis- [l- (p-sulfophenyl) -3-carboxy-pyrazolin-5-one- (4)] - trimethi-multilayer, multicolor photographic materials noxonol, which at least contain two layers with different 12.- [1- (p-sulfophenyl) -3-methyl-pyrazolin-5-one (4)] - trimethi spectral sensitivity on a support, noxonol z. B. at least one red-sensitive silver halide emulsion 13. Bis- [l-phenyl-3-carboxy-pyrazolin-5-one (4)] trimethinoxonol layer, a green-sensitive silver halide emulsion layer and / or a blue-sensitive silver halide emulsion cyan :

sion layer. The arrangement of these layers can be varied as desired, depending on the purpose of use. In general methinoxonol

7

630 732

15. Bis- [1-n-butyl-3-carboxymethyl-hexahydro-2,4,6-trioxo-pyri- 18.4- [3-methyl-2 (3H) -benzoxazolylidene) -butenylidene] -3-methyl-

midin- (5)] - pentamethinoxonol 16. Bis {l- (p-sulfophenyl> 3-carboxy-pyrazolin-5-one- (4)] - penta-methinoxonol

1 - (p-sulfophenyl) pyrazolin-5-one 19. Bis- (p-diethylaminophenyl) -3,4-bis (sulfomethyl) phenylmethine

17. bis- [l- (2,5-dichloro-4-sulfophenyl) -3-methyl-pyrazolin-5-one- 5 20. C.I. Acid Green 5 C.I. No. 42095 (4)] - pentamethine oxonol 21st C.i. Acid Blue 22 Gl. No. 42755

2nd

Component (2) (hardening agent)

h2? \

h2c

n — ch2ch2so2ch2ch ^ -n <;

^ ch2

ch,

0

ch3n (ch2ch) 2

(de-ps 1 547 758)

(BE-PS 663 984)

3. (ch; f = chs02ch2ch2) 2 ~ n ^ ^ 3-

ch "

(U.S. Patent 3,409,911)

4. ch3s020ch2ch ^ n —ch2ch20s02ch3 (fr-ps 1 196 359)

5.

7.

8th.

9.

ch- ch,

N N-

ch,

I.

(dt-os2 514425)

(German OS 2 503 657)

[c1ch2ch2c0nhc0nh (ch2) 3j 2— n-

ch ~

I.

[ch2 = chconhconh (ch2) 3] 2 n- (dt-os2503657)

45

[ch2 = chconhconh (ch2) 3] 2 n n - (dt-os2503657)

[ch2 = chconhconh (ch2) 3] 2 n (us-ps3977881)

Component (4)

(water-insoluble polymer, as an aqueous latex)

1.Methyl methacrylate 70%, 2-ethyl hexyl acrylate 30%, polymer content 30%

2. Butyl acrylate 50%, styrene 50%, polymer content 40%

3.butyl acrylate 90%, methacrylic acid 10%, polymer content 21%

4. styrene 60%, isoprene 40%, polymer content 44%

5.Methyl methacrylate 100%, polymer content 30%

6.Vinylacetate 90%, 2-ethylhexyl acrylate 10%, polymer content 35%

example 1

Casting solutions with the composition given in Table 1 below are prepared as follows:

55 To 3.5 ml of a 6% solution of an alkaline-degraded gelatin with an isoelectric point of about 4.8, 0.1 ml of an 8% solution of saponin (wetting agent), 0.17 to 0. 33 ml (depending on the solids content, the casting solution at the end containing 68 60 to 70 mg latex in each case) latex (water-insoluble polymer), 4 ml deionized water, 0.5 ml 1% aqueous dye solution (for the dye 4 the concentration is 2.5%) and 1.2 ml of a 0.025 molar aqueous hardener solution are added and the pH is then adjusted to 5.0 ± 0.1 in-65 with acetic acid.

The casting solutions obtained in this way are then cast onto triacetate foils (subbed, on glass plates) with a size of 13 x 18 cm. The samples are then stored for one week at 43 ° C and 69% relative humidity.

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8th

Strips are cut from the samples and immersed in deionized water at 20 ° C for 30 minutes.

Table 1 contains the density decreases determined as a percentage of the density before treatment with water.

The results show that the layers according to the present invention have a significantly stronger pickling effect than the layers which have been hardened with a hardener which contains no free amino groups after the reaction with the gelatin. The comparison also shows that different types of acidic dyes can be very well pickled in the layers according to the present invention and that the pickling effect is only insignificantly influenced by the latex used.

Table 1

Sample No.

Dye hardener

latex

Decrease in density after 30 minutes in water

1

2nd

8th

5

51%

2nd

comparison

100%

3rd

3rd

7

1

27%

4th

comparison

99%

5

7

8th

5

45%

6

comparison

98%

7

11

8th

5

0%

8th

comparison

95%

9

16

7

2nd

0%

10th

comparison

87%

The comparative hardener corresponds to the formula cho

^ O-C N BF, U

\ / 4

N = C CH3

Example 2

Casting solutions are prepared and cast as described in Example 1, but instead of an alkaline-degraded gelatin, an acid-degraded gelatin with an isoelectric point of about 7.8 is used. The mixture is then stored and treated as described in Example 1.

Table 2 contains the components used and the observed decreases in density.

Table 2

Sample No.

Dye hardener latex

Decrease in density after 30 minutes

Sample No.

Dye hardener latex

Decrease in density after 30 minutes in water

18th

comparison

10%

19th

15

8 6

0%

20th

comparison

19%

The one from Example 10 is used as the comparative curing agent.

If the hardener (9) is used instead of the hardener (7) and (8), good results are also obtained which are comparable to those of the hardener 7 and 8.

15 Example 3

A casting solution is prepared as follows:

To 3.5 ml of a 6% aqueous gelatin solution, 0.5 ml of an 8% solution of saponin (wetting agent), 0.3 ml of a 1% solution 20 of the dye (11), 0.23 ml of latex (5), 4.0 ml of water and 1.2 ml of a 0.025 molar solution of hardener (8) are added, and the pH is then adjusted to 5.0 ± 0.1 with acetic acid.

The casting solution thus obtained is poured onto a 13 × 18 cm triacetate film 25 (which is glued to glass plates). The sample is then stored for one week at 45 ° C. and 69% relative atmospheric humidity and treated as described in Example 1. There is no decrease in density. This means that hardeners which have a tertiary amino group 30 in the molecule give good staining layers.

Example 4

Samples 3, 4, 13, 14, 15, 16, 29 and 20 were subjected to the following processing.

40

Develop temperature

Fix watering

Processing 1 27 ° C

105 seconds (developer 1) 60 seconds 60 seconds

Processing 2 37 ° C

25 seconds (developer 2) 25 seconds 25 seconds

Composition of processing solutions (amounts based on 1000 ml):

Developer 1 45 sodium sulfite, 31 g anhydrous

Potassium bromide 1.5 g hydroquinone 22 g metol so boric acid, 7.5 g crystallized

Potassium metabisul- 7.5 g fit

Paraformaldehyde 22 g 55 potassium carbonate -

Fixing bath:

Sodium thiosulfate, anhydrous potassium metabisulfite

Developer 2 40 g

7g

10g lg

30 g

160 g 25 g

water

60 After these processing steps, according to the

Invention samples 3, 13, 15 and 19 produced no higher

11

4th

8th

2nd

5%

Residual color than that of the corresponding comparative samples 4,

12

comparison

49%

14, 16 and 20.

13

10th

8th

3rd

0%

These results show that the acidic dyes

14

comparison

23%

65 under conventional processing conditions from Invention

15

19th

7

5

0%

remove it just as easily according to compound layers

16

comparison

24%

leave like layers hardened with a hardener

17th

20th

7

4th

0%

which contains no tertiary amino groups.

G

Claims (3)

630732 PATENT CLAIMS (1) at least one water-soluble organic dye containing acidic groups, (1) at least one water-soluble organic dye containing acidic groups, one with a 1. Photographic light-sensitive silver halide material which contains at least one photographic silver halide emulsion layer and at least one colored, silver halide-free layer on a photographic support, characterized in that this layer (2) a curing agent containing 2 or 3 reactive groups capable of reacting with the binder and at least one 20 has tertiary amino group, which is optionally part of the reactive groups, (3) a crosslinkable water soluble colloidal binder and (4) contains a water-insoluble polymer 25. 10. The method according to claim 9, characterized in that the casting solution is applied to the front and / or back of the carrier material. or r 35 It is known in certain layers of photosensitive 5.6 Materials containing silver halide, dyes N whose job it is to ensure that the I wanted to absorb light and thereby improve the image sharpness to a - r - C-R - A (filter layers, anti-halo layers). 3 2 1 40 These layers can be on the same side of the '' Carrier material such as the photosensitive silver halide R containing layers or as backing layers be educated. Backing layers or backing layers correspond, in which Ri alkyl with 1 to 5 carbon atoms, which is on the back of a photographic support, which is optionally substituted with aryl, alkoxy, acylamino, sulfo-45 on the front, the photographic (photosensitive) nylamino, aryloxy, Contains cyano or dialkylamino, aryl, given emulsion layers. Antihalo backing layers, if substituted with alkyl, alkoxy, acylamino, sulfonylamino, may additionally contribute to the prevention of halogen, hydroxy, cyano or dialkylamino, cycloalkyl, and the charging of the photographic material. -R2A1 or -R3A is, R2 and R3 are alkylene with 1 to 6 carbon atoms- Usually water-soluble, diffusing and atoms are, R4 is hydrogen, alkyl with 1 to 6 carbon atoms- so washable and / or bleachable men or aryl during processing is, Rs and Re alkyl with 1 to 6 carbon atom dyes used in these layers, since the material according to men, are -R2A1 or -R3A or R5 and Rö together with the processing no longer have an undesirable coloration nitrogen atom to which they are bound are a 5- or 6-link. However, these dyes have the disadvantage that they form a long-lasting contact of the colored backing layer with cyclic ring, which optionally contains further heteroatoms, and A and Ai form the methanesulfonic acid 55 with the light-sensitive layer, as is the case in storage sol group, Epoxy group, the vinylsulfonyl group, which is aldehyde-rather materials, diffuse locally into the photosensitive group or groups of aldehyde-bisulfite adducts, acetal layer and there the photogra- phic sensitivity or anil groups or the N-acryloyl urea, N- (ß-chlorinability This leads to undesired Flek-propionyD-urea or aziridinyl group of the processed material (cf., for example, DE-OS 2 517 143). 4. Photographic light-sensitive silver halide material. So as to overcome this disadvantage, the usual material according to claim 1, characterized in that a so-called pickling agent, colloidal binder gelatin, gelatin derivatives, methylcellu- added to the dye-containing layer as the acidic colorless in particular, hydroxyethyl cellulose, carboxymethyl cellulose, poly substances form a diffusion-resistant complex. Vinyll alcohol or mixtures thereof are used as dressing agents. compounds were used that have one or more pri- 5. Photographic light-sensitive silver halide 65 mary, secondary or tertiary amino groups, quaternary material according to claim 1, characterized in that the ammonium or phosphonium groups or guanidino water-insoluble polymers used are those which contained groups. Derive ethylenically unsaturated monomers under the usual conditions. (pH 4 to 8) these groups are mostly cationic 2. Photographic light-sensitive silver halide material according to claim 1, characterized in that the organic water-soluble dye is an oxonol, styryl or tri-phenylmethane dye. 3. Photographic light-sensitive silver halide material according to claim 1, characterized in that the hardening agent of the formula A - R. - NO. 2 - / CH2 CH A - R - N / N - R, - A CH — CH2 / 6. Photographic light-sensitive silver halide material according to claim 5, characterized in that the polymers have an average particle size of <1 µm. 5 7. Photographic light-sensitive silver halide material according to claim 1, characterized in that the colored layer is located on the back of the support material. 8. Photographic light-sensitive silver halide material according to claim 1, characterized in that the colored layer is a filter or antihalation layer. 9. A method for producing photographic light-sensitive silver halide material according to claim 1, characterized in that one on the photographic 's carrier applies at least one casting solution which (2) Crosslinking agent which has 2 or 3 reactive groups capable of reacting with the binder and at least one tertiary amino group which may be part of the reactive groups (3) colloidal binder and (4) contains a water-insoluble polymer. 3rd 630732 form and are capable of interactions with the anionic groups of the dyes. In the case of low-molecular mordants, the dye-mordant complex formed frequently fails. Such low molecular weight pickling agents have therefore not been able to prevail in practice 5. On the other hand, high molecular weight pickling agents that cannot diffuse themselves are much more advantageous. Such mordants, which are normally water-soluble polymers, are described, for example, in the following patents: US Pat. Nos. 2,548,564.2,675,316; Patents 1 245 952.1 249 591 and 1 249 592. Polymeric mordants normally bring about a significant reduction in the diffusion of the dyes present in the colored layers. However, it has the disadvantage that these polymers generally do not have a uniform molecular weight and, in turn, low-molecular weight components diffuse and can influence the photographic properties of the layer. The formation of such low molecular weight polymer components must therefore be avoided 20. It has also been shown that in casting solutions that simultaneously contain a so-called latex, i.e. H. contain a water-insoluble polymer in the form of very small particles, often coagulates with polymeric mordants which lead to an undesirable cloudiness of the backing layer (US Pat. No. 3,615,545). Because photographic materials containing such latex in one or more layers can be processed more quickly, cause less bath carry-over, are less brittle and have improved dimensional stability, they are increasingly being used in practice today.