DE1924721C - Process for the production of polymer images - Google Patents

Description

means in the presence of a vinyl compound or

is represented, wherein A is an oxygen atom or vinylidene compound the formation of a silver image an imino group, B an optionally substituted and the polymerization of the aforementioned iertePhenylgruppe, R ₁ , R ₂ and R ₃ each a water, vinyl or vinylidene compound at the same time or a Alkyl group with 1 to 6 carbons can find. Examples of such specific belenstoffatomen and R ₄ a hydrogen atom, a known reducing agent are resorcinol and m-amino-alkyl group with 1 to 6 carbon atoms, a phenol and their derivatives. By utilizing aryl group or a carboxyl group, the aforementioned polymerization reaction is where (a) the pyrazolidine and the reducing agent 45 it is possible to obtain a colored image by using an image of a compound of high in the same solution Molecular pyrazolidine in an amount less than weight forms with charges and then colors the image. Reducing agent, expressed in molar proportions, however, since such reducing agent is generally used or (b) the layer mostly with a weaker reducing power than the usual one of a solution of the pyrazolidine and then with a solution for the photographic development of the reducing agent and the vinyl-used silver halide- The processing of the polymer in each case requires the vinyl monomer to be polymerized selectively in the image development for a considerably longer period of time, which is the areas of the and also leads to a lowering of the photolatent image of the silver halide layer - 55 graphic sensitivity
to speak. On the other hand, a common silver halide

2. The method according to claim 1, characterized marked Entwitklerverbindungen, z. B. p-methylaminophenol draws that as a reducing agent resorcinol, or hydroquinone, no effect to initiate the m - N, N - dimethylaminophenol, 3,4 - dimethyl polymerization of a vinyl compound or vinylidene-5-pyrazolone or o-xylenol is used. 60 connection. On the contrary, the usual silver

3. The method according to claim 1, characterized in that the halide developer compounds themselves or their draws that the weight ratio of the Pyrazo Oxydalionsprodukte often as inhibitors for the lidine or a tautomer thereof to the radical polymerization. G. O s t e r notes in the introduction of polymerisation Reducing agent lowercase in U.S. Patent 3,019,104 and in is expressed as a tenth in a molar ratio. 65 "Nature", Vol. 180, p. 1279 (1957), states that benzenoide

4. The method according to claim 1, characterized in that compounds with an OH group and —NH ₂ —dignify that in the presence of sulfite ions ent- group in the 0 and p positions, which usually winds as wild. Usual developers used to have an effect

to initiate the polymerization of a vinyl compound own, but this in his experiments only through the changes in optical density and of the hue of the silver images formed by development and no direct evidence for the formation of polymer images were given.

The object of the invention is an improved method for the production of polymer images by developing a photographic halogen silver emulsion layer, which has a latent image, with a reducing agent, the image-wise polymerization a vinyl or vinylidene compound with simultaneous reduction of the silver halide in the photographic Emulsion layer can initiate to indicate. The development speed should be and the speed of formation and the image density of the polymer image can be increased.

The object of the invention is based on a Verfahien for producing Polymerisatbildern in which a contained in an imagewise exposed photographic silver halide latent image of silver halide particles, which are held in a binder, monomer in the presence of water and at least one normally solid or liquid vinyl or vinylidene compound by treating the layer with at least one resorcinol, a m-aminophenol, a hydroxy- or aminonaphthalene or a derivative thereof, a dihydroxy-, diamino- or monohydroxymonoaminonaphthalene, the functional groups of which are in the 1,6-, 1,8- , 2,5- or 2,7-positions, a pyrazolin-5-one, or a substituted phenol (substituted with alkyl groups, substituted alkyl groups, acyl groups or halogen atoms) as reducing agent and with a silver halide developer compound is developed and is characterized by this that the development g carries out the same in the presence of a pyrazolidine or a tautomer, the pyrazolidine being represented by the general formula 1

The silver halide developing agent of the above given general formula can exist as tautomer, as shown below:

C-O

C-OH

R,

10
R ₁ C. N NH R4 ^C. N N B. or B. R ₁
R ₂ C.
I. R ₁
NH
R, C- -C-NH ¹⁰ D
R, C. ^N N NH "R ₃
R ₁ C. K N

R ₁ .

R ₃

R ₁

NH

in which A is an oxygen atom or an imino group, B is an optionally substituted phenyl group, R ₁ , R ₂ and R _{3 are} each a hydrogen atom or an alkyl group with 1 to 6 carbon atoms and R _{4 is} a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, represent an aryl group or a carboxyl group using (a) the pyrazolidine and the reducing agent in the same solution using the pyrazolidine in an amount smaller than the reducing agent in terms of molar ratios, or (b) the layer first is treated with a solution of the pyrazolidine and then with a solution of the reducing agent and the vinyl or vinylidene monomer, the vinyl monomer being selectively polymerized in each case in the areas corresponding to the areas of the latent image of the silver halide layer.

² SBB

The invention achieves the production of polymer images with increased image density. That day in addition, the addition of the pyrazolid

Compounds, the rate of formation of the polymer image is increased.

According to one embodiment of the invention, the reducing agent used is resorcinol, m-N.N-dimethylaminophenol, 3,4-dimethyl-5-pyrazolone or o-xylenol is used.

Reducing agents of the type indicated above are for reducing silver halide in one Halogen silver emulsion and at the same time for initiating polymerization of a vinyl compound or a vinylidene compound suitable.

The 3-oxopyrazolidines according to the invention apply and are represented by the general formula (1) given above, are compounds commonly called photographic

Silver halide developing agents are useful and which are described in various publications. For example, such compounds are described in the following publications: AJ A xf ο rd and JD K e η da! 1 in "Journal of Photographic Science", 2, 21 to 27 (1954); GE F icke η and BGSanderson;!, C. 11: 157-164 (1963); A. 1. A χ f ο rd and JD K e η da 11; "Scientific Photographic (Results of the International Conference for Scientific Photographic, Cologne, 1956)"; and W. E i 1 he,
O. H e 1 gave way, etc .; "Publisher
400 to 404 (1958), Darmstadt.

Typical examples of these compounds are l-phenyl-3-oxopyrazolidine, l-phenyl ^ -methylO-oxo-

pyrazolidine, l-phenyl-S-oxopyrazolidine-S-carboxylic acid, l-p-tolyl-3-oxopyrazolidine, l-p-methoxyphenyl-3-oxopyrazolidine, l-Phcnyl-4-ethyl-3-oxopyrazolidine, 1-phenyl-4-isopropyl-3-oxopyrazolidine, l-phenyl-4,4-dimethyl ^ -oxopyrazolidinJ-phenyl-S-methylO-oxopyrazo-

lidine, 1-phenyl-SS-dimethyl-S-oxopyrazolidine, 1-phenyl-4,5-dimethyl-3-oxopyrazolidine or 1,5-diphenyl-3-oxopyrazolidine.
The 3-iminopyrazolidines of the general formula (1)

gp

H. Frieser and Dr. O. H e 1 w ι c h «,

5 6

are also effective as usual photographic lionsmiltcls with the polymerization inducing wit-

Silver halide developers are used and are e.g. B. kung and weak development activity

in British Patent Specification 757,840 and eased; the second mechanism steals

German patent 870 418 described. Typical in that the polymerization reaction by the oxy-

Examples of the 3-iminopyrazolidines are 1-phenyl- 5 dation of the polymerization reducing agent

3-iminopyrazolidine, l, 5-diphenyl-3-iminopyrazolidine, with the oxidation product of the silver halide

i-p-Hydroxyphcnyl-3-iniinopyrazolidin or i-p-Methwicklerverbindungencn of the structural formula (I) introduced

oxyphynyl-3-iminopyrazolidine. will.

Ice cream is well known that with common vcr- The fact that by the weak developing

Conversion of the above-mentioned 3-oxopyrazolidine io with the deviating agent of the structural formula (I) and

with a p-aminophenol or hydroquinone a subsequent kinking with the enlivening

so-called superaddition behavior is achieved, means that the effect of initiating the polymer

d. H. has a greater speed of development than the salion, the effect of initiating the poly

Value that is promoted by simply adding the results in merization is used as a support for the

Use of every single component received 15 first mechanism viewed

will. With regard to the superaddilion behavior, on the other hand, the oxidation-reduction potential

various mechanisms voi beaten. It is essential to the silver halide developing agent

but it should be noted that the combination according to structural formula (I) is lower (stronger reduction

Invention of the customary combination both capable of) and that of the polymerization component

with regard to the type of reducing agent as well as the reducing agent, usually around

the purposes are different. In other words is 200 to 300 mV lower, if the concentration

in the usual combination the purpose of the tration ratio of the latter to the crslere nichl

Use of the two reducing agents (developer- is sufficiently high, neither the reduction of silver-

medium) only the reduction of silver halide halide nor the reduction of the Oxydalions-

to silver and the superaddition behavior is possible in relation to the ice. This is the reason

borrowed <k'i education ^ ¹ », obtained vhwindigkcil from silver. that the amount of silver halides

In contrast, in the combination according to connection with the structure (I) must be less than

the! turn the reducing agent, which has an effect on the amount of the polymerisalionseinlcitenden reducing

has to initiate the polymerization, a Wirungsmiltcl.

effect for the reduction of a silver halide / u silver 30 when using the polymerization initiator

and at the same time to introduce the radical polymer reducing agent and the silver halogen developer

sation of a Vmy compound or a vinylidene compound of structure (1) is the weight ratio,

compound, while the pyrazoline derivative of the pre- although the optimal ratio of the latter to the r

The general formula (!) given in the following is a first according to the types of compounds

Effect for reducing a silver halide * can be varied to 35, preferably smaller than eir

Silver must have, but no one-tenth, expressed in molar ratio, and is present

conduction of the polymerization must have. Such as, for example, in the molar ratio range from 1:20 to 20

As shown in the examples, l-phenyl-3-ox-o- has 1: 20,000.

Pyrazolidine has a strong developmental effect, also in the process variant in which the layer

however, there is no effect in initiating the poly- 40 first with the silver halide developing bond

mcrisalion of the monomer. Thus, the mark is based on the structure (I) developed and then with a solution

times of the invention in one respect that be by the polymcrisationseinlcitcnden reducing agent

the use of the reducing agent with a trades \ wrd. there is no particular limit to be

strong developability (silver halide- plus the concentration of the latter, but it is

Winder connection) together with the reduction 45 expedient and desirable, a washing tool between

agent which has an effect of initiating the polymer both development treatments. dal

cation of the monomer, but a slight excess of the silver halide content of all

Has reducing power, the introduction of the poly compound does not ge into the PolymerisationsssyMun

merization by the latter reducing agent will wear quickly.

can be executed, and also a high 50. According to a further embodiment, dir i rt ..-. nm \

Sensitivity to halogen photographic is the weight ratio of the pyrazole.J.ω in:.: A

silver emulsion layer can be obtained. Taulomere of the same to the polymer! · Τ, μίπ

The development mechanism, in particular the conductive reducing agent smaller than an Ahiitel

Initial or initiation mechanism of development expressed in molar ratio,

development of the silver halide photographic emulsion at 55 It was also recently found that di <

the method according to the invention is not yet the same effect as according to the invention by Ver

sufficiently clarified and it is therefore not unambiguous. Usage of p-aminophenol, pyrocatechol ode

in what way the combination according to uer Erhn-Amidol together with the reducing agent, the dii

tion is effective, however, the following two effects will have to initiate the polymerization

Mechanisms considered: 60 can be obtained.

The first mechanism is that, however, since the Oa is p-amino in this earlier procedure

Silver developed itself catalytically in the course of the phenol. Pyrocatechol, amidol or the like have an effect

Development on each exposed silver halide part - to inhibit radical polymerization in space

acts that have common silver halide developer properties, their amount is extraordinarily important

the structural formula (I) with the high development * - it is limited, while the pyrazolidines, since they are close

activity initially no or completely no effect on the developing nuclei / «.« Inhibition

acts to reduce the size or dimension of the radical polymerisation , in deem larger ones

larger, with the development effect of the reduction, compared with those mentioned above

Common compounds can be used be able.

Examples of vinyl compounds or vinylidene compounds, which are used according to the invention are acrylamide, acrylonitrile. N-hydroxymethylacrylamide, Methacrylic acid, acrylic acid, calcium acrylate, sodium acrylic, methacrylamide, methyl methacrylate, Methyl acrylate, ethyl acrylate, vinyl pyrrolidone, vinyl methyl ether, vinyl bulyl ether, vinyl · · isopropyl ether, vinyl isobutyl ether, vinyl butyrate, 2-vinylpyiidine, 4-vinylpyridine, 2-methyl-N-vinylimidazole, Potassium vinyl benzene sulfonate, vinyl carbazole. N, N'-methylenebisacrylamide, Ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, Polyethylene glycol dimethacrylate, divinyl ether or divinyl benzene.

According to a further embodiment of the invention, development is carried out in the presence of Sullitions. By l ^; A color image can be produced from the polymer image formed by the process according to the invention. According to a further embodiment of the invention, the pyrazolidine is used in a bath in which the halogen silver emulsion layer is developed prior to the treatment with the polymerization-initiating reducing agent.

The silver halide photographic emulsion layer is after the development in the bath mentioned and before the treatment with the polymerization initiator Washed reducing agent with water.

The turn is explained in more detail below using examples. In the following examples the case is explained in which the formed using methacrylic acid as a monomer Polymerisatbildcr were colored with basic dyes, whereby by the conversion of the Polymerisatbilder in color images, the effect or advantage according to the invention is clearest and moreover can be shown numerically. However, the invention is not limited to these cases.

example 1

A photographic light-sensitive material having a gelatin-chloroiodobromide silver photographic layer was exposed and then developed in a developing solution containing 8-A.mino-1 - naphthol - 3,6 - disulfonic acid, 1 - phenyl - 3 - oxopyrazolidine and sodium methacrylate.

The photographic light-sensitive material was prepared as follows: After applying intermediate or auxiliary layers to the two surfaces of a polyethylene terephthalal film, an antihalation layer was applied to one surface thereof and the other surface was coated with a fine-grained gelatin-halosilver emulsion, which was about 0.7 Moles of chlorine, about 0.3 moles of bromine, about 0.001 moles of iodine and about 100 g of gelatin per 1 mole of the silver, coated, said halide silver emulsion also contains a mero..yanine dye with a maximum sensitivity of 550 πιμ as a sensitizing dye, mucochloric acid in one Amount of about 1.5 g per 100 g gelatin as a hardening agent and a suitable stabilizer and surfactant contained. The application was carried out in such a way that the halogen silver emulsion layer contained ^{50 mg of silver per 100 cm 2.} A protective layer of gelatin was then applied over the emulsion layer to a thickness of about 0.8 microns. The photographic light-sensitive material so prepared was of a type commonly used for the production of line and half-tone images for the graphic arts.

From the photographic material thus prepared, three samples were cut out, and each of the samples was passed through a siliconometric optical wedge for 1 second with a 50 lux lamp exposed with a density increase of 0.15 per step ίο and then in a developer with the following Composition developed.

Sodium methacrylate 75 g

8-amino-1-naphthol-3,6-di-

sulfonic acid as below

specified

1-phenyl-3-oxopyrazolidine .... as below

specified

Potassium metabisulphite 3 g

2n - NaOH required amount

for setting

the pH value to 9.0 water remainder to 150 ml

8-Amino-l-naphthol-3,6-disulfonic acid ..
i-phenyl-3-oxo-

pyiazolidine

Trial number

1 I 2 1 3

8.5 mg

14.4 g j 14.4 g

8.5 mg

After development for 10 minutes at 30 C, the sample was 30 seconds with l, 5 ⁿ / _o acetic acid washed and then fixed in the following fixing solution:

Sodium thiosulfate (anhydrous) 150 g

Potassium metabisulphite 15g

Water rest to 1000 ml

After fixing, the sample was washed with water and cut into two parts. One of these Parts were dissolved in an aqueous 0.1 "solution of a red basic dye, namely Rhodamine 6 G.C.P. (CJ. Basic Redl), immersed for 5 minutes,

for 5 minutes with an aqueous 5% acetic acid solution washed, washed with water, in a Farmer's reducer (blood liquor salt) treated to completely remove the silver image, washed with water and dried.

A silver image was formed on one of the samples that was not subjected to the coloring treatment, while on the other of the samples subjected to the coloring treatment and bleaching treatment had been, a colored polymer image produced

forms was. Each image was measured for optical density through a green filter. The results of this are shown in FIGS. 1 and 2 shown in the form of characteristic curves.
F i g. Fig. 1 shows a characteristic curve derived from the silver image

was obtained.

F i g. Fig. 2 shows a characteristic curve obtained from the colored image and the amount of formed Polymer corresponds. In the F i g. 1 and 2, the number 1 denotes the results of experiment no. 1,

the number 2 the results of experiment no. 2 and the Number 3 the results of experiment no.3.

From Fig. 1, referring to the silver image, it was seen that the result of the experiment was Ni. 3 with

ίο

a content of l-amino-8-n; -iplithol-3,6-disulfonic acid and l-phenyl-3-uxopyrazolidine almost the same the sum of the result of Experiment No. 1 and the result of Experiment No. 2, each of which contained a single compound, wai.

On the other hand, on the basis of Experiment 1 according to F i g. 2 confirms that there was no development of the exposed emulsion layer with 1-phenyl-3-oxopyrazolidine Color image was obtained, d. That is, the formation of polymer according to the amount or extent the exposure was not observed. However, if l-amino-8-naphthol-3,6-disulfonic acid together with 1-phenyl-3-oxopyrazolidine (Example 3) was used, a color image was quickly formed and the polymer image was observed even in the areas where the amount of exposure was low. In other words, it can be seen that 1-phenyl-5-oxopyrazolidine alone has no effect with respect to the formation of a polymer image, however, the formation of the polymer image through promotes l-amino-8-naphthol-3,6-disulfonic acid.

If z. B. the two results at the point at which log E = 0 (E is the exposure amount) are compared, the density is increased by only 0.03 of fog in experiment 2 ei, while the density is increased by about 0.4 of fog was increased in Experiment 3, and if the two results are observed at the exposure amount that gives a density of 0.1 above fog, the exposure amount in Experiment 3 is about 0.6 (as the logarithm of the exposure image) lower than that Exposure to the maximum in Experiment 2, showing that the effective speed of Experiment 3 was increased about 4 times that of Experiment 2.

Example 2

The same type of photographic photosensitive Material as described in Example 1 was exposed as in Example 1 and then in a solution developed with the following composition:

Sodium methacrylate 75 g

Reducing agent having an effect of initiating polymerization as in Tab. I.

specified

Pyrazolidine derivative as in Tab. 1

specified

ao potassium metabisullite 3.0 g

2-n-sodium hydroxide required

Amount to adjust the pH value to the one shown in Tab. I.

specified value water remainder to 150 ml

Reducing agent crowd table ; I. crowd PH A. B. C. D. E. F. with an effect
Finleitiing No. the polymerization 4.95 g Pyrazolidine derivative 11.5 7th 10 10 0.18 0.14 0.04 Resorcinol 4.95 g 8.6 mg 11.5 5 13th 10 0.33 0.16 0.17 4a Resorcinol _ b 8.22 g l-phenyl-3-oxo- 8.6 mg 11.1 10 10 10 0.47 0.45 0.02 N, N-dimethyl pyrazolidine 5a methamino - phenol 8.22 g 8.6 mg 11.1 10 12th 10 0.60 0.33 0.27 N, N-dimethyl b methamino l-phenyl-3-oxo- phenol 2.80 g pyrazolidine 10.0 20th 0 5 0.16 0.16 0 3,4-dimeihyi- Oa 5-pyrazolone 2.80 g -. 8.6 mg 10.0 20th 11th 5 1.06 0.22 0.84 3,4-dimethyl b 5-pyrazolone 3.15 g l-phenyl-3-oxo- 10.0 40 9 5 0.60 0.25 0.35 o-xylenoI 3.15 g pyrazolidine 8.6 mg 10.0 40 12th 5 1.32 0.43 0.89 7a o-xylenol b 4.95 g l-phenyl-3-oxo- 11.0 15th 4th 5 0.19 0.19 0 Resorcinol 4.95 g pyrazolidine 10 mg 11.0 15th 12th 5 1.63 0.30 1.33 8a Resorcinol b 4.95 g l-phenyl-4-methyl- 10 mg 11.0 15th 10 5 1.37 0.23 1.14 Resorcinol 3-oxopyrazolidine C. 4.95 g l-phenyl-5-methyl- 10 mg 11.0 15th 11th 5 1.34 0.21 1.13 Resorcinol 3-oxo-pyrazolidine d 4.95 g 1-hydroxyphenyl 11.0 10 0 10 0.17 0.17 0 Resorcinol 4.95 g 3-iminopyrazolidine 10 mg 11.0 10 13th 10 0.98 0.19 0.79 9a Resorcinol b 4.95 g 1-p-methoxyphenyl- 11.0 20th 8th 5 OJ0 0, i9 Resorcinol 4.95 g 3-iminopyrazolidine 10.3 mg 11.0 20th 12 i 5 0.94 0.17 0.77 Oa Resorcinol 4.95 g 10.3 mg 11.0 20th 12th 5 1.00 0.16 0.84 b Resorcinol l-phenyl-5-carboxy-
3-oxopyrazolidine
l-phenyl-5-cafboxy- C. 3-oxopyrazojidine

I 924 721

After developing as described above for a period of time indicated in column Λ of Table I, the sample was subjected to fixing, washing, bleaching, washing and drying. The number of steps of maximum density at which the color image was observed was determined with the naked eye on the sample, and the results obtained are shown in column B of Table I. In addition, at a certain stage, the density of the color image was measured on each sample, and the results are compared with respect to each sample. In Table 1 above, the step number used in the above measurement is in column C, the density of the color image at the step in column D, the density of the color image in the fog region in column E, and the true density of the color image (ie, D to E) in Column F shown. Thus, the value in column F corresponds to the amount of polymer formed as a result of the specific amount of exposure given to the emulsion layer. In all tests it was found that the addition of the pyrazoline derivatives increased the number of stages at which the formation of the color image was observed and that the F value was increased at the same time. This shows that the rate of formation of the polymer image was increased and the effective sensitivity was also increased.

Moreover, when the pyrazoline derivative was used alone instead of using the combination of the reducing agent with the effect of initiating the polymerization and the pyrazolinedine derivative, the density corresponding to the value shown in column F of Table I did not fall below same conditions as shown in Table I were obtained. Accordingly, it is clearly seen that the increase the density and sensitivity in this case not just from the sum of the effects of the two Reducing agent, but is brought about by a superaddition behavior from it.

Example 3

The photographic light-sensitive material as described in Example 1 was used exposed and pretreated in an aqueous alkaline solution of l-phenyl-3-oxupyrazoiidine and then developed using resorcinol to carry out the polymerization.

After exposure of the sample for 10 seconds at 50 lux, as described in Example 1, the sample was pretreated in an aqueous solution containing 0.1 g / l of 1-phenyl-3-oxopyrazolidine, the pH of which was added by adding of sodium carbonate had been adjusted to 10.5 was the pre-treatment at 30 ⁰ C during the below in Table II given period of time executed, after which the sample was then given 3 times 15 seconds each washed in distilled water and in a solution having the following Composition was immersed for 30 minutes at 30 ⁰ C to carry out the development and polymerization.

Sodium methacrylate 54 g

Resorcinol 4.95 g

Potassium metabisulphite 1.5 g

2-n-sodium hydroxide required amount

to adjust the pH value to 10.5

Water rest to 150 ml

The sample thus developed was treated as described in Example 2, and the same measurements as in Example 2 were carried out. The results obtained are summarized in Table II. In tables, A denotes the time (hours) required for the pretreatment, B the number of stages of the maximum density at which a color image was observed, C the number of stages used in the density determination, Z) the ίο density of the color image of the stage, E is the density of the color image in the fog region and F is the true density of the color image (D to E).

Ii Table Il O E. F. A. 6th Γ 0.32 0.13 0.19 0 (con 10 0.34 0.12 0.22 trolls) .. 15th 5 1.07 0.21 0.86 ao 30 see .... 20th 5 2.67 0.56 2.11 1 min .... 5 4 min .... 5

Even if the development and polymerization a5 with the resorcinol methacrylate system after 15 minutes was interrupted, a color image, i.e. H. a polymer image observed; However, if the pretreatment using 0.1 g / l catechol under the same conditions as above indicated, was carried out after the treatment for a period of 15 minutes no polymer image formed. A polymer image was only obtained after a treatment time of 30 minutes received. It is believed that this is due to the fact that in the latter case a There was a polymerization inhibiting effect, while in the case of the use of pyrazolidines almost none such inhibitory effect occurred.

Example 4

The same procedure as described in Example 3 was repeated, using an iodobromide silver emulsion has been used.

After applying intermediate or auxiliary layers to both surfaces of a cellulose triacetate carrier and after applying an antihalation layer to one surface of this, the other surface was coated with a fine-grained gelatin-halogenated silver emulsion containing 0.012 mol of iodine, 0.988 mol of bromine and about 204 g of gelatin each 1 mol of silver contained, and was sensitized with a rhodan complex salt of monovalent gold, and further 0.3 g of 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene per 1 mol of silver as a stabilizer, about 0, 7 g of mucochloric acid per 100 g of gelatin as a hardening agent and also contains a suitable surface-active agent. The layer was applied in such a way that 60 mg of silver were contained in 100 cm ^{2 of} the emulsion layer . In addition, a gelatin layer 0.8 microns thick was coated on top of the emulsion layer as a protective layer. Such a photographic light-sensitive material is usually used for the production of internal images

used after the photogravure process and continuous positive images of soft tone.

After exposure of the sample produced in this way for 1 second at 50 lux, as in Example 1

3075

wrote, the Prohe was in an aqueous solution of l-phenyl-3-oxopyrazolidine; pretreated as in Example 3, washed with water 3 times each for 15 seconds using distilled water and then immersed for 15 minutes at 30 ⁰ C in a solution of the composition indicated below, to perform the development and polymerization time.

Sodium methacrylate 54 g

l-amino-ß-naphthol ^ o-disulfonic acid 10 g

Potassium metabisulphite 1.5 g

2n - NaOH required amount

to adjust the pH to 10.5

The sample developed in this way was as in Example 3 indicated, treated further and the measurements carried out in Example 3 were also carried out.

The results obtained are in the following

Table III listed below. Columns A to F in Table III refer to the same as in Table II above.

S. A. B. Table HI D. E. F. 0 0 (con C. 0.06 trolls) ... 3 0.06 0.06 0.56 ¹⁰ 30see .... 5 5 0.12 0.06 1.96 1 min 14th 5 0.66 0.10 2 min 18th 5 2.16 0.20 5

From the above results, the effect of the pyrazolidine derivative is clear and unambiguous confirmed. In addition, these pyrazolidine derivatives showed the same effects as Metol or Amidol and therefore, these can be applied and used together with these compounds

ao an appropriate amount of the same can be better Results are achieved.

1 sheet of drawings

Claims (1)

1 2 p "" nfo "c -. . . 5. The method according to claim 1, characterized in ratentansprucne. shows that the pyrazolidine in a bath 1. Process for the production of polymer is used, in which the halogen silver emulsion images, one in an image-wise exposure layer before treatment with the polymer photographic silver halide emulsion 5 initiation reducing agent! developed layer containing latent image of silver will. halide particles which are solid in a binder 6. The method according to claim 5, characterized in that are kept in the presence of water and draws that the photographic halogen at least one monomeric, normally solid, silver emulsion layer after development in octer liquid vinyl or vinylidene compound io the bath mentioned and before the treatment with by treating the layer with at least the polymerization initiating reducing agent one resorcinol, one m-aminophenol, one washes with water. Hydroxy- or Aminonaphlhalin or a 'Derivative thereof, a dihydroxy, diamino or Monohydroxymonoaminonaphthalin, whose 15 The invention relates to a process for the Herfunctional group in the 1,6- 1,8-, 2,5- or position of polymer images, in which a are in a 2.7-position, a pyrazoline- 5-one, image-wise exposed photographic silver halide or a substituted phenol (substituted with a genide emulsion layer containing latent image of alkyl groups, substituted alkyl groups, acyl silver halide particles, which are held in a binder groups or halogen atoms) as reduction 20, in the presence of water and medium and with a silver halide developer - at least one monomeric, normally solid compound is developed, characterized in that the development treatment of the layer with at least one Res. · in the presence of a pyrazolidine or a tauto- a , an m-aminophenol, hydroxy or amine
meren of the same executes, the pyrazolidine 25 naphthalene or a derivative, of which dihydrox \ by the general formula I - diamino or monohydroxymonoaminonaphthalm, R whose functional groups are in the 1,6-, 1,8-, ^1N ρ CA 2.5 or 2.7 positions, a pyrazolin-5-one, or a substituted phenol (substituted R-2 30 with alkyl groups, substituted alkyl groups, acyl ¹ groups or halogen atoms) as a reducing agent R3 [; and with a silver halide developing agent Q Nu is developed. η ν. It is known that by developing a photographic ¹ 35 graphic shark silver emulsion layer with a '' latent image by means of a specific reduction