DE2006710A1 - - Google Patents

Description

"Pyrrolidonyl-polyacroleine, hydrogen sulfite adducts thereof" and their use for the production of gelatin containing ■ photographic layers "

Priority: February 13, 1969, V.St.A., No. 799 072.

- "'" No. 799 089

¹¹ . . π Hr-. 799 108

The invention relates to pyrrolidonyl polyacrylic lines.

Polyacrolein. Is. Produced by radical polymerization, as in "Acrolein" by "CW Smith, John Wiley & Sons Inc., New York (1962) p. 225, and in" Kinetics and Mechanisms of Polymerization "j Vol.1, Part 1 "Vinyl Polymerization" by RC Schulz, M. Dekker, New York (1967), p 410. It is known that unstabilized acrolein spontaneously forms a solid, infusible and insoluble on standing

009843/1947

Polymerizes product which has been termed "disacryl" (see Redtenbacher, Liebigs Ann. Chem. 47 (1843), p. 113).

Polyacrolein appears to work well for several purposes, but there are some difficulties in handling it. In particular, it has heretofore been difficult to maintain the solubility of the polymeric acrolein high molecular weight and aldehyde functionality. U.S. Patent 3,235,524 shows that high molecular weight produced by radical polymerisation Polyacrolein is insoluble in all conventional organic solvents and that it is a macromolecular, infusible and insoluble acrolein homopolymer, which has essentially no free aldehyde groups, in aqueous sulfuric acid Solution at elevated temperature can convert into a soluble product by reaction with the sulphurous acid. the The amount of acid used in the reaction is sufficient to dissolve the reaction product.

It is further known that high molecular weight polyacrolein at temperatures below 80 ⁰ C in all organic solvents, such as dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, dioxane, benzene or ethyl acetate is insoluble.

It has now been found that one normally insoluble polyacrolein can solubilize by reaction with pyrrolidone to such an extent that it can be dissolved in various polar solutions at room temperature. agents, such as dimethylformamide, is soluble. In general, such polyacroleins are suitable for the reaction, for example, which from <*, / X-ethyleni8Ch unsaturated aldehydes, e.g. acrolein, <* - or

009843/1947

mm "^ S mm '

-substituted acroleines, such as (-Ethy! acrolein, oC-tsobutylacrolein, oc-chloroacrolein, / S -phenylacrolein, e ^ -decylacrolein orflC-cyclohexylacrolein, have been prepared .. Preferred aldehydes are, for example, -, γS-monoethyls with 3 "to 12 carbon atoms, in particular theot- and β- substituted acroleins, in which the substituent inoC- and / or ^ -position is an alkyl, cycloalkyl or aryl radical with not more than 8 carbon atoms -Alkenals with up to .8 'carbon atoms are of particular importance.

■ ■■; ·. '■: ■■ - ■ ■ ■ · · ■■■■■' i

• As already mentioned, acrolein polymerizes in the presence of free radical-forming catalysts to polymers ,, which in conventional are insoluble in organic solvents. Suitable catalysts are e.g. peroxides, such as benzoyl peroxide, hydrogen · perpxide, potassium persulfate, alkali perborates, diacetyl peroxide, ■ tert-butyl hydroperoxide, tert-amyl hydroperoxide, di-tert-butyl peroxide, Di% tert-hexyl peroxide, acetylbenzoyl peroxide, cumene hydroperoxide, tetralin hydroperoxide, phenylcyclohexane hydroperoxide, tert-butyl-isopropyl-benzene-hydroperoxide, tert-butyl-

'■■■ - ■■ ■■■■ < ι

peracetate, tert-butyl perbenzoate, di = tert-butyl phthalate, di-tert-butyl-peradipat or tert-butyl percarbonate, azo compounds, wieixi _'t ^ ^l * 3-azo-bis-isobutyronitrile _f o <f, oC'diisobutyrate, o (, oc ¹ -azo-bis- (o <l, ^ - dimethylvaleronitrile), oC , »^ - azo-bis-isobutyramide, oC, ö ^ -azo-bis - ^ - cyclopropylprapionitrile), <^, od ¹ - (oi-methyl-, yS-phenylpropionitrile) ,, ^ - (carbon amylazoisobutyronitrile), o ^, o (-azobia- (o {-cyclohexylpropionitrile), 1,1 'razodicyclo-oxanecarbonitrile , Diazoaminobenzene or 1,1'-azo-bis-O-phenylethane). Or various aldoximes, ketoximes or azines.

009 8 4 3/194 7

The polyacroleins suitable for making the pyrrolidonyl polyacroleins of the invention are made by. Obtained polymerization of the double bond and have a molecular weight of over 50,000, preferably between 100,000 and 2,000,000. These are values that are determined using the light scattering method. The preferred molecular weight range corresponds to intrinsic viscosity numbers (determined on the solubilized polymer) of 0.9 to 5.0 dl / g. These values advertising. '"The determined by the .for the measurement of .Polyelektrolytviskositäten usual method at 2'5 ^0G.

It has been found that the high molecular weight polyacroleins when brought into contact with pyrrolidone up to a concentration

: from about 15% by weight dissolve relatively quickly. This solubility is stirring

from the formation of a new product, namely a pyrro-

lidonyl polyacrolein. In addition, the polymer dissolves without any significant impairment of the molecular weight of the polyacrolein. The aldehyde remains ER w ^ hold, as is evident from the rapid reaction with aqueous SOP or sodium bisulfite to form Hydrogensulfitaddukten ·

The pyrrolidonyl polyacrolein of the invention is stable; when treating with dilute hot acid or when reacting with No pyrrolidone is split off with SOp or with metal hydrogen sulfites. The reaction with metal bisulfites is extremely surprising, since the entire polymer turns out to be a hydrogen sulfite adduct Dissolves in water without any pyrrolidone residues being split off.

[■■ ". 0 0 9 8 A 3/1 9 A 7

In general, the empirical formula provides for the new, polymers of the invention so that at least one pyrrolidone molecule comes to 4 'acrolein building blocks. Thus possesses the pyrrolidonyl polyacrolein about the following / structural formula:

The ratio of acrolein building blocks

preferably is preferably from about 3-1 to 2: 1 to NEN Pyrrolidoneinhexten about 7: 1 to 2: * \ _f and pyrrolidonyl polyacroleins generally have a relatively low nitrogen content, of about 2.5 to 6 x is fo.. In addition, other products with lower ratios of acrolein building blocks to pyrrolidone units with significantly higher nitrogen contents were also manufactured.

The pyrrolidonyl polyacroleins of the invention are very suitable, either in the form of the pyrrolidone solution or as an aqueous hydrogen sulfide adduct, for the crosslinking of, for example, polyalcohols or polyamides, such as polyvinyl alcohol, cellulose, polyethylene glycol or gelatin. In addition, the pyrrolidonyl polyacroleins can be dissolved in polar organic solvents, such as dimethylformamide or N-methylpyrrolidone, and cast from these solutions to form clear, brittle films.

00 9 843/1947 BATH ORIGINAL

Copolymers of acrolein with other ethylenically unsaturated monomers, such as those which have at least one C = C - grouping, preferably a CII ₂ = C = grouping, such as styrene, oC -methylstyrene, butadiene, isoprene, methylpentadiene, ethylene, Propylene, isobutylene, isooctene, vinyl acetate, vinyl propionate, vinyl pyridine, vinyl naphthalene, vinyl cyclohexane, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylic acid esters such as methyl methacrylate, ethyl acrylate, ethyl methacrylate, allyl methacrylate, allyl alcoholate, allyl alcoholate, allyl alcoholate, allyl alcoholate, allyl alcoholate, such as allyl alcoholate, allyl alcoholate, allyl alcoholate, allyl alcoholate, allyl alcoholate, such as allyl compounds, Allylcyclohexanecarboxylate or allylamine are accessible to reaction with pyrrolidone. In these polymers, the aldehyde polymer groups are essentially accessible, while the / at the same time are more soluble in conventional solvents than the pyrrolidone-free polyacroleins.

The inventive reaction of the polyacroleins with pyrrolidone can be carried out at room temperature, but the reaction proceeds more rapidly at an elevated temperature. However, in addition to accelerating the reaction, temperatures above 150 ^° C. can favor side reactions which have a disadvantageous effect on the end product. In general, the pyrrolidonyl polyacroleins are formed when the polyacrolein is added to the pyrrolidone. The proportions of the starting compounds depend on the desired end product. In ^% most cases it is easier to use an excess of pyrrolidone over and above the calculated amount, since the desired end product is deposited as a precipitate in the pyrrolidone.

009843/1947

It is believed that the reaction product of pyrrolidonyl polyacrolein and sulfur dioxide or hydrogen sulfite as follows. Structure has: ■. ".. '.

Hydrogen sulfites suitable for the inventive reaction of pyrrolidonyl polyacrolein have the general formula M (HSO ₅ ), in which M is a metal atom and m is the valence of the metal M. "Examples are the hydrogen sulfites of groups IA, HA and IHA of the Periodic Table, as described in "Handbook of Chemistry and Physics", 38th edition, pp. 394-395, for example sodium, potassium, calcium, magnesium or aluminum bisulfite. Ammonium bisulfite can also be used. The suspension of the bisulfite can be achieved by adding the metal bisulfite as such to the reaction medium or using the corresponding pyrosulfite (meta bisulfite), which forms the bisulfite upon addition. In addition, an aqueous one can also be used 'Use sulfur dioxide solution.

00984 3 / '1-9.4 7

The pyrrolidonyl polyacrolein-II hydrogen sulfite adduct can be produced in this way that nan the pyrrolidonyl polyacrolein and the metal hydrogen sulfite of the general formula M (HSO,) in one single-phase liquid, which consists essentially of water, suspended. The reaction can be carried out by the following reaction equation shown v / earth:

CH ₂ -CH-CH

+ M (HSO ₃ ) -

CH ₂ -CH

CHOH

SO ₃ -

in which M and m have the aforementioned meaning. If M is a bivalent or polyvalent metal, then this is with 2 or more acro-Iein basic building blocks linked in the reaction product. It is well known that polyacrolein has a very complex structure and it is believed that polyacrolein has both free aldehyde groups and masked aldehyde groups in the form of aldehyde hydrates and has acetal bonds (cf. e.g. R.C. Schulz, loc.cit.). In the reaction according to the invention, however, reacts the polymer in each case with the hydrogen sulfite in the manner described with formation of the adduct.

In the preparation of the hydrogen sulfite adduct according to the invention, temperatures are preferably used which are not above the Boiling point of the aqueous sulphurous acid or hydrogen sulphite solutions lie.

00984 3/1947

The invention also relates to the use of the pyrrolidonyl-polyacrolein-hydrogen sulfite adducts. of the invention for the production of photographic layers.

It is of great importance for photographic material to be able to have layers that are more resistant to water and aqueous solutions, swell to a lesser extent and have a higher softening point than pure gelatin layers. This is generally achieved by the fact that the gelatin, with various compounds that are ' _Λ

■ '■■ ■ -' ■ - I

have a wetting effect on the protein chains. This process is known as hardening. However, hardening is supposed to result in the gelatin do not lose their water permeability. When using known hardening agents die'Härtung begins after Drying of the layer and reaches the maximum after a few weeks. A large number of compounds are known which are certainly very "effective, but harden in an unpredictable manner. Therefore the hardening process cannot be precisely controlled. so that the photographic material can be

■ ι

is subject to changes in its sensitivity.

To the so far; Proposed hardeners include, for example, metal salts such as chromium, aluminum or zirconium salts, aldehydes or salt-forming aldehydes such as formaldehyde, dialdehydes or <tf, / 3-dichloro ^ -formyl-acrylic acid, 1,2- or 1,4-diketones, such as cyclohexane-1,2-dione, quinones, chlorides of dibasic organic acids, dianhydrides of tetracarboxylic acids, compounds with reactive vinyl groups, such as vinyl sulfones, acrylamides, compounds with at least two heterocyclic rings, = dl ⁼ e light

009843/1947 / BAD

can be opened, such as Äthylenoxid oder'ätthylenimin, or polyfunctional methanesulfenic acid esters. Own this hardener generally low molecular weight.

Some of the foregoing compounds are photographically active and can therefore be used for certain photographic halide emulsions Not used. Other known hardeners have other disadvantages. For example, metal salts increase the brittleness of the photographic layer, dialdehydes cause colorations and

Anhydrides and acid chlorides change the pH of the emulsion in the initial stage of hardening. All low molecular weight compounds have the disadvantage that their hardening is not restricted to certain layers of a photographic multilayer, since they can diffuse through all sub-layers.
In addition, the hardening can be carried out with the aforementioned hardeners
cannot be controlled as this begins after drying and increases during storage. This effect is known as post-curing. In the case of some emulsions for photographic papers, this effect is extremely disruptive, since it changes the toning of the silver image developed on such papers with prolonged storage. For photographic papers, in particular for papers with a brown tint, it is therefore important to find a hardener that reacts to the
Layer, even if it has been stored for a long time before processing, only has a slight influence, but during development it increases the softening temperature of the layer considerably. The developed papers can then be stored for a relatively long time, with the image toning only. is easily changed.

009843/1947

■ '■■;■'. ■■■ - - ^; - ^: - ■ - ίΐ - - ·.

In contrast to the aforementioned, low molecular weight hardeners, the previously known high molecular weight hardeners, such as poly aldehydes, have eg. the regular acid oxidation products of starch, only a slight hardening effect, since even in the most favorable case there are only 2 aldehyde groups, η per hexose basic building block. The Maleinsäürehalbester ^by: hoohmOlekularen, alcohols, such as polyvinyl alcohol, possess similar disadvantages.

cause beyond the disadvantages described above

the aforementioned hardeners numerous, undesirable photographic Effects. E.g. some hardeners of the aldehyde type tend to be stronger -Fogging in the emulsion. Other types of hardener tend to have hardening intensity during storage of the emulsion to subside. It is therefore desirable that the gelatin hardeners, especially when used in photographic emulsions are used, do not adversely affect the photographic properties of the emulsion. This also applies to photo ■ graphic gelatin layers often associated with photographic Emulsion layer are in contact.

.. ■ "■ '■■■ ^{.:::: Λ'} ν · _^';:.: .. ■■■■ .. ·: ■ ι

In addition, the gelatin hardeners used up to now tend to be special those of the: chrome alum type, in addition, their hardening properties at ^^ higher pH of the photographic development Lose S and toner solutions. .

It is a benefit of the pyrrolidonyl polyacrolein hydrogen sulfite adducts the invention that they cause no disadvantageous .phptographic effects during gelatin hardening and that they also with the normally used in photographic processes

009843/1947

v / ended higher pH values v / are effective. In addition, act they are delayed and have an effect even if the pH value changes Emulsion does not adversely affect the photographic effect.

If the pyrrolidonyl polyacrolein hydrogen sulfite adduct of the invention is a gelatin solution that is used to produce a Surface layer used for the gelatin-silver halide emulsion layer is added, a photographic one is obtained Material in which during storage before use only

^ very little hardening occurs. If, however, see the photograph If material is treated at a relatively high pH of about 7 to 12 during the development process, one obtains a very good, very fast curing product. The water-soluble pyrrolidonyl polyacrolein hydrogen sulfite adducts are the mixture containing gelatin either added directly before coating, or the gelatin containing mixture is immersed Mixture in a solution of the pyrrolidonyl polyacrolein hydrogen sulfite adduct. In general, the amount is about 1 to •% by weight, based on gelatin. However, it can be used for special

For the purposes of this, slightly smaller or larger amounts can also be used. If an aqueous solution of the pyrrolidonyl polyacrolein hydrogen sulfite adduct is used, the concentration is about 1 to 10 wt .- ^.

All conventional gelatin-silver halide emulsions are purely the hardeners according to the invention suitable, e.g. those containing silver bromide, silver iodide or chloride, or mixtures thereof.

00984: 3/1947

■■ - ■■. ■ "■ - 13 -

In addition, the pyrrolidonyl-polyacrolein-hydrogen sulfite adducts can be used in conjunction with all conventional developer systems which are generally used for the development of layers based on gelatin-silver halide. ¹

HydXQgen Recently it has been proposed to use polyacrolein / süTiit adducts as hardeners for photographic gelatin layers and gelatin '. To use silver halide emulsion layers. These compounds cure satisfactorily 'alkaline Bedingun- _v gene jedoch- have the disadvantage that they must be added to the gelatin layers in a very narrow pH range, the tolerance of only 0.1 pH Einheiten.beträgt. The well-known polyacro-

Drugs ■ '' ■■■ '

lein / süTfit adducts work satisfactorily, so only within a pH range of 5.2 to 5> 3 and cause considerable fogging when the pH value drops to 5 »4 ■ ■ increases to 5.6. In contrast, the pyrrolidonyl polyacrolein hydrogen sulfite adducts of the invention used without any disadvantage within a pH range of 5.0 to 6.0 will. -

The hardeners according to the invention can also be used in conjunction with others inorganic or organic hardeners are used,

. or

such as alum or potassium chrome alum, formaldehyde, glyoxal / 5-dichloro-A-formyl-acrylic acid. This hardener combinations cause a temporary cure before the alkaline process property Renon, while the pyrrolidonyl polyacroleine-bisulfite adduct causes the complete and permanent cure during the alkaline treatment of photographic · layer.

. 009843/1947.

-H- The examples illustrate the invention. . '

example 1 Manufacture of polyacrolein

A 2 liter multi-necked round-bottomed flask equipped with a stirrer, condenser, thermometer, temperature control and nitrogen inlet tube is equipped, is charged with 1354.4 g of water and 175.1 g of freshly distilled acrolein. The mixture is flowing under.

heated to 45.degree. C. using nitrogen. After adding 25.0 g

'Potassium persulfate with stirring, the reaction mixture at 45 ° C stirred under nitrogen for 2 days. During this time, the polyacrolein separates and the base * becomes white and thick. The sludge obtained is filtered, washed well with water on the filter and dried in a vacuum drying cabinet. 61.2 g of a white powder, the IR absorption band, are obtained at 2.9, 3.42, 5.8, 6.12, 6.86, 7.17, 7.35, 7.52, 9.75 and 12.05 at.

Example 2

■ t 25 g of polyacrolein, which have been produced by redox polymerization of acrolein with potassium persulfate and silver nitrate in an aqueous medium, are added to 475 g of 2-pyrrolidone. The mixture is then ^{heated to 80 °} C. for 4 hours with stirring. The viscous yellow solution is filtered through a glass frit and then poured into 3% acetone. The pale yellow powder which separates out gives 26.1 g after drying at room temperature. Analysis: C, 59.66 95} H, $ 7.54 \ N, 4.54%

009843/1947

- 15 - ■ -

Example -3 . . "·

90 g of Polyacroleins prepared according to example are .erhitzt together with 450 g 2-pyrrolidone under stirring for 4 hours at 80 ⁰ C. Working up according to. Example 2 gives a

".. wle__in_ example 2
similar product Γ. The fancy; Pyrrolidonyl-polyacrolein is soluble in II ^ methyl-2-pyrrolidone ^{:, · pyrrolidone, - dimethylformamide 1} and hexamethylphosphoramide. Analysis of the product shows that there is at least one pyrrolidone unit on .4 aero-, leingruhdliaustine * ■■. ■■■ - ■■ ', ..- ■'

Example 4 - (J

21 g of polyacrolein from Example 2, 200 ml of benzene and 28 g, pyrrolidone are refluxed for 4 hours. Filter the solid is washed off repeatedly by slurrying the solid in benzene and, after drying, a product is obtained with it $ 3.61 nitrogen content. This corresponds to one pyrrolidone unit per 5.28 basic acrolein constituents. '■

Example 5

By ~ 4 hours of heating at 80 ⁰ O a mixture of 1.5 g of pyrrolidone, 16.5 g of N-methylpyrrolidone and 2, .O g of Polyacro- I! One of Example 1 to obtain a solution of pyrrolidonyl polyacrolein. A film cast from this 10-gel solution and dried under reduced pressure is clear and brittle.

Example·. 6th * ·

A mixture of 5.6 g of the polyacrolein from Example 2, 100 ml Benzene and 8.5 g of pyrrolidone are heated under reflux for about 6 hours while stirring, using a water-cooled reflux condenser and a water trap is used. After parting

009843719 ^ 7

After filtering and drying for 2 hours at 1 Torr, 0.5 ml of water is obtained 6.07 g of a product which gives the following analysis: C, 57.54 ^C M H, 7.50 ^c / o \ N, 5.66 ^c / t>.

Example 7

25 g of a spontaneous polymerization prepared PoIyacroleins v / ground with 150 g pyrrolidone for 4 hours at 80 ⁰ O heated. After filtering the viscous solution through a glass frit, the filtrate is poured into 3 l of acetone. A product is obtained which gives analytical values similar to those of Example 2.

w ■

Example 8

26.1 g of the pyrrolidonyl polyacrolein prepared according to Example 3 are stirred at room temperature with 225 g of 8% aqueous sulfur dioxide for 4 hours. After this time, the solution is complete. After filtering the pale yellow solution, nitrogen is bubbled through this solution for 4 hours. The pH of the solution is adjusted to a value of 5.5 by adding 10% sodium hydroxide dropwise. Then the difference is made up to 261 g with water. Part of this solution is removed and dried at 40 ° C. in a vacuum drying cabinet. A pale yellow substance is obtained which is still water-soluble even after heating to 100.degree. The analysis (0.38.37 ^c fa H, 5.60 fa N, 2.49 1 ° \ S, 9.72 #;) shows that the substance has an S / N ratio of about 1.7 having.

Example 9

A portion of the pyrrolidonyl Polyacroleins prepared according to Example 3 is heated in a concentrated aqueous sodium bisulfite solution for about 4 hours at 60 ⁰ C. After the fiI-

00984.?/1947

2008710

.- ■■■ .. "": ■■■. «. it -;

■ dripping the yellow solution for 4 hours passed LÖstmg nitrogen through this'. The ρίί value is adjusted with 10% sodium hydroxide. If part of the solution is dried in a vacuum drying cabinet at 40 ^{0 0} , a solid substance is obtained which, even after heating to 100 ⁰ G, is still water-glass a rod filter similar to that produced in Example 10 with a similar S / B ratio. '' ■

Example 10 ._ ■ '■'"i

The Pyrrölidönyl-ltoiyäcrQlein of Example 4 is reacted according to Example S with Schwedfeldiqxid * Me obtained solution is set to a buffer of 5.5. The product obtained in this way is incorporated into gelatine, which is then tested according to the usual methods. Above a pH value of 5, the pyrrolidonyl-polyacrolite-hydrogen sulphite adduct is more stable than the polyacrolein ^> -hydrogen sulphite-A ^; ddukt _r as the complete absence of the veil shows.

Example 11 . · "

1 g of the pyrrolidonyl-polyacrolein-hydrogen sulfite adduct prepared in Example 10 is incorporated into one kg of a silver bromide chloride emulsion as used for the production of portrait papers for high magnification. The bromide / chloride ratio is 70:30. the emulsion contains 7 wt -. ° / o gelatin and the silver halide equivalent to 18 g of metallic silver. The pH of the emulsion is adjusted to a value of 5.5, then the emulsion is applied to a suitable surface by means of a 20.4 cm stirrer. from

009843/194?

2 Comparative emulsions are also produced in layers, ■ © in © without the use of a hardener and the other with the use of polyacrolein-hydrogen sulfite adduct as hardener. The layers are 1.5 minutes "at 20 ⁰ G in a Ehtwiökierlösung d © r following composition developed:

Sodium hexametaphosphate 1.0 g

Potassium metahydrogensulfite · · 3 * 5 g

■ p-methylaminophenol sulfate 0.5 g

H '1 ~ phenyl-3-pyrazoidone. . 0.1 g

■ sodium sulfate 12.0 g

Hydroquinone ". 3.5 g

Sodium carbonate (monohydrate) 24.0 g

Potassium bromide. 0.3 g

Benzotriazole 0.03 g

Water, added to 1 liter

Bi @ developed layers are stopped solution in a dilute glacial acetic acid Wk, fixed with a sodium thiosulfate solution and ffiit a commercially available toner solution containing a mixture of sodium sulfide, sulfur and Hatriumselenid in an alkaline medium "at a pH of about 11.4, treated The following softening points are obtained in ⁰ G:

uncured polya.pol.la- ISJ ₈₀ ^ JSS =

Material hydrogen sulfite hydrogen sulfite

© developed 35 120 115

toned 35 H5136

009843/1947

^: 20CR710

pie photographic properties of all layers are im essential, equal. The veil value. ; amounts to

O, O-9.j _; dsr log; E speed value 8.7 and the maximum density 1.47. ... ... -.-: ■■ -. . ...; ·. ·

When the above-described experiments are repeated at a pH of 5.7, the photographic properties are retained when using pyrrolidonyl-polyacrolein-hydrogen sulfite adduct, while the fog value when using polyacrolein-hydrogen sulfite adduct is 0.09 0.21 increases and the log E speed value drops from 8.70 to 8.50 fl. The differences become even clearer if the development is carried out for 8 minutes in a "GAi ¹ Vividol developer". In this case, the haze value increases

when using polyacrolein hydrogen sulfite adduct. to 0.31. '-.

So while the pyrrolidonyl polyacrolein hydrogen sulfite adduct tolerates the increase in the pK value from 5.3 to 5.7 without further ado, If polyacrolein-hydrogen sulfite adducts are used as hardeners, a considerable decrease in the photo- f graphical properties. · ■

Example 12 .

According to Example 11, using pyrrolidonyl-polyacroleic hydrogen sulfite adduct photographic layers produced as hardeners, which are then coated with a 2-strength gelatin surface layer be coated. Developing and toning are carried out as in Example 11 with the exception of the following Toner solution is used

00 9 8 43 / 19A7

200R710

Sodium polysulfide potassium carbonate water, supplements too

7.5 g 2.0 g 1.0 liter

The results are compiled in Tables I and II. Table II shows the softening temperatures of the unprocessed and toned layers after aging
visible from 20 days.

Table II

layer

No.

Softening temperature ( ⁰ C)

unprocessed toned

fresh after 20 days fresh after 20 days

1 2 3

54 53 61

52.

62

106 124 153 155 157 164

009843/1947

Part I

CjO CO ■ fc "»

Shift. Hardener system mg hardener /
No. - "■ kg of emulsion .70-160 pH
emulsion value
Surface * 5.2 egg
unchanged
is working • 53 • softest
Blackness
te eat- ■
procedure temperature ( ⁰ Q)
'tinted 1 potassium chrome alum 0.8 g / kg Formaldehyde (37%) 3 ml / kg 5.2 54 132 106 2 potassium chrome alum 0.8 g / kg 70-160-
800 Formaldehyde (37%) 3 ml / kg 5.2 61 Pyrrolidonyl polyacroleiri-
Hydrogen sulfite adduct (5- ^ ig! 5.3 147 153. 3 potassium chrome alum 0.8 g / kg 70-160- Formaldehyde (37- ⁶ Ag) 3 ml / kg 1200 Pyrrolidonyl polyacrolein Hydrogen sulfite adduct (5 - $> ig 5.3 . 134 157 \

Claims (1)

- 22 claims 1. Pyrrolidonyl polyacroleins. 2. Pyrrolidonyl polyacrolein according to. Claim 1, characterized marked,. that the ratio of acrolein preferably about 3: 1 to 2: 1, basic building blocks to pyrrolidonyl units 7: 1 "to 2: _t 1, is. > 3 · pyrrolidonyl polyacrolein according to claim 1, characterized A characterized in that they have a nitrogen content of 2.5 to 6 5 ». 4. pyrrolidonyl polyacroleins according to claim 1 to 3 »d a through characterized in that the acrolein basic unit is optionally substituted in the or- or Α-position <*, (3-ethylenically unsaturated aldehyde, preferably an <x, / i-mom> ethylenic unsaturated monoaldehyde with 3 to 12 carbon atoms, in particular mono ^ - or ^ -substituierteraf, ^ - monoethylene unsaturated monoaldehyde, in which the substituent in «<- or ψ (> position is an alkyl, cycloalkyl or aryl radical with up to carbon atoms. 5. pyrrolidonyl polyacroleins according to claim 4, characterized in that the acrolein basic building block 2-alkenal with up to 8 carbon atoms, preferably acrolein. 6. A process for the preparation of pyrrolidonyl Polyacroleir NaOH to claim 1 to 5, characterized in that 'the polyacroleins with pyrrolidone, gege jnenfalle under heating at (temperatures up to about 150 ⁰ C, - 009843/1947 20G6710 7. Use of the pyrrolidonyl polyacroleins according to claim 1 to 5 in the form of their hydrogen sulfite adducts for the production of Photographic emulsions or layers containing gelatin. 009843ΜΉ7