HU196519B - Process for making photographic layers containing water soluble stabilizer and/or fog inhibitor complex with inhibited mobility - Google Patents

Abstract

The invention relates to a process for the preparation of black-and-white or colored photographic materials, which also contain water-soluble stabilizer and / or antifoggant complexes with greatly reduced or completely suppressed mobility, these materials from a paper carrier with a barite layer with a gelatin and or polymer content or with a polyethylene coating or from a film base, photosensitive layer (s) and protective layer (s). According to the invention, in the aqueous cast solution required for producing the photosensitive layer or protective layer of the photographic material or the auxiliary layer of the carrier (barite or substrate layer), a complex compound formed from a water-soluble cyclodextrin polymer and a stabilizer and / or antifoggant in a concentration of 10 to 100 g complex / mole of silver halide or in the other layers of 5 to 120 g complex / kg gelatin, preferably from 20 to 40 g complex / mole silver halide or 30 to 50 g complex / kg gelatin, wherein the molar ratio of polymer / stabilizer and / or antifoggant is between 1: 1 and 30: 1, preferably between 2: 1 and 5: 1.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing black and white or color photographic layers containing inhibited mobility, water-soluble stabilizer and / or veil complexes based on gelatin and / or polymer based on barite paper or polyethylene (RC )reein coated 'paper or film substrate. , consisting of photosensitive layer (s) and protective layer (s).

In photographic practice, when manufacturing both black and white and color materials, it may be necessary to fix certain additives (such as stabilizers and veil inhibitors) for a specific purpose in one layer of photosensitive photographic material, i.e., to prevent these additives from being deposited during manufacture or development ( (s) of the product.

In order to accomplish this goal, C12-C18 alkyl chains are generally introduced into the molecule of the additive. It is well known, for example, to prevent diffusion of colorants or precursors in this way (G. F. Duffin, Photographic Emulsion Chemistry, Focal Press, London, 1966, 1976). However, the materials prepared in this way have very poor water solubility and therefore either have to be dissolved in an organic solvent which requires a special procedure for their introduction into the aqueous phase or the incorporation of additional water-solubility-promoting group (s) into the molecule. (G. F. Duffin: Photographic Emulsion Chemistry, Focal Press, London, 1966, p. 197).

Inhibition of diffusion of photographic stabilizers and veil inhibitors may be necessary in the production of both colored and black-and-white materials, however, to prevent the formation of rock-like effects;

It is known to employ cC, O, or N-cyclodextrin in photographic layers to increase the sensitivity of the photographic material. This is disclosed in Japanese Patent Publication No. 53/78, 48,735 (C.A. 90946543 r). The photographic activity of these cyclic oligosaccharides is similar to that of oligo- and linear polysaccharides (lactose according to British Patent No. 978,880, dextran according to U.S. Patent No. 39,714, Polyfructose according to U.S. Patent No. 3,137,575). however, their solubility in water is moderate. Therefore, the complexes of such cyclodextrins with a stabilizer or an anti-veil can only be added to the latter in an order of magnitude smaller than usual and also diffuse freely in the layers of the photographic material.

SUMMARY OF THE INVENTION The object of the present invention is to form water-soluble systems that are water-insoluble or poorly soluble in stabilizers and / or veil inhibitors, without the use of organic solvents, having a very limited diffusion capacity in their photographic action and perfectly compatible with other components of the photosensitive system.

The present invention is based on the discovery that stabilizers and / or veil stabilizers commonly used in the photographic industry form an inclusion complex with the water-soluble polymer derivatives of cyclodextrins, the solubility of which reaches the concentration required by the technology.

The present invention is further based on the discovery that in the presence of an excess of cyclodextrin polymers, the equilibrium of the stabilizer and / or veil-blocking cyclodextrin complex is shifted toward the undissociated complex to such an extent that the present stabilizer and / or present.

The present invention is also based on the discovery that stabilizer and / or veil complexes formed with water soluble polymers of cyclodextrin derivatives exhibit very limited mobility in photographic layers when the polymer contains ionizable groups that may interact with the gelatin and / or polymer matrix and interact with the matrix. and / or the veil-blocking moiety is fixed in the layer.

Cyclodextrins are cyclic, non-reducing oligosaccharides composed of 6, 7 or 8 glucopyranose units and are produced by the enzymatic degradation of starch. Their practical application is mainly based on their ability to form inclusion complexes (J. Szejtli, Cyclodextrins and their Inclusion Complexes, Akadémiai Kiadó, Budapest, 1982). The reactivity of the primary and secondary alcoholic hydroxyl groups on the six-membered thi, the seven-membered β, the eight-membered β-cyclodextrin ring allows the preparation of high molecular weight derivatives (cyclodextrin polymers).

The literature distinguishes water-soluble but water-swellable cyclodextrin polymers. The former can be prepared in two ways: c.clodextrin is prepared and polymerized with an unsaturated monomer (J. Polym. Sci. Lett, 13/1975/357) or with a suitable bifunctional reagent, preferably diepoxy compound or epichlorohydrin, cyclodextrin. British Patent No. 990; and Hungarian Patent Publication No. 181,733). Both processes yield a medium average molecular weight product which is highly soluble and forms inclusion complexes. The stability of their complexes is generally higher than that of the monomeric cyclodextrins, which is explained by the advantageous spatial arrangement of the linked rings and, in the case of β-cyclodextrin, by the higher solubility of the polymer. (Macromolecuies 9/1976/705;

Proceedings of I. Int Symp. on Cyclodextrins, 1981. 345. p.).

Water-soluble cyclodextrin polymers (generally referred to as sCDP) may be neutral or ionic.

In water-soluble cyclodextrin polymers substituted with ionic groups, in particular cyclodextrin derivatives containing a structural unit of formula (I) and having from 2 to 10 cyclodextrin ring interruptions, the ionic groups may be on the cyclodextrin rings and the both on related bridges and side chains.

According to the present invention, water-soluble cyclodextrin polymers substituted with ionic groups are disclosed in Hungarian Patent Application No. 191,101. In the general formula (I)

CD can be derived by removing p + s or 1 + t + r hydroxyl from the oC, /} or? -Cyclodextrin molecule,

R and R 'are independently -CH 2 -, -CHOH-CH 2 -, -CH 2 O- (CH 2) 2 -O-CH 2 -CHOH-CH 2 -, -CH 2 -O-CH 2 -CHOH-CH 2 -, or -CH 2 -O (CH2) 4-O-CH2-CHOH-CH2,

X represents -OR ¹ or -OR ² or -NR ^{4 1} : ^{5 in} which

^R1 is hydrogen or, if different from zero r represents an a-, 3JJ cyclodextrin molecule: represents a group derived by removing a hydroxy,

R ² is hydrogen,

-PO (OH) 2 or -SO 2 OH imine group, -R ³ - (C 00 H) u, -R ¹ SO ² OH, -R ³ -NR ⁴ R ⁵ , or a hydroxy group from an oC, 3 or 1-cyclodextrin molecule by removing a group,

R ² 'has the same meaning as R ² other than the above derivative of cyclodextrin,

R ^{3 is} a u + 1-valent C 1 -C 10 alkane derivative, the end-carbon of which is optionally substituted with an oxo group,

R ⁴ and R ⁵ each independently represent hydrogen or C 1 -C 4 alkyl, m and n are each independently an integer from 1 to 10, an integer from 0 to 23, an integer from p 1 to 24, s and t independently of one another is an integer from 7 to 7 and u is an integer from 1 to 5, with the proviso that m, n, r, t and u may vary within a unit,

and if CD one ° cyclodextrin derived group, then p + t <17, and if + s 4. 18 and r + CD one 6-cyclodextrin derived group, then p + t <20, and if + s i 21 and r + CD one ϊ-cyclodextrin derived

group, then p + s 4. 24 and r ++ t <23.

The above chemically characterized polymeric products are solid, highly soluble in water and in some organic solvents such as dimethylformamide, pyridine, capable of forming salts in addition to forming inclusion complexes, having a cyclodextrin content of between 30 and 70% and an average molecular weight of 2000 to 15000 can be changed.

By stabilizer according to the invention is meant a compound which prevents a change in the sensitometric characteristics during storage, while the veil suppresses the development of veils during development. These compounds must contain a substituent suitable for inclusion complexation. The substituent may be phenyl, isopropyl, isobutyl, tert-butyl, isopentyl, tert-pentyl, and must be located such that the cyclodextrin moiety in the resulting complex of stabilizer and / or blocking cyclodextrin polymer complexes do not interfere with the function of the stabilization group. Types of compounds that can be used as described above are:

1) A five- and six-membered heterocyclic compound of formula II wherein:

R is phenyl or C 1-4 alkyl,

-Z C- is a triazole, tetrazole or '- pyrimidine ring.

2) A benzo ring-fused heterocyclic compound of formula III containing a mercapto group, wherein

R is C 1 -C 5 alkyl,

B is sulfur or oxygen or NH

3) Triazole derivative of formula (IV) fused to a pyrimidine ring

R 1 is C 1 -C 4 alkyl.

4) an imidazole derivative of the general formula (V) - in the formula

R 1 is phenyl or C 1-4 alkyl.

5) Triazole derivative of formula VI.

As used herein, the term "stabilizer complex" refers to an inclusion complex formed in water or in the dry state, consisting of a water-soluble cyclodextrin polymer and the aforementioned stabilizers and / or veil inhibitors.

The stabilizer complex useful in the process of the present invention is formed by the interaction of the cyclodextrin polymer and the stabilizer and / or anti-fouling agent in the presence of water. The molar ratio of Q = [CD] / [ST] in the polymer to monomers in the polymer may vary from 3: 1 to 15: 1, preferably from 5: 1 to 10: 1, based on the stabilizer and / or the barrier. (For the calculation of Q, CD = = (0.01 cm) / 1135, where c is the amount of CD polymer in 1 liter of solution in g, m is the CD monomer content of the polymer in X; Molecular weight of CD monomer).

The stabilizer complexes useful in the process of the invention may be prepared by the gradual addition of the (crystalline) stabilizer in an aqueous solution of the cyclodextrin polymer at a temperature of 5 to 90 ° C, preferably 40 to 50 ° C. The stabilizer complex can be recovered from the solution in a solid state after removal of the bulk of water (e.g., by distillation).

According to the invention, it is convenient to use the stabilizer complex in aqueous solution without recovering the solid product.

The stabilizer complex may also be prepared by adding the stabilizer in the form of a solution in a suitable solvent (e.g., ethanol, acetone, etc.) to an aqueous solution of the cyclodextrin polymer.

In the process of the present invention, a complex compound consisting of a water-soluble cyclodextrin polymer and a stabilizer and / or a web inhibitor, wherein the molar ratio of CD monomers in the polymer to the stabilizer and / or web inhibitor is 3: 1 to 15: 1, preferably 5: 1 to 10 : 1 to 5 to 60 g complex / mole silver halide, preferably 15 to 30 g complex / mole silver halide, in an aqueous molding solution to form the photosensitive layer, protective layer or auxiliary layer of the photo material (barite and substrate layer). or 15-80 g complex / kg gelatin for other layers, preferably 25-50 g complex / kg gelatin.

Advantages of the process according to the invention are as follows:

(a) Water-insoluble stabilizers and / or veil inhibitors may also be added to the photoemulsion or other gelatin-containing solutions in aqueous solution in complex with the cyclodextrin polymer, thus eliminating the need to use organic solvents adversely affecting the colloid chemistry of the system,

(b) allow for solvent savings,

c) Stabilizers and / or veil stabilizers present in the ε complex form do not diffuse from the layer they have been subjected to either during the process, during storage or during development, i.e. they act only in the desired layer.

The following embodiments illustrate the process of the present invention.

Example 1

200-200 g BaSOi pulp is thoroughly mixed with 80 ml distilled water, 200 ml 12.5% gelatin solution at 50 ° C is added with stirring and stirred for 45 minutes. Thereafter, 20 ml of buffer solution (pH 5.2-5.8), 15 ml of 10 tX Blankophor optical whitening solution, 5 ml of glycerol and 12 ml of 10 tX chromium (III) acetate solution are added. 0.2 ml of 1% 1-phenyl-5-mercaptotetrazole (FMT) solution (B) and 20 ml of stabilizer complex solution (C) are added to the suspension, and without veil (A), 3 g / dm 2 is applied to photo paper.

The stabilizer complex solution is prepared to give 20 g of a compound of formula I (wherein R ¹ : hydrogen, R ² : CH ² COOH, R ² ': CH ² COOH or hydrogen, R and R': CH 2; m = 1, s = 2, t = 0, n = 1, r = 12, p = 4), i.e., a carboxymethyl-d - <: cyclodextrin polymer (abbreviated as CCD) having an average molecular weight of M = 10,000, 3-cyclodextrin (monomer content: 56.6%, 1.2 equivalents of carboxyl group per unit of cyclodextrin) - dissolved in 200 ml of water, then 0.2 g of FMT is added at 45 ° C and dissolved with stirring for 1 hour. The complex is hereinafter designated as FMTCD. [CD] / [ST] = 8.9).

The baritized carrier according to the process described is applied with an Ag / Cl, Br) emulsion (silver content of 20 g Ag / kg) with a surface silver content of 1.0-1.1 g / m ² , with the usual additives (1 mole Ag (Cl, Calculated for Br) 50 ml of 0.05 tX 3,3'-diethyl-1'-phenylbenzoxazolidene (ethylidene-2'-thiohidantoin) color sensitizer, 10 ml of 50 tX glycerol solution, 20 ml tX formalin tanner, 40 ml of 4 tX saponin solution moisturizer) but without veil blocker (a) or 1 kg emulsion containing 0.25 mole Ag / Cl, Br), 10 ml 1 t by addition of% FMT solution (b).

The sensitometric properties of the resulting photo papers are shown in Table 1. (See, inter alia, Hungarian Patent No. 192,135 for methods of measurement and notations, definitions)

Table 1

barite Emulsion Sensitometric characteristics FMT FMTC FMT Average Relative do gradi- sensitive- Dux (30 ° 12 ') ens ness G Srel THE - (the) - 1.78 100 1.82 1:16 (b, + 1.74 57 1.90 0:23 B + (the) - 1.76 84 1.92 0:58 (b) + 1.68 53 1.86 0:20 C + (the) - 1.80 103 1.90 1:15 (b) + 1.76 60 1.86 0:21 The From data it turns out that the barit 20 emulsions were applied up the weights described

The applied FMTCD does not diffuse into the emulsion layer since the sensitivity of the C / a layer is not reduced compared to the A / a layer without the veil blocker. Similar results are obtained when a cyclodextrin polymer having a carboxymethyl group as described in Hungarian Patent Application No. 191,101, Example 2 has a cyclodextrin content of 57.3% and a carboxyl content of 7.3%. which represents 2.8 equivalents of carboxyl group per unit of cyclodextrin. 8% by weight, corresponding to 2.0 equivalents of carboxyl group per cyclodextrin (average molecular weight: 2560).

specimens (surface silver content 1.0-1.1 g / m ² ) but without photographic stabilizer (A), FMT (10 ml 1% solution / kg emulsion) (B), respectively. with the FMTCD stabilizer complex described in Example 1, (from 10% w / v solution of Example 1 to 35 ml per kg emulsion) (C) ([CD] / [ST]) = 8.9; 18.9 g complex / mole silver halide, 40 g complex / kg gelatin). To the resulting emulsion layer was poured 2% gelatin solution (additives per kg solution: 2 ml 50% glycerol, 2 ml 5% formalin and 10 ml 4% saponin solution), containing no stabilizer (a) or containing the FMTCD complex prepared according to Example 1 (8 ml of a 10% solution per kg of gelatin solution) (b).

The sensitometric properties of the photosensitive layers prepared as described are given in Table 2.

Example 2

For the baritic support prepared according to Example 1 (A), Ag (Cl, Br) described therein

Table 2

Emulsion gelatine solution - Sensitometric characteristics FMT FMTC relative sensitive- ness Srel Dmax do (30 °, 12 ') FMT FMTCD average graphite gradient G THE - - (the) 1.76 100 1.82 1:14 (B) + 1.74 104 1.88 1:05 B + - (a) - 1.70 40 1.92 0:20 (B) + 1.69 42 1.90 0:21 C - + (a) - 1.73 57 1.93 0:23 (B) + 1.75 59 1.92 0:22 The data it show that FMTC put on the same veil-blocking effect no diffuses out but it is emtl- 65 out like FMT. As given in the table

The same result is obtained when the acid-sulfuric acid ester of the K-cyclodextrin polymer of Example 14 of Hungarian Patent Application No. 191,101 (chemically bonded? means 1.86 equivalents of phosphate moiety with an average molecular weight of 6600) or

The β-cyclodextrin polymer containing the diethylamino group of Example 16 (containing 55.5% by weight of cyclodextrin and 1.3% by weight of nitrogen, corresponding to 2.07 equivalents of diethylamino group per cyclodextrin, has an average molecular weight of 5200). .

Example 3 An kg of Ag (Cl, Br) emulsion having an AgBr ratio of 60 mol% and containing 20 g of silver per kg are provided with the usual additives such as 3- (p-carboxybenzyl) benzothiazole allylrodanine-3. 15 ml of a 0.05% solution of 0.05% solution of ethyl 4,5-diphenylthiazole-dimethyl merocyanine in red sensitizer (P. Glafkides, Photographic Chemistry, London, Vol. 2, p. 860). , ml of a 2% solution of alkyl succinic polyglycerol (BM Derjagin, SM Levi: Film Coating Theory, Focal Press, London, 1964, p. 162), 2,4-dichloro-6-oxy-S-triazine Na 82 ml of a 10% solution of TH James in TH James, The Theory of the Photographic Process, Mac Millan, London, 4th Edition, p. 82 (GF Duffin, Photographic Emulsion Chemistry) (Focal Press, London, 1966, p. 200). 420 ml of a 25% dispersion of dibutyl phthalate-gelatin were added, followed by 10% by weight of the FMTCD complex stabilizer prepared in Example 1. aqueous solution (30 ml). The additive-prepared emulsion is then applied to a polyethylene backing coated with a yellow color-forming emulsion layer or a protective layer and a purple color-forming emulsion layer (A) ([CD] / [ST]) = 8.9; 16.7 g complex / mole silver halide). The procedure is repeated with an emulsion containing the above additives in 10 ml of a 1% solution of FMT in 10% de FMTCD (B) or with an emulsion containing all of the above additives in addition to a stabilizer. The results (Table 3) show that the photographic characteristics of the peach synergist layer 15 are essentially the same in the case of the blue-green layer without the stabilizer and the FMTCD, with the blue-green layer containing the FMTCD indicating that the FMTCD does not diffun adjacent layer. Similar results are obtained when a β-cyclodextrin polymer containing cyclodextrin having a dimethylamino group according to Example 5 of Hungarian Patent Application No. 191-101

54.3% by weight with a nitrogen content of 1.45% by weight, which represents 2.1 equivalents of dimethylamino group per cyclodextrin. Average molecular weight: 4300), ³ θ (49.5% by weight, sulfur content) of β-cyclodextrin polymer containing sulfopropyloxy group as in Example 6

1.6% by weight, corresponding to 1.25 equivalents of sulfopropyloxy per cyclodextrin. Average molecular weight: 4860) or the acidic phosphoric ester of the β-cyclodextrin polymer of Example 13 (content of chemically bonded β-cyclodextrin is 52% by weight, and its content is 1.5% by weight, which is 1.15 equivalents of phosphate group per cyclodextrin). : 4800).

Table 3

Teal emulsion Characteristics of a purple syngeneic layer Relative sensitive- ness gradation Dmax A (with FMTCD) 100 2:11 1.92 B (FMT) 78 1.89 1.70 C (without veil blocker) 100 2:06 1.95

Example 4 A kg of silver halide emulsion containing 65/33/2 and 30 g of silver in AgBr / AgCl / Agl is provided with the usual additives, such as 3-propyl-5-ethoxy-6-methylbenzthiazole-3-ethylrhodanine. -4,5-diphenyl-3-ethylthiazole-dimethine-merocyanine red-sensitizing dye (P. Glafkides, Photographic Chemistry,

Fountain Press, London, 1960. 859. p.)

11 ml of 0.05% w / v solution, 10% w / v solution of sodium salt of 2,4-dichloro-6-oxy-S-triazine60 11% w / v, 5% saponin solution 480 ml of an oil-soluble blue-green syngeneic 28% dibutyl phthalate-gelatin dispersion were added, followed by the FMTCD stabilizer complex prepared in Example 1.

26 ml of a 10% solution are added. Ez7

-612 by adding 5 ml of a 1% solution of FMT to the blue-green emulsion (B) instead of FMTCD, or without adding a veil blocker (C).

The results are shown in Table 4.

afterwards, the emulsion with additives is poured onto a film carrier, and a gelatin layer, a hydrophobic purple layer and another gelatin layer are applied thereto (A) ([CD] / [ST]) = 8.9; 9.34 g complex / mole silver halide). We also do the test

Table 4

It is blue-green in color Purple-colored layer emulsion features Relative Gradá- Daax sensitive- ness tion (A) FMTCD 100 3:18 3:06 (B) FMT 82 2.86 2.79 (C) Without veil blocker 100 3:15 3:12

The data show that the veil blocking complex does not diffuse out of the blue-green layer.

Example 5

In each case, the procedure of Example 2 was followed except that, instead of FMTCD, the compound of formula III, 2-isobutyl mercaptobenzthiazole, prepared in an analogous manner to Example 1 (0.25 g of stabilizer in 200 ml of 10% CCD solution). The stabilizer complex thus obtained is designated MBTCD. Dosage: 40 ml of 10% solution / kg of emulsion and 10 ml of 10% solution / kg of gelatin solution having the following characteristics: [CD] / [ST] = 8.8;

21.6 g of complex / mol silver halide; 50 g of complex / kg of gelatin.

£. spreadsheet

Emulsion Gelatin- Photographic Features Solution

FMT MBTC FMT MBTC G Srel. Daax do (30 ° C 12 THE - - (the) 1:26 100 1.92 1:14 (B) - + 1:27 101 1.93 1:10 B + - (a) - - 1:20 40 1.92 0:20 lb) - + 1:22 41 1.90 0:22 C - + (a) - - 1:25 72 1.95 0:30 lb) - + 1:27 73 1.94 0:29

Example 6

All proceed as in Example 2, except that instead of FMTCD, the compound of formula (V) (R 1 = phenyl) was prepared in a manner analogous to that described in Example 1 (0.30 g of stabilizer in 200 ml of 10% w / w).

CCD solution). The stabilizer complex thus obtained is designated MIPCD. Dosage: 36 ml of 10% solution / kg emulsion; 10 ml of a 10% solution / kg gelatin solution, which complies with the following specification:

[CD] / [ST] = 7.6; 19.4 g of complex / mol silver halide; 50 g of complex / kg of gelatin.

Table 6

Emulsion

FMT MIPCD

Gelatin solution -

FMT MIPCD G

Photography features Srel Daax

Do (30 °, 12 ')

A - - (a)

2.36 100 1.98

1:19

-714

Emulsion Gelatin solution His photographs are typical Srel Deax do (30 °, 12 ') FMT MIPCD FMT MIPC G (B) + 2:38 103 1.96 1:16 B + - (a) - 2:23 63 1.90 0:21 (B) + 2:26 63 1.92 0:22 C - + (a) - 2:31 83 1.93 0:29 (B, + 2:33 82 1.94 0:28 Example 7 song). That's it won stabilization tor-complex is designated MTACD. Dosage: 28 ml We do everything in Example 3, 15 10% solution / 1 kg emulsion, this is equivalent to with with the difference that instead of FMTCD a for the following characteristics: (VI) 1. in the example [CD] / (ST] = 8.94; 15 g complex / mole silver complex halide). The results are a Table 7 (0.25 g stabilizer 200 ml 10 t% CCD tat. 7th spreadsheet

Blue-green color-forming emulsion Characteristics of a purple syngeneic layer Srel G Dmx A (with MTACD) 100 2:04 1.96 B (FMT) 75 1.91 1.78 C (without stabilizer) 100 2:07 1.92

Example 8

Example 2 was repeated except that the cyclodextrin derivative used was a diethylaminomethyl-O-cyclodextrin polymer, designated ACD. [R ² = diethylaminomethyl), R ¹ = hydrogen, s = t = 0, n = m = 2, r = 1, p = 2] having an average molecular weight of 5400 and a CD content of 63 % and nitrogen content 2.08%.

From the stabilizers used (in formula III, B = NH = R = isopentyl (BIM) or B = oxygen R = isopropyl (BOX)).

Complex lexes (0.19 g BIM and 0.68 g BOX in 200 ml 10% ACD solution) were prepared as described in Example 1B. They are called BIM / ACD or BOX / ACD. Dosage: 5 ml of 1% BIM or BOX solution / kg emulsion; 53 ml of complex solution / kg of emulsion; 12 ml of complex solution / kg of gelatin solution corresponding to the following characteristics: [CD] / [ST] = 11.1 and 3.5, respectively;

28.6 g of complex / mol silver halide; 60 g complex / kg gelatin.

The characteristics of the layers thus obtained are shown in Figure 8.

Table. The results show that the stabilizer complex does not diffuse out of the protective layer.

Table 8

Emulsion BIM Gelatin solution Sensitometric characteristics BIM / ACD BIM BIM / ACD G Srel Dmax do 30 ° 12 ' (THE) - - (the) - 1.80 100 3.90 1:16 (B) - + 1.78 101 1.88 1:10 (B) + - (a) - - 1.70 69 1.82 0:25 (B) - + 1.68 68 1.81 0:26 (C) - + (a) - - 1.72 74 1.86 0:27 Ib) - + 1.70 73 1.85 0:28 BOX BOX / ACD BOX BOX / ACD (THE) - - (the) - 1.83 100 1.91 1:13

-816

Emulsion BIM BIM / ACD gelatine BIM solution BIM / ACD G Sensitometric characteristics do 30 °, 12 ' Stel Dean BOX BOX / ACD BOX BOX / ACD (B) - + 1.82 102 1.90 1:10 (B) + - (a) - - 1.74 78 1.90 0:34 (B) - + 1.73 75 1.88 0:32 (C) - + (a) - - 1.70 76 1.89 0:35 (B) - + 1.70 73 1.88 0:35 9th example In 15, R1 = tere- • butyl group (symbol: IR) in Figure 1. Example written way the ferry THE Example 2 Following away with that lexes (0.375 g of TA, 0.125 g of P1, and 0.25 g

difference that the used cyclodextrin derivative: amphoteric jB-cyclodextrin polymer, a sign FCD [Formula (I) wherein R ¹ = CH 2 COOH, R ² = dimethylamino-ethyl, s = t = 0, n = m = 2; , r = 1, p = 2] having an average molecular weight of 5440, a CD content of 62%, a nitrogen content of 2.05% and a carboxyl content of 0.8%.

From the stabilizers used (in the general formula (II), -Z C- = symmetric tria-V / sol-ring, R = phenyl, (denoted TA), respectively

-ZC- = pyrimidine ring, R = tert-pentylcarbonate / powder (denoted by P1) or formula IV (in 200 ml of 10% FCD). They are designated FCD / TA, FCD / PI, FCD / IR. Dosage: 6 ml of 1% 20% stabilizer solution / kg emulsion, 96 ml of complex solution / kg emulsion, 3 respectively; 15 and 5 ml of complex solution / kg gelatin solution, corresponding to the following characteristics: [CD] / [ST] = 5.15, 14.8 and 9.4; 51.8 g complex / mol silver halide; 15, 75 and 25 g complex / kg gelatin, respectively.

The results are shown in Table 9.

From the data it appears that the stabilizing tor complexes do not diffuse out of the protective layer.

Table 9

Emulsion TA Gelatin solution Sensitometric characteristics FCD / TA TA FCD / TA G Srel Daax do 30 ° 12 ' (THE) - - (the) - - 1.90 100 1.96 1:10 (B) - + 1.86 98 1.95 1:08 (B) + - (a) - - 1.86 80 1.92 0:18 (B) - + 1.82 76 1.91 0:18 (C) - + (a) - - 1.83 81 1.94 0:20 (B) - + 1.80 80 1.92 0:21 E.g FCD / PI E.g FCD / PI (THE) - - (the) - - 1.85 100 1.90 1:12 (B) - + 1.83 103 1.91 1:10 (B) + - (a) - - 1.80 90 1.90 0:33 (B) - + 1.76 91 1.88 0:34 (C) - + (a) - - 1.79 95 1.92 0:30 1.80 92 1.92 0:31 IRISH FCD / IR IRISH FCD / IR (THE) - - (the) - - 1.88 100 1.96, 1:17 (B) - + 1.80 96 1.92 1:12 (B) + - (a) - - 1.80 89 1.90 0:40 (B) - + 1.78 86 1.89 0:41 (C) - + (a) - - 1.82 88 1.91 0:38 (B) - + 1.83 87 1.92 0:36

Claims (1)

Patent Claim Point A process for producing black-and-white or color photographic materials containing barrier or polyethylene coated paper or film, photosensitive layer or layers and a protective layer or layers, comprising water-soluble stabilizer and / or veil-blocking complexes, to form a photosensitive layer, a protective layer, or a support layer of a support barite or substrate in an aqueous casting solution of 30-70% by weight of cyclodextrin polymer of the formula I having an average molecular weight of 2000-15000 CD can be derived by removing p + s or 1 + t + r hydroxyl from the oC, 8- or? -Cyclodextrin molecule, R and R 'are independently -CH 2 -, -CHOH-CH 2 -, -CH 2 -O- (CH 2) 2 -O-CH 2 -CHOH-CH 2 -, -CH 2 -O-CH 2 -CHOH-CH 2 -, or -CH 2 -O - (CH2) 4-O-CH2-CHO-CH2 X is -OR ¹ , or -OR ^2, or -NR ⁴ R ^{5 in} which R1 represents a hydrogen atom or, when it is different from 0, represents a group deriving from the removal of a hydroxyl group from an oC-, β- or γ-cyclodextrin molecule, R ² is hydrogen, -PO (OH) 2 or -SO 2 OH, -R ³ - (COOH) _U , -R ³ -SO 2 OH, -R ³ -NR ⁴ R ⁵ , or an oC-, p- or by removing a hydroxyl group from the u-cyclodextrin molecule, R ² 'has the same meaning as R ² other than the above derivative of cyclodextrin, R ^{3 is} a u + 1-valent C 1 -C 10 alkane derivative, the carbon end-of-polymer of which may be optionally substituted with an oxo group, R ⁴ and R ⁵ independently represent hydrogen or C 1 -C 4 alkyl, m and n independently represent an integer from 1 to 10, r 0 to 23, p 1 to 24, s and t independently 0 and 7 is an integer and u is an integer from 1 to 5, with the proviso that m, n, r, t and u may vary within a unit, and if CD one ° cyclodextrin derived group, then r + t <17, and if p + s 4 18 and CD one ° cyclodextrin derived group, then r + t ζ 20, and if p + s 21 and CD one .alpha.-cyclodextrin derived group, then r + t í 23 - p + s f 24 and and (II) 1 heterocilkusos ve- from the congregation - in the formula R is phenyl or C 1-4 szén_ _x -alkyl, -Z6- is a triazole, tetrazole or pyrimidine ring - or a heterocyclic compound of formula III R is C 1 -C 5 alkyl, B is sulfur or oxygen or NH - or a triazole derivative of formula (IV) R 1 is C 1 -C 4 alkyl or imidazole derivative of general formula (V) R 1 is phenyl or C 1-4 alkyl or a triazole derivative of the Formula VI and is incorporated in a 5 to 60 g complex / mol of silver halide, preferably 15 to 30 g / complex / mol silver halide. or in the other layers in an amount of 15 to 80 g of complex / kg of gelatin, preferably 25 to 50 g of complex / kg of gelatin having a molar ratio of polymer / stabilizer and / or web blocking agent in the range of 3: 1 to 15: 1, preferably 5: 1 and It's between 10: 1.