DE2113381A1 - Polymers with guanidyl ketimine structural units - Google Patents

Description

47 652

Applicant: Konishiroku Photo Industry Co., Ltd., Tokyo, Japan

Polymers with guanidyl ketimine structural units

The present invention relates to polymers with g-uanidyl ketimine Structural units and light-sensitive, silver halide-containing photographic recording materials containing these polymers as new stains to improve the sharpness of the images obtained contain.

It is known that for the prevention of irradiation or halation in the photosensitive A _u fZeichenmaterialien and achieved thereby improving the sharpness of the images obtained this photosensitive Aufzeichenmaterialien have a layer containing a material capable of absorbing said excess light. In this sense, it is known, for example, that an antihalation layer is provided on the back of the support, that an antihalation layer is provided between the support and the light-sensitive photographic layer or that an anti-irradiation dye is provided directly in the light-sensitive photographic layer.

Generally these contain anti-irradiation or antihalo layers Light absorbers such as dyes, colloidal silver, colloidal manganese or penance. The above-mentioned light absorbers however, affect the photographic emulsions and

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cause various disadvantages such as desensitization, increase in haze, etc. when they are photosensitive photographic layer or an adjacent layer are incorporated, even if there are essentially no problems, when applied to the back of the carrier. When an antihalation layer containing a dye is adjacent is present on the photosensitive photographic layer, the dye accordingly diffuses into the photosensitive photographic layer Layer and also absorbs necessary light to desensitize the photographic layer. Even if, if a layer containing a light absorber such as colloidal silver or a similar compound is adjacent to photographic emulsion layer is provided, fog increase, desensitization and the like Caused disadvantages in the photographic emulsion layer. Accordingly, a light absorber is only incorporated into the photosensitive photographic layer or a "layer adjacent thereto" incorporated when increased sharpness is required at the expense of sensitivity, such as the This is the case with light-sensitive photographic recording materials with a high resolution.

In order to overcome the above-mentioned drawbacks and to effectively improve the sharpness of the image obtained, it has been proposed to use a mordant which does not diffuse itself and which has the property of temporarily or permanently scavenging a dye and preventing its migration. If such a mordant is incorporated together with a dye in, for example, a layer adjacent to the photosensitive photographic layer, the diffusion of the dye into the photosensitive photographic layer is controlled and the deterioration of the photographic properties is avoided. In addition, one or more of the following phenomena occur during the subsequent development stage : the trapped dye is decolorized, the mordant releases the dye into the treatment solution, or

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the stain to flow into the treatment solution without that it releases the intercepted F ₈ rbstoff can be eliminated whereby the adverse effects of the dye on the image after its formation.

Accordingly, the use of the stain has the advantage that a non-diffusing dye layer is desired can be provided in those parts in which previously a dye could not be used, and in particular can now an antihalation layer in one layer of a multilayer Light-sensitive be presented on drawing material. In addition, the stain can not only prevent the Halation and irradiation are used but it can also be used for other layers such as a filter layer, and it can be used as a carrier for a filter dye. With regard to the uses explained above the mordant should have excellent dye-retaining property and no adverse effects on the photographic emulsion.

The dialkylamines disclosed in US Pat. No. 2,326,057 and the urea-polyethylenirain reaction products disclosed in German Pat. No. 1,095,120 are known as pickling agents of this type. However, these mordants do not have sufficient dye-scavenging property, so that when these mordants are incorporated in layers adjacent to light-sensitive photographic layers, considerable amounts of the dyes retained by the mordants diffuse and migrate into the photographic layers and thus adversely affect their photographic properties . In addition, these mordants must be used in large amounts, so that due to the mordants themselves, the photographic properties of the photographic layers are deteriorated and the physical properties and the coating properties of the photosensitive films obtained are deteriorated. So there are still no pickles known that are capable of meeting the various requirements that pickling -4-

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be made to meet in a satisfactory manner.

After extensive research it has now been surprisingly found that polymers containing the following guanidyl ketimine Have structure, are excellent stains.

■ σι

CH,

-C-CH ₂ -C = N-NH-G-NH ₂ .

CH

NH

where X is an acid radical and η is the number 1 or 2.

The present invention accordingly relates to new polymers with guanidyl ketimine structural units of the formula

-fOH ₂ -

f 3

COIm-C-GHp-C = H-NH-C-NH _9. (HX)

I I K

CH, GH, NH

where X is an acid radical and η is the number 1 or 2.

The present invention further relates to the avoidance of these Compounds used as mordants in photographic wash-on materials.

Have polymers with the above guanidyl ketimine structure compared to known compounds of this type, an extremely smaller influence on the photographic emulsioneti and them have a very excellent ability to hold dyes, so that even if they are in considerably smaller quantities Amounts used are equivalent in effectiveness to the known compounds of this type. The new polymers are obtained in that the carbonyl ^ groups of polymers

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containing the ij- (1,1, -dimethyl-3-oxobutyl) mentioned below acrylamide are condensed with aminoguanidine or salts thereof.

COlTH-G-CHpO OCH,

I ^C ° CH,

In the above compounds, the molar content of N- (1,1-dimethyl-3-oxobutyl) acrylamide is in the starting polymers which contain the H- (1, i-dimethyl-3-oxobutyl) acrylamide, expedient at least 30 MoI ^, and the molar content of monomer units, which have the guanidyl ketimine structure, in the polymers containing the guanidyl ketimine structure, which are formed by condensation of the above-mentioned polymers with aminoguanidine or salts thereof "is advantageously at least 10

U- (1,1-Dimethyl-3-oxobutyl) acrylamide is extraordinary easily copolymerizable with other vinyl monomers being modified Copolymers are obtained. These other vinyl monomers are for example acrylic acid esters, methacrylic acid esters, acrylamides and derivatives thereof, styrene, vinylpyrrolidone, 2-alkylvinylimidazole derivatives and vinyl esters such as vinyl acetate, Vinyl butyrate, vinyl propionate and acrylonitrile ',. However, are Monomers that contain -COOH and -SO ^ H groups, such as acrylic, Methacrylic and methylene sulfonic acids for the purpose of the present Invention undesirable and they destroy the ability to hold dyes. The molecular weights of the polymers with the above-mentioned guanidylketirain structure, which according to the Invention used are preferably about 8,500 up to 80,000 considering the compatibility of these compounds with gelatin, polyvinyl alcohol and the like hydrophilic colloidal layers to which the polymers are added.

lypisohe examples of polymers with the above- mentioned ffuani-

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dylketimine structure are given below in the context of synthesis examples specified for their manufacture. The polymers usable in accordance with the present invention are not limited to these Examples limited.

Synthesis Example 1 ■

To. a solution of 30 g of N- (1,1-dimethyl-3-oxobutyl) acrylamide in 300 ml of isopropanol 0.3 g of azobisisobutyronitrile was added and the resulting mixture was gsrührt 8 hours at 70 ⁰ O under nitrogen atmosphere. The mixture was then gradually poured into running water with stirring, 13.3 g of a white powder of poly-ET- (I, i-dimethyl-5-oxobutyl) acrylamide being precipitated. The molecular weight was 9 »55O measured in 1,4-dioxane (by the method of osmotic pressure), intrinsic viscosity (\) O.O3O in 1,4-dioxane at 30 ⁰ C.

Elemental analyzes:

calculated (#) G 62.22 H 8.99 found (96) 0 62.18 H 9.02

N 8.05 (H ₂ O 0.25) N 7.90

9.16 g of this polymer were dissolved in 60 ml of 1,4-dioxane. To the solution obtained 9:04 g of aminoguanidine bicarbonate and 15 ml of glacial acetic acid were added, and the resulting mixture was stirred at 50-55 ⁰ C for 2 hours allowed to react. 55 ml of pure water, 2 g of zinc powder and 6 ml of glacial acetic acid were then added to the mixture, stirred for 20 minutes and then filtered off with suction. The piltrate was poured into 200 ml of 10% sodium hydroxide solution to precipitate a resinous product. After the reaction mixture was allowed to stand overnight, the resinous product was recovered by decantation, washed twice or more with 100 ml of 40 # aqueous sodium hydroxide solution, poured into a mixture of 100 ml of pure water and 50 ml of glacial acetic acid, filtered and then to a G _e mix aua 1 1 acetone and 10 ml aqueous sodium chloride added. The precipitated resin was collected by filtration, dissolved in 200 ml of ethyl alcohol, filtered and then precipitated in 800 ml of ether. The resin was then collected by filtration, washed with ether and _ ^ _

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ORIGINAL fNSPSCTE &

then dried, with 7 * 6 g of a pale yellowish brown Resin, N content $ 16.79 were obtained.

Synthesis example 2

0.5 g of azobisisobutyronitrile was added to a solution of N- (1,1-dimethyl-3-oxobutyl) acrylamide in 500 g of carbon tetrachloride and the resulting mixture was refluxed under nitrogen atmosphere for 6 hours. After cooling, the mixture was poured into 3 l of naphtha, 50.5 g of a resin having a molecular weight of 20,800 being precipitated. Intrinsic viscosity (h) 0.085 in 1,4-dioxane at 3O ⁰ C.

Elemental analyzes:

calculated (fo) C 61.89 H 9.00 N 8.06 (H ₂ O 0.3) found (#) C 61.90 H 8.87 N 7.72

9.16 g of the polymer mentioned were dissolved in 70 ml of 1,4-dioxane. To the resulting solution were added 18 g of aminoguanidine bicarbonate and 25 ml of glacial acetic acid, and the resulting mixture became the the same reaction and the same aftertreatment as in Synthesis Example 1, 12.1 g of a yellowish Resin, N content 18.65%.

Synthesis example 3

To a solution of 23.6 g of N- (1,1-dimethyl-3-oxobutyl) acrylamide and 8.16 g of 2-ethyl-4-methyl-1-vinyl-imidazole in 400 ml of tert-butanol were added 0.4 g under a nitrogen atmosphere Azobisisobutyronitrile was added, and the mixture obtained was ^{stirred at 80 °} C. for 8 hours. After cooling, the mixture was poured into running water, 22.19 g of a polymer with an N content of 11.29 # being obtained. «9» 35 g of this polymer were dissolved in 100 au 1,4 ~ Dio3cari »6.4 g of aminoguanidine bicarbonate were added to the resulting solution and 10 ml acetic acid added, and the resulting mixture was allowed to ^{react for 2 hours at 50-55 0} O * Then the same after-treatments were carried out as in Synhtesebelspiel 1, with 10.8 g,. -8th-

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of a pale yellowish, brown resin with an N content of 19.32 $> were obtained.

Synthesis example 4

To a mixture of 35.4 g of IT- (I, 1-dimethyl-3-oxobutyl) acrylamide, 7.8 g of vinyl acetate monomer and 200 ml of carbon tetrachloride, 0.4 g of 1-t, ol-azobisisobutyronitrile was added under a nitrogen atmosphere, and the mixture was 7 Heated to reflux for hours. After cooling, the mixture was poured into 3 liters of naphthi to precipitate a precipitate, which was then collected by mitration, washed with 200 ml of naphtha and dried. This 36 g of a white polymer with the
N content 7.51 i » obtained.

15.3 g of this polymer were dissolved in 120 ml of 1,4-dioxane. To the obtained solution 14 g and 25 ml Aminoguanidinbicarboiiat Bisessig were added, and the resulting mixture was 2 hours at 50-55 ⁰ G allowed to react. Then the mixture was mixed with 55 ml of pure water. 2 g zinc powder and 6 ml glacial acetic acid added, 20 min. stirred and then suctioned off. The filtrate was
Poured into 200 ml of 10% sodium hydroxide solution to precipitate a resin. After the reaction mixture was allowed to stand overnight, the resin was collected by filtration, twice
or washed more often with 100 ml of 4O? 6 sodium hydroxide solution each time and
then dissolved in 100 ml 10biger dilute hydrochloric acid. The resulting solution was filtered and the filtrate was poured into a mixture of 1 liter of acetone and 10 ml of sodium chloride solution to precipitate the resin. This resin was collected by filtration, dissolved in 150 ml of ethyl alcohol, filtered and then in 1 1
Ether pleases. The resin was then filtered through
recovered, washed with ether and under reduced pressure
dried, with 11.4 g of a yellowish resin, N content
$ 20.95 > i were received.

Synthesis example 5

To a mixture of 35.4 g of N- (1 »1-dimethyl-3-oxobutyl) acryl amide, 10 g of N-vinylpyrrolidone and 200 ml of [Petrachlorkohlen- ^ _q _

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0.4 g of butyronitrile were given under a nitrogen atmosphere. After cooling, the mixture was poured into 2.5 liters of ligroin to precipitate a precipitate, which was then collected by filtration, washed with 200 ml of ligroin and dried. 42 g of yellow polymer, N content 9 «18 <fo _{t were} obtained.

15.2 g of this polymer were dissolved in 120 ml of 1,4-dioxane. 14 g of aminoguanidine bicarbonate and 25 ml of glacial acetic acid were added to the resulting solution, and the resulting mixture was then subjected to the same reaction conditions and post-treatment as in the synthesis example. 19 g of a yellowish resin, IT content 19 · 1 ° were obtained.

Synthesis Example 6

0.6 g <<, <, * '-azobisisobutyronitrile was added to a mixture of 60.8 g of N- (1,1-dimethyl-3-oxobutyl) acrylamide, 2 g of acrylonitrile and 400 ml of isopropyl alcohol under a nitrogen atmosphere, and the mixture was 10 Allowed to ^{react at 70 °} C. for hours. After the reaction, hydroquinone was added and about half of the solvent was removed by distillation under reduced pressure. The residue was then poured into running water, 59 g of a polymer with an N content of 9.14% being precipitated.

15.8 g of this polymer were dissolved in 120 ml of 1,4-dioxane. 14 g of aminoguanidine bicarbonate were added to the solution obtained and 25 ml of ice-cream acid were added, and the resulting mixture was subjected to the same reaction and post-treatment as in the Synthesis Example 1 subject. This gave 18.4 g of a yellowish resin, N content 18 · 52 #.

The polymer obtained according to any of the above Synthesis Examples can be used in a photosensitive recording material for example by incorporating an aqueous solution of this polymer in a hydrophilic colloid such as gelatin or polyvinyl alcohol dispersed and the obtained

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Dispersion rait a suitable dye and then added applied to the support, photosensitive photographic layer or filter layer of the photosensitive material will. Alternatively, the aqueous solution of the polymer can be previously incorporated into the light-sensitive photographic layer have been incorporated.

In this case, the hydrophilic colloid can be coated with a Yehicel such as an anionic, cationic or amphoteric surface active agents and with common photographic additives such as hardeners, stabilizers etc. have been added. If desired, »the polymer can be used in combination with a known Pickling can be used.

photosensitive recording materials in which the polymers can be used according to the invention are those containing various silver halides, such as silver chloride, Silver chlorobromide, silver bromide, silver iodobromide etc .. It ·· Black and white or color photographic recording material can be used be. The amount of the polymer incorporated in a photosensitive recording material varies depending on the Type of light-sensitive recording material, the purpose of the Application and the type of layer to which the polymer is added. In general, however, the amount is, for example 2 to 40 g per. 100 g dry gelatin. In this case, the amount of dye carried by said polymer is can be, preferably 1 to 20 g. As the dye carried on the polymer is particularly preferred an acidic dye with a sulfonic or carboxyl group. Typical examples of such dyes are given below.

-11-

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Dye (fabric

. c;

C '"

Il O

-ί V

SO ^ K

Dye (2) substance

HO, 3—

K H N 0 ! N = η I. = σ

- COOH

Dye (3) substance

SO ^ H

"ν. _ / - ίιτ _ rep _ σι

-c

II

CH,

SO

( material

CH, - G-- - C = CH - CC - CH-

⁵ U! !! I -

N C = O HO-C N \ / \ /

N N

SO, H

SO ₃ H

Dye (5) substance

CH,

H ₂ N-

SO ₇ Well

SOjNa

so"

NH-,

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Dye (6) fabric

- 12 -

CH ₇

C C = CH

N 'C = O-CH = CH-C

0 -

N ι HO-C IT

SO ₃ H SO ₃ H

Dye

HOOC -

C-C = CH

Il!

IT C-O

- CH =

CH - C C

C IT

· - COOH

\ HO-C

SO ₂ K

SO ₃ K

Dye (8) fabric

Dye (9) fabric

HOOC-C- C = CH-CH = CH-CH = CH-C C-CuOH

Il Jl Si "

N C = O HO-C N

N IT

SO ₃ H ι
SO ^ H

CH ^ -C C-CH-CH = GK-CH-C! J - C - C-CH

^ H! Il Il

N C = O HO-C N

ν ν

' ^0H

KO ₂ S

COOK

KOOC

SO ₃ K

Color (10) material

NaO ₃ S

OH 0 N-CH
i! t '

H ₃ C-NH 0 OH SOy Na

-13-

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The present invention is illustrated by the following examples further explained.

example 1

4 ml of a 5% strength aqueous solution of the polymer obtained according to Synthesis Example 1 were added to 50 ml of an aqueous solution containing 3 g of gelatin and 200 g of saponin. In addition, 5 ml of an aqueous solution containing 1 % of the dye No. 7 was added. The resulting mixed solution was admixed with a customary amount of a hardening agent and then adjusted to pH 6.3. The volume of the solution was then made up to 100 ml, whereby Sample A was obtained. In order to demonstrate the effect of the polymer, a sample B was prepared in the same manner as described above, except that the polymer was not used. A control sample was also prepared in the same way, except that the polymer and dye were not used.

The above three samples were each coated on subbed cellulose triacetate film supports to have a dry emulsion layer thickness of 1.5 Ji and then dried. A high-sensitivity silver iodobromide emulsion was applied to each of the films thus prepared, whereby photosensitive films were obtained. These films were in a sensitometer Model KS-I (manufactured by Konishiroku Photo Industry Co., Ltd.), and with 160 lux (5,400 ⁰ K) ηιμ by blue and green filters with transmission maxima at 450 and 525 mp exposed. The exposed samples were then developed for 5 minutes at 20 ^° C. with a developer of the following composition.

Developer:

Metoi (N-methyl-p-aminophenol sulfate) 3 g

anhydrous sodium sulfite 50 g

Hydroquinone 6 g

Sodium carbonate (monohydrate) 29 x 5 g

Potassium bromide 1 g water except for 2

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2113331

After developing, fixing and washing with water, the photographic sensitivities and sharpnesses became of the films were measured, the results shown in Table 1 being obtained. In it is the photographic Sensitivity a relative sensitivity measured on the assumption that the sensitivity of the Control film was set at 100.

photographic
Sensitive
speed against
blue light Table 1 Veil Sharpness sample Control 100
(A) 95 photographic
Sensitive
speed against
green light 0.07
0.07 strong ver
improves 100
82

(B)

0.07

As is apparent from Table 1, having the film sample A, containing the polymer with said Guanidylketimin structure improved to the same degree of field as the film sample B, does not contain this polymer without ^w ie the sample B of Veil is raised. After microscopic examination, it was found that in the case of the film sample B, the diffusion of the dye into the emulsion layer was remarkable, while in the case of the film sample A, such diffusion was essentially not observed.

A film sample 0 was also prepared in the same manner as described above, but with the dye No. 6 was used in place of Dye No. 7. In addition, a film sample D was prepared in the same manner as described above but no polymer was used. Samples C and D were also photographic Sensitivity and sharpness were measured, the results shown in Table 2 being obtained.

-15-

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photographic sample sensitivity to blue light

Control 100

(C) 93

(D) 85

- 15 Table 2 photographic sensitivity to green light

100 80

veil

0.06 0.06

0.06

Sharpness

greatly improved

Film samples C and D were rinsed with running water for 20 minutes treated to study the diffusion of the dye in water. The result was that in the case of the film sample D the dye diffused significantly, while in the case of film sample C the dye did not diffuse at all. While the dye is easily discolored during development.

It has thus been proven that the polymers with the above-mentioned guanidyl ketimine structure have an excellent effect to retain the dye and that there is no risk of an increase in the fog, a desensitization or similar deleterious effects on the photographic properties.

Example 2

To 50 ml of an aqueous solution containing 4 g of gelatin and 200 mg of saponin was added 10 ml of a 6% aqueous solution of the polymer from synthesis example 2 and in each case Vml of 1 # igen aqueous solutions of the dyes No. 2, 6 and 8 mentioned for example. The resulting mixed solutions were A hardener was added to each and the total amounts were made up to 100 ml. Any of these solutions were made Applied as a black anti-halo solution to a transparent film carrier to a dry layer thickness of 3M. On the so The films produced were panchromatically sensitized silicon chloride bromide emulsions applied to make film samples.

Control film samples were prepared by using dye solutions used in the same way as "described above", -

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- 16, but no polymers were used.

The photographic sensitivity and sharpness of the images were measured on these film samples. The result was such that the film samples containing the above polymer have an improved sharpness to the same extent as the film samples, which did not contain this polymer showed, however, a reduced decrease in photographic properties by comparison Sensitivity was caused. During development were the antihalation layers completely into transparent layers ^ discolored.

Example 5

Between the red-sensitive layer and the green-sensitive layer of a color photographic light-sensitive material each of the two colored dye layers prepared in the manner described below were used provided: To 50 ml of an aqueous solution containing 3 g geläine and 100 mg saponin were each (e) 5 ml of a 6% solution of the polymer from synthesis example 4 and 10 ml of a 1% aqueous solution of the example mentioned Dye No. 7 and (f) 5 ml of a 6 # aqueous solution of the polymer of Synthesis Example 6 and 10 ml of a 1 # aqueous solution of the dye no. 7 mentioned for example. Then the total amounts of Mixtures of solutions made up to 100 ml.

Not only did these dye layers have no disadvantage Effect on the red sensitivity of the lower red-sensitive emulsion layer, but they also had the effect that it cut off the unnecessary green sensitivity and thus improved the color sensitivity of the emulsion layer and reinforced. On top of the top green-sensitive emulsion layer, the non-diffusing dye layer had the Effect that the harmful halation is successfully prevented and thus the sharpness of the image obtained is strong has been improved. _

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In the case of the light-sensitive recording material with a dye layer, which was produced in the same way as described above with the only difference that the polymer was not used, however, diffusion and migration of the dye occurred into the upper green-sensitive emulsion layer and green light was absorbed with the result that the green sensitivity was greatly decreased.

Example 4

Containing red-sensitive and green-sensitive emulsions a coupler was coated on a support. A yellow filter layer was produced on the layer obtained by that a solution was applied which was obtained by adding 10 ml of a 6% aqueous solution of the polymer of Synthesis Example 5 and 20 ml of a 1 $ aqueous solution of the dye No. 3 mentioned for example to 60 ml of a aqueous solution containing 3 g gelatin and 200 mg saponin had been prepared. Then a blue-sensitive Emulsion containing a coupler is additionally applied to the yellow filter layer, with a light-sensitive color photographic drawing material was obtained. That so The color photographic recording material obtained became the color development and the photographic sensitivity of the blue-sensitive emulsion was measured. That The result was that no desensitization due to diffusion of the dye was found. The filter layer had the characteristic filter property that they successfully cut off unnecessary blue sensitivity of the lower layer.

This further proves that the above polymer itself has firmly bound such a dye as the dye No. 3, which contains only one acidic group. During the development, the filter layer became completely Transparency discolored.

Patent claims:

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Claims (2)

Claims 1. Polymers with guanidyl ketimine structural units of the formula - £ CH ₂ -CK) - _CH ^ CONH-C-CH ₂ -C = N-NH-C-NH ₂ - (HX) _n CH, CH, NH where X is an acidic radical and η is the number 1 or 2. 2. A light-sensitive photographic material containing silver halide which has an acidic dye in any which contains the layers forming the photographic recording material, marked thereby ei without t that it is in the said acidic dye containing layer additionally contains a compound according to claim 1 as a stain. In that it contains 3 · The light-sensitive silver halide photographic recording material, characterized in that in an anti-Irradiations- or antihalation layer a compound according to ^A nspruch 1 as a mordant. 109850/1796