JPS61189530A - Photographic recording material with stabilized photosensitivity - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to photographic recording materials containing at least one light-sensitive silver halide emulsion layer, optionally other layers, and at least one UV-absorber present in high molecular weight form.

It is known to incorporate UV-absorbers into silver halide materials. UV absorbers eliminate the undesired effects of UV radiation during the exposure process or electrostatic loading. UV-absorbers can be introduced into the recording material, for example in dissolved form or in oil-forming agents such as tricresyl phosphate. However, this comes with significant disadvantages. For example, aminoallylidenemalondinitrile is known as a UV-absorber for photographic recording materials. However, they exhibit a significant tendency to aggregate formation, resulting in undesirably broad absorption bands of low absorption. Therefore, both sides of the absorption band extending into the growth sensitive region of the spectrum cause yellowing of the final image and reduce the growth sensitivity of the recording material. To overcome this problem, UV
- Attempts have been made to introduce absorbents in highly dispersed form into so-called loaded latexes; German Patent Application Publication Nos. 2,541,230 and 2.54.
See No. 1.274.

It is also known that photographically useful compounds can be incorporated into recording materials in polymeric form.

The use of polymeric UV-absorbers is described, for example, in German Patent Application Nos. 3,313,574 and 1327.
, 464, US Pat. No. 4,307,184 and German Patent Application No. λ 401,455.

Neither of these implementations is completely satisfactory.

The polymers known, for example from U.S. Pat. No. 4,307,184, are either water-soluble products that reduce the strength of the film due to strong swelling, or water-insoluble solid products that require a considerable amount of money. This requires expensive emulsification. Generally, emulsions must be used in extremely large quantities, so that the photographic layers are very heavily loaded with emulsions. In addition to loading the photographic layers, large amounts of emulsion result in other negative effects such as unsatisfactory resolution bubbling during processing, reduced breaking strength and sweating during storage.

The object of the present invention is to provide an improved U that does not have any of these drawbacks.
It is an object of the present invention to provide a photographic recording material containing a V-absorber.

Photographs having at least one light-sensitive silver halide emulsion layer and optionally other layers, at least one of which contains a high molecular weight compound HM containing a repeating group G derived from an aminoallylidene malonic acid derivative This time, the recording material was discovered.

According to the invention, the compound HM is a polyadduct or polycondensate containing urethane or ester bonds.

In a preferred embodiment, the amino nitrogen atom of the aminoarylidenemalonic acid derivative, but not the remainder of the derivative, forms part of the compound HMO backbone.

In one particularly preferred embodiment, the group G has the following structure; in which AI is a linking group, in particular a 01-C1° alkylene group, such as a methylene group, an ethylene group, a trimethylene group, a 2-hydroxytrimethylene group, a penta- A methylene group, a hexamethylene group, an ethyl-ethylene group, a propylene group, or an arylene or cycloalkylene group, and X is CN, C00RI, C0NHR,l, C
0RI.

SO, 几1 represents optionally substituted alkyl, in particular alkyl containing 1 to 20 carbon atoms, optionally substituted alkyl, in particular optionally substituted alkyl; phenyl, and the group G connects to the residue of compound It is connected.

In another particularly preferred embodiment, the group G has the following structure: where 1 and N! are the same or different and are a linking group, in particular an alkylene group containing 1 to 20 carbon atoms, such as methylene, ethylene, trimethylene, 2-hydroxytrimethylene, pentamethylene, hexamethylene, ethylethylene. , fluoropylene group or arylene or cycloalkylene group, X is CN, C0OR, I, C0NHRI, C0RI
.

SO, hail 几1, Y is CN, COOR1, C0NH 几2, CO 几! , S.O.
, 几! and R1 are the same or different, optionally substituted alkyl, especially alkyl containing 1 to 20 carbon atoms, optionally substituted aryl, especially optionally substituted or 1 and R2 together complete a ring, and X is O or 1;

In another particularly preferred embodiment, the group G has the following structure: where 1, 82 and Aa are the same or different, the linking group
In particular alkylene radicals containing 1 to 20 carbon atoms, such as methylene radicals, ethylene radicals, trimethylene radicals, 2-hydroxytrimethylene radicals, pentamethylene radicals, hexamethylene radicals, ethylethylene radicals, phlopylene radicals or arylene or cycloalkylene radicals Hail, X is CN, C0OR, l XC0N) iRI 5CO
R,I.

80, R1 is optionally substituted alkyl, especially alkyl containing 1 to 20 carbon atoms, optionally substituted aryl, especially optionally substituted phenyl Bs is optionally substituted alkyl, in particular alkyl containing 1 to 6 carbon atoms, n is 1 to 10, and X is O or 1.

In another particularly preferred embodiment, the group G has the following structure: in which AI and A2 are the same or different and are a linking group, in particular an alkylene group containing 1 to 20 carbon atoms, such as a methylene group, Ethylene group, trimethylene group, 2-hydroxytrimethylene group, pentamethylene group, hexamethylene group, ethylethylene group, 7'RohiL'7Jl! ” or an arylene or cycloalkylene group, X is CN, (“0ORI, C0NHR,l, C
0RI.

So, R1 is optionally substituted alkyl, especially alkyl containing 1 to 20 carbon atoms, optionally substituted aryl, especially optionally substituted phenylene. R8 is optionally substituted alkyl, in particular alkyl containing 1 to 6 carbon atoms, and X is O or 1.

Particularly preferable groups 1 and 2 include, for example, optionally substituted alkyl groups having 1 to 20 carbon atoms [e.g., methyl group, ethyl group, n-butyl group, n-hexyl group, cyclohexyl a, n- y' syl group. -dodecyl group, n
-octadecyl group, eicosyl group, methoxyethyl group,
Ethoxypropyl group, 2-ethylhexyl group, hydroxyethyl group, chloropropyl group, N,N-diethylaminepropyl group, cyanoethyl group, phenethyl group, benzyl group, G"-butylphenethyl group, l) j-octylphenoxyethyl group , 3(2t4-di-t-amylphenoxy)-propyl group, ethoxycarbonylmethyl group, 2-(2-hydroxyethoxy)-ethyl group, 2-furylethyl group, Nato], or 6 to 20 carbon atoms Containing aryl groups [e.g. tolyl group, phenyl group, anisyl group, mesityl group, chlorophenyl group, 214-di-t-
amyl phenyl group, naphthyl group, etc.). In addition to this, R1 and R1 can be taken together to form a 5- or 6-membered ring, such as a 1,3-dioxocyclohexane ring [e.g. dimedone ring, 1,3-dioquine-5
, 5-diethylcyclohexane ring, etc.), 113-diaza-2,4,6-drioxocyclohexane ring [e.g., barbyl a ring, 1 t 3 y methylbarbylic acid 3jl, 1-phenylbarbylic acid L 1-methyl-3-octylbarbylic acid ring, l-ethyl-3
-octyloxycarbonylethylvalpituric acid ring,
etc.],]1,2-diaza-3,5-dioxocyclopentane ring e.g. 1,2-diaza-1,2-dimethyl-3
, 5-dioquine cyclopentane ring, 1,2-diaza-1
, 2-diphenyl-3,5-dioxocyclopentane ring, etc.] or] 2,4-diaza-1-alkoxy 3,
5-dioxocyclohexene ring [e.g. 2,4-diaza-1-ethoxy-4-ethyl-3,5-dioxocyclohexene ring, 2,4-diaza-1-ethoxy-4=ethyl-3,5-di oxocyclohexene ring, 2゜4-diaza-1-nitoxy-4-C3-(2,4-di-t-amylphenoxy)-propyl]-3゜5-dioxo-cyclohexene ring, etc.) I can do it.

In a particularly preferred embodiment, X is a cyano group or 18o, R1, and Y is CN
or C0OR", Bt and R1 are the same or different, and 1 to 1 carbon atom, which may be optionally substituted.
Alkyl groups containing 20 carbon atoms, preferably 1 to 6 carbon atoms, or optionally substituted aryl groups containing 6 to 20 carbon atoms.

Particularly preferred specific compounds are: M2 M3 M4 1N
It is within the range of 00. Higher molecular weight compounds are also suitable, but they are more difficult to produce. in general,
A molecular weight in the above range is sufficient to achieve adequate diffusion resistance of the polyadduct or polycondensate.

The polyesters according to the invention can be used, for example, in Ullmans Encyclopédie der Technicien Hemie
Manns Encyclopadie der t
e-chnischen Chemie), 4th edition, volume 19, page 61 and subsequent editions, Verlag Chemie
Wine High A (VerlagChemie, We
It can be produced by known methods for polyester synthesis of the type described in Inbeim. The starting materials used for the esterification are UV-absorbing diols and dicarboxylic acids, activated dicarboxylic acids or dicarboxylic acid derivatives such as esters, acid chlorides, acid anhydrides,
Reaction product between carbodiimide and dicarboxylic acid, reaction product between dicarboxylic acid and 2-chloro-2-methylpyridinium iodide [Macromolecular Chemistry]
! J-(Macro-mo 1.Chem, )
185.2347 (1984)), a dicarboxylic acid imidazolide.

Compounds corresponding to formula 4 correspondingly contain U containing both an OH- and a (substituted) COOH-functional group.
Produced by polycondensation of V-absorbers.

Polyurethane (x = 1 in formula 3) is a UV-absorber using the method described in Ullmann's Encyclopedia der Technicien Hemi-1 4th Edition, Volume 19, Page 301 and its can be synthesized by polyaddition with diisocyanate.

It is also possible to combine the synthesis of polyesters and polyurethanes by reacting UV-absorbing polyesters containing two terminal OH groups corresponding to formula 3 with diisocyanates in a chain-extension sequence reaction ( (See "Polyesters as Starting Materials for Polyurethanes" in Ullmann's Encyclopédie der Technicien Hemi-1 4th Edition, Volume 19, Page 62).

The esterification reaction can be catalyzed by the addition of acids, bases and transition metal compounds. Preferred catalysts are titanium, antimono, tin, other compounds of lead, pp.
Used in m-amounts. In the first stage, the esterification reaction is carried out in an inert gas atmosphere (Cnitrogen/carbon dioxide), and the condensation water is rapidly distilled off through a column at a temperature of 30° C. or higher.

After reaching an acid value of 30, either a vacuum is applied (“vacuum-melting method”) or a propellant gas, typically carbon dioxide, is introduced (
The reaction must be accelerated by facilitating the removal of the water of reaction from the esterification equilibrium, either by using a circulating entrainment agent such as toluene or cycrene (the ``propellant gas-melt method'') or by using a circulating entrainer such as toluene or cycrene (the ``azeotropic method''). ◎ Diols or polyols, which preferably do not have a UV-absorber structure, can also be used for the production of polyesters, since they favorably influence the mechanical properties, solubility or compatibility of the compounds according to the invention. It is. Examples of suitable diols or polyols of this type are 1.2
-ethanediol, diethylene glycol, triethylene glycol, 5-ethylene glycol, polyethylene glycol, 1,2-propanediol, diethylene glycol, triflopylene gelicol, 3-chloro a-
1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol,
1,4-butanediol, 2,2-dimethyl-1,3-
Propanediol, 1,6-hexanediol, 3-methyl-1,5-bentanediol, trimethyl-1,6
-hexanediol, 2-7'tanediol, 2-butyne-1,4-diol, 1,2.6-hexanediol, and pentaerythritol. The proportion of polyol used is preferably 50% by weight, based on the product of the invention.
It is as follows.

In addition to this, optionally substituted diamines can also be used in amounts of up to 10% by weight when X=1. Suitable examples of optionally substituted diamines are ethylenediamine, lysine and (2-aminoethyl)-2-aminoethanesulfonic acid sodium salt.

The preparation of the compound is described below as an example.

Compound HMA 3-acetanilide arylidene malononitrile 118.
5M and jetanolamine 157.5M are dissolved in methanol 500M at room temperature and the reaction mixture is stirred for 2 days. After cooling to 0° C., the precipitate is treated with P and recrystallized from methanol.

A yellow product 601 is obtained which melts at 127-128°C.

M4 succinic acid 5.9f, 3-(N,N-dihydroxyethylamino)-allylidenemalonitrile 10.42,
Triethylamine 14.811/and dry butanone 10
Heat 0 ml to 50° C. under nitrogen. Next is Pig Fu 20
m! 20.6 f of dicyclohexylcarbodiimide was added thereto, and the mixture was stirred at 80° C. for 10 hours. The precipitated dicyclohexylurea is then filtered off, the P solution is concentrated, and the remaining solution is dissolved in petroleum ether/ethyl acetate and reprecipitated.

6.25 f of the product obtained by K
Dissolve in 1.8f, then 20t of 3% gelatin and 10
% sodium lauryl sulfate and then emulsification. The solvent is then evaporated off. A dispersion according to the invention is obtained in which the UV-absorber is finely dispersed in gelatin.

Compound HM5 3-(N,N-dihydroxyethylamino)-allylidenemalonitrile 10.4f, trimethyl-2,2,4
10.5 F of diisocyanato-1,6-hexane and 0.21 F of diazabicyclooctane are combined in 80 F of dry butanone under nitrogen and heated to boiling temperature for 8 hours.

The reaction product is then concentrated, precipitated with petroleum ether and dissolved in acetone/petroleum ether and then reprecipitated.

The preparation of a dispersion of the compound obtained in gelatin is carried out analogously to UV2.

M5 3-acetanilide arylidene methyl cyanoacetate 126? and 2-methylaminoethanol 75f are stirred in methanol 25Qaj at room temperature for 6 hours. O'CK
After cooling, the precipitate is separated and recrystallized from methanol. 12
3-(N-Methyl-N-2-hydroxyethylamino)-allyritin methylcyanoacetate melts at 8°C 7
Get 8f.

Thereafter, the obtained product 105f and ethylene glycol 124f were stirred, and the mixture was mixed with 2% of the potassium chloride. Heat to 70° C. for 3 hours in a water jet vacuum in the presence of water. After cooling and long standing, the precipitate is filtered, stirred with isopropanol, filtered again and dried. 3-(N-methyl-N-
2-Hydroxyethylamino)-allylidene ethylene glycol cyanoacetate) (melting point 115-117°C) 6
Get 5f.

This compound, which is not present in dispersion form, is dispersed for use in photographic materials. When the dispersion step is carried out in an aqueous solution of gelatin, the organic solvent used for dissolution can be removed from the mixture before the dispersion is used to form a coating.

Suitable solvents are those which exhibit such solubility in water that they are suitable for removal by washing with water in the form of gelatin noodles, and those which are suitable for removal by spray drying, vacuum or steam expulsion. It is of this type.

Other examples of organic solvents suitable for removal include esters (
(e.g., lower alkyl esters, etc.), lower alkyl ethers, ketones, norogenated hydrocarbons (e.g., methylene chloride, trichloroethylene, etc.), fluorinated hydrocarbons, alcohols (e.g., methyl alcohol to butyl alcohol), and combinations thereof. .

It is possible to use any type of dispersion medium for dispersions of hydrophobic polymeric UV-absorbers.

However, preference is given to ionic surfactants, especially anionic surfactants. The dispersing medium is preferably used in an amount of 2 to 1551; based on the compound used. In addition to this, it is possible to use amphoteric surfactants, such as C-cetylbetaine, N-alkylaminopropionates and N-alkyliminodipropionates.

To improve the stability of the dispersion and the flexibility of the applied emulsion coating, permanent solvents, i.e. water-immiscible organic solvents with a high boiling point (i.e. above 200°C), such as dibutyl phthalate and/or tricresyl phosphate, etc. It is possible to add a small amount (not more than 50% by weight of the repeating unit). The concentration in which the permanent solvent is present must be low enough that it plasticizes the polymer while maintaining solid particle morphology. Moreover, when using permanent solvents, it is preferred to use as little soaking as possible, thereby reducing the thickness of the final emulsion layer or hydrophilic colloid layer and maintaining good resolution.

The compounds used according to the invention can be incorporated into the binder layer or the photosensitive silver halide layer, for example. The silver halide emulsion layer can be divided into component layers having the same spectral sensitivity but different degrees of sensitivity.

The compounds used according to the invention can be used, for example, for sensitive growth.
It can be incorporated into the photosensitive layer. In another preferred embodiment, they are introduced into an upper UV-filtration layer placed above all photosensitive layers.

The amount used depends on the particular application and is easily optimized in a conventional manner. A preferable amount is, for example, 50 to 1000111p
/m”.

In addition to the layers already mentioned, other light-insensitive auxiliary layers can be present in the color photographic material according to the invention, such as coupling layers, anti-exposure layers or cover layers, More specifically, it is an intermediate layer between photosensitive layers, which is intended to effectively prevent developer oxidation products from diffusing from one layer to another. .

Color couplers that react with color developer oxidation products to form non-diffusible dyes are preferably associated with the light-sensitive silver halide emulsion layer. The color coupler is best housed in non-diffusive form within the photosensitive layer itself or in a portion adjacent thereto.

Thus, the red-sensitive layer may contain a non-diffusive color coupler, generally a phenol or alpha-naphthol type coupler, for example to produce a cyano component color image. The green-sensitive layer may contain at least one non-diffusive color coupler, for example to produce a magenta component color image, typically color couplers of the 5-pyrazolone type. The photosensitive layer may contain at least one non-diffusing color coupler, typically a color coupler containing open chain ketomethylene groups, for example to produce a yellow component color image.

Color couplers can be, for example, 6-14- and 2-14-color couplers.

Suitable color couplers are known, for example, from the following publication: "Mitteilungen aus den Forschungeslaboratorien der Agua, Leverkusen/Munich".
Us den Forschungs-1aborat
Orien der Agfa, Leverkusen
/munchen”), Vol ISp, 111 (
"Farbkupple" by W. Pe1z in 1961)
R''), K. Venkataraman, ``The Chemistry of Synthetic Dies'' (K, Venka
Taraman.

” the Chemistry of 5ynthe
tic Dyes") Vol, 4. p, 341~
387.7 Academic P
ress”) (1971), and T.H.
James, ``The Theory of the Photographic Process'' (ToM.

James, “The Theory of
the Photographic Process
), vK4 edition, pp. 353-362, and Industrial Opportunities Limited, Homera.
El, Norvant, Normpshire, PO91EF, Great Britain (Industrial 0ppor
tunnelies Ltd, Home-well, Ha
vant, Hampshire, POS 1 BF.

Research Disclosure published by Great Britain
e) No.

17643. December 1978, Section ■.

may contain a tocoupler. Inhibitors that can be liberated from DI metalloids can be liberated directly or via non-inhibitory intermediate compounds: GB 95 formula 454, US 3,632,345, GB 4,2413. ,9
See No. 62 and British Patent No. 207S363.

The light-sensitive silver halide emulsions used can contain chlorides, bromides and iodides or mixtures thereof as silver halide. In one preferred embodiment, the halide component is AgIQ ~12 mol%, AgC10-50
It consists of at least one layer of 50 to 100 mol % of AgBr, the sum of these percentages being 100%. In a preferred embodiment, the norogenide component consists primarily of tight crystals, such as cubic or octahedral or transition forms. They may be characterized by having a thickness essentially greater than 0.2 μm. The average diameter to thickness ratio is preferably 8:1 or less, and the diameter of the particle is defined as the diameter of a circle corresponding to the projected area of the particle. However, in another preferred embodiment, all emulsions or individual emulsions are essentially tabular and have a diameter to thickness ratio of 8=1.
It can also contain silver halogenide crystals larger than .

Emulsions can be chemically sensitized. The common types of sensitizers can be used to chemically sensitize the silver halide grains, with sulfur-containing compounds such as allyl isothiocyanate, allylthiourea and thiosulfate being particularly preferred. Other suitable chemical sensitizers include gold, platinum,
Noble metals and precious metal compounds such as palladium, iridium, ruthenium or rhodium. This chemical sensitization method was
E) / 57 E (Z, Wiss, Phot
), 46.65-72 (1951), in an article by R. Koslowsky. Emulsions can also be sensitized using polyalkylene oxide derivatives; see Research Disclosure No. 17643, supra, Section Summer.

The emulsions may be sensitized by optically known methods, for example using common polymethine dyes such as neutrocyanine, basic and acidic carbocyanine, rhodacyanine, hemicyanine, styryl dyes, oquinol and the like. can. Such sensitizers are known as 1.
yanineDyes and Re1ated Co
mpounds"), (1964) by F.M., No. R-(F6M,
Volume 18, pages 431 et seq. and the above Research Disclosure No.

17643, section ■, with particular reference.

In addition to the compounds used according to the invention, it is possible to use the usual fungicides and stabilizers. Particularly preferred stabilizers are azaindenes, preferably tetra- or penta-azaindenes, especially those substituted with hydroxyl or amino groups. Such compounds are, for example, Zeitschrift Φ Huitssenschaftlisch Fotografie, 47, (1952), 2-5.
It is described in the article by Hirr on page 8. Other suitable stabilizers and antifoggants are described in Research Disclosure No. 17643, supra, Section 1.

The components of the photographic material can be combined using standard known methods. If the compounds are water- or alkali-soluble, they can be added in the form of an aqueous solution, optionally together with a water-miscible organic solvent, such as ethanol, acetone or dimethylformamide. If they are insoluble in water and alkali, they can be incorporated into the recording material in dispersed form by known methods.

For example, solutions of these compounds in low boiling organic solvents are mixed directly with the silver halide emulsion or first with an aqueous gelatin solution and the organic solvent is then removed. The resulting dispersion of the specific compound is then mixed with a silver halide emulsion.

So-called oil formers, which are generally relatively high-boiling organic compounds, can additionally be used in the form of oil cylinders containing the compounds to be dispersed. In this regard, see, for example, U.S. Pat.
No. 3,689,271, No. 1764.336 and No. 3,765.897. It is also possible, for example, to incorporate the coupler in the form of loaded latex; German Patent Application No. 2541.27
See No. 4 and European Patent Application No. 14.921. The components can also be incorporated into the material in the form of polymers; for example, German Patent Application No. 2.044,992,
U.S. Pat. No. 3,370,952 and U.S. Pat. No. 4.080,
See No. 211.

Common layer supports can be used for the materials of the invention, such as supports of cellulose esters such as cellulose acetate and supports of polyesters.

Other suitable supports are paper supports, which can optionally be coated with, for example, polyolefins, in particular polyethylene or polypropylene. Regarding this, please refer to the above Research Disclosure No. 0817643.
, Section XvII.

Protective colloids or binders for the layers of the recording material are customary hydrophilic film-forming agents, such as proteins, especially gelatin. In this connection reference is made to the binders described in Research Disclosure 17643, Section 3.

The layers of photographic material can be hardened using conventional methods, for example using hardeners of the epoxide type, heterocyclic ethyleneimine type and acryloyl type. The layer is also described in German Patent Application No. 2, in order to obtain a photographic material suitable for high temperature processing.
It can also be cured by a method according to No. 218.009. It is also possible to harden the photographic materials, or rather the color photographic multilayer materials, with hardeners based on diazine, triazine or 1,2-dihydroquinoline or with hardeners of the vinylsulfone type. Other suitable curing agents can be found in the German Patent Application Publication! No. 2,439,551, No. 2
．． No. 225,230, No. 4317,672, and Research Disclosure No. 17643, Section X.
known from.

Other suitable additives include Research Disclosure 17643 and 1 Product Licensing Index.
Index''), December, 1971, 107-11
It is stated on page 0.

Suitable color developer materials for the materials of the invention are particularly those of the p-phenylenediamine type, e.g.
N-diethylaniline salt fi salt: 4-amino-3-methyl-N-ethyl-N-β-(methanesulfonamide)
-Dithylaniline sulfate aqueous product; 4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-
p-toluenesulfonic acid and N-ethyl-N-β-hydroxyethyl-p-fluoride diamine. Other suitable color developers are described, for example, in the Journal of the American Chemical Society (J.

Amer, Chem, Soc, ) 73.3100 (19
51') and G. Haist, Modern Photographic Processing, 1979, John Riley & Sons, New York (G. Haist
.

Modern Photographic Process
ssing.

1979, John Wiley and 5on
s, New York), pages 545 et seq.

After color development, the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together. Suitable bleaching agents are the customary compounds, 3+ such as Fe-salts and F6-complex salts, such as 7-erycyanide, dichromate, water-soluble conolate complex salts, etc. Particularly preferred bleaching agents are FAs of aminopolycarboxylic acids, especially eg ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids.
(1) Complex salts and corresponding complex salts of phosphonic acids. Persulfates are also suitable bleaching agents.

EXAMPLES The comparative compounds described in the examples below have the following structures: UV-1 (comparative example) UV-2 (comparative example) According to the example of U.S. Pat. No. 4.307.184 Compound (copolymer of acrylamide/diallylaminoallylidenemalonitrile) Example 1 A casting solution containing a UV-absorber, gelatin and sodium dodecylbenzene sulfonate is applied to a triacetate support in a conventional manner at 0.2 microIJmol per square meter. of the specific UV-chromophore. Gelatin concentration is 1m! 1) Adjustments were made so that 1f of gelatin was applied. 1m for this UV absorber layer! A pure gelatin layer containing 1 ton of gelatin per layer was applied. A dispersion of the UV-absorber was prepared by first dissolving the compound in ethyl acetate, mixing the resulting solution with gelatin using a high-speed stirrer, and then homogenizing in a high-pressure homogenizer.

The produced film was measured in a spectrometer using the JV-absorber-free film as a reference.The UV-spectrum shown in Figure 1 was obtained. Dihedral line 1: Material containing UV-absorber UV-1 (comparative example) Curve 2: UV-absorber HM4 (invention) + t[3:
UV-absorber HMs (invention) Curve 4: UV-4
Absorbent UV-2 (comparative example) It can be seen that the UV-absorber according to the invention exhibits a more favorable absorption.

Example 2 A standard color photographic negative material was obtained by applying the following layers to a standard support in the order listed: Slow light - light sensitive layer r1 Fast red - light sensitive layer R1 Slow edge - light sensitive layer g , high-sensitivity edge-photosensitive layer G, yellow filter layer with colloidal silver filter yellow, low-sensitivity growth-photosensitive layer b1 high-sensitivity growth-photosensitive layer B1 UV-absorber layer according to Example 1, according to Example 1 gelatin layer.

The samples were imagewise exposed and subjected to standard color negative development, as is known, for example, from German Patent Application No. 3.029.209. The following results were obtained by comparison with a sample without UV-absorber: Growth-photosensitive layer lUV-10,16If (Ixt) 0.068 colors (comparative example) 2 HM4 0.101r (Ixt) 0.0 brown (invention) 3 HM5 0.091y (Ixt) 0.01 brown (
present invention) 4 UV-20,071f (Ixt) o, 01
Stained Purple (Comparative Example) Decrease in sensitivity: An increase of 0.3 units in the value given by 1 (Ixt) corresponds to twice the sensitivity.

Dmin2IIk Small Color Density Brown Reproduction: A brown object color of intense radiation in long wavelength UV was photographed and reproduction evaluated based on a neutral copy.

The table above shows that Samples 2 and 3 according to the invention achieve an improvement in sensitivity over Sample 1 and an improvement in color reproduction over Sample 4.

[Brief explanation of drawings]

Claims (1)

[Scope of Claims] 1. A polymer comprising at least one silver halide emulsion layer and optionally other layers, in which at least one layer contains a repeating group G derived from an aminoallylidene malonic acid derivative. A photographic recording material containing a molecular weight compound HM, characterized in that the compound HM is a polyadduct or polycondensate containing a urethane bond or an ester bond. 2. Claim 1, characterized in that the nitrogen atom of the amino group of the aminoarylidene malonic acid derivative, rather than the remaining part of the group G, is a part of the main chain of the compound HM. Photographic recording material as described. 3. The group G has the following structure▲There are mathematical formulas, chemical formulas, tables, etc.▼1) In the formula, A^1 is a bonding group, and X is CN, COOR^1, CONHR^1, COR^1
, SO_2R^1, where R^1 represents an optionally substituted alkyl group or an optionally substituted aryl group, and the group G is a free bond between an oxygen atom and a nitrogen atom. 2. The photographic recording material according to claim 1, wherein the photographic recording material is linked to the remaining part of the compound HM through an oxygen atom and a free bond at an X-substituted carbon atom. 4. The group G has the following structure ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ 2) In the formula, A^1 and A^2 are the same or different and represent divalent bonding groups, and X is CN, COOR^1 , CONHR^1, COR^1
, represents SO_2R^1, Y is CN, COOR^2, CONHR^2, COR^2
, SO_2R^2, and R^1 and R^2 are the same or different and represent an optionally substituted alkyl group, an optionally substituted aryl group, or together complete a ring. The photographic recording material according to claim 1, characterized in that: and x is 0 or 1. 5. Group G has the following structure ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ 3) In the formula, A^1, A^2 and A^3 are the same or different, 2
Represents a valent bonding group, X is CN, COOR^1, CONHR^1, COR^1
, SO_2R^1, R^1 represents an optionally substituted alkyl group or an optionally substituted aryl group, R^3 represents an optionally substituted alkyl group, n The photographic recording material according to claim 1, characterized in that x is an integer from 1 to 10, and x is 0 or 1. 6. The group G has the following structure ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ 4) In the formula, A^1 and A^2 are the same or different and represent a bifunctional bonding group, and X is CN, COOR^ 1, CONHR^1, COR^1
or SO_2R^1, R^1 represents an optionally substituted alkyl group or an optionally substituted aryl group, R^3 represents an alkyl group, and x is 0 or 1. A photographic recording material according to claim 1, characterized in that it has the following. 7. A photographic recording material according to claim 1, characterized in that the compound HM is present on a light-sensitive silver halide emulsion layer or in a highly sensitive blue-sensitive silver halide emulsion layer. 8. Compound HM is a polyadduct or polycondensate containing a urethane bond or an ester bond,
Repeating group G derived from aminoallylidene malonic acid derivative
A high molecular weight compound HM containing.