HU192135B - Process for production light sensitive argent halogenid emulsion with phisycal-chemical and photogrphic characteristics by utilizing soluable in water, substituated by ion groups cyclodextrin polimers - Google Patents

Abstract

According to the invention to the emulsion a cyclodextrin polymer having a cyclodextrin content of from 30 to 70 %, an average molecular mass of from 2,000 to 15,000 and containing structural units of formula (I> <IMAGE> is added in an amount of from 2 to 80% calculated on the weight of the gelatin. In the general Formula I the substituents have the following meanings: CD stands for a group obtained from alpha , beta - or gamma -cyclo-dextrin by cleaving p+s or l+r+t hydroxy group; the remaining substituents are as defined in the specification. m and n stand independently for an integer from 1 to 10, r stands for an integer from 0 to 23, p stands for an integer from 1 to 24, s and t stand independently for an integer from 0 to 7, with the proviso, that when CD stands for a group obtained from alpha -cyclo-dextrin, then p+s </= 18, r+t </= 18, when CD stands for a group obtained from beta -cyclo-dextrin, then p+s </= 21, r+t </= 21, when CD stands for a group obtained from gamma -cyclo-dextrin, then p+s </= 24, r+t </= 24.

Description

The present invention relates to a process for the preparation of a photosensitive silver halide emulsion with improved physico-chemical and photographic properties using water-soluble cyclodextrin polymers substituted with ionic groups.

High molecular weight polymers are often recommended for improving the physico-chemical and photographic properties of photosensitive silver-halide emulsions. They are used either as additives or as partial substitutes for gelatin, and may be aqueous polymer dispersions or water soluble polymers.

As an additive, for example, British Patent No. 1,406,752 proposes water-soluble polymers of acrylic acid or methacrylic acid esters to improve the physical and photographic properties of the emulsion generally. The use of acrylate latices is suggested in German Patent Publication No. 2,218,218. French Patent Nos. 1,518,085 to Acrylamide / Styrene Copolymer, 3,063,838, and U.S. Patent 3,137,575 describe dextran and polybructose for increasing coverage. The photosensitivity can be increased by polyvinyl oxazolidone according to U.S. Patent No. 3,006,762.

The polyacrylamide proposed in British Patent 1,073,238, in addition to its opacifying effect, strongly increases the viscosity and, after drying, promotes the formation of dark rings in the layer and is therefore problematic in its use. Polymers of N-methylol-methacrylamide or N-methylol-methacrylamide ether described in British Patent No. 1,069,944 have a waxing effect. Similarly, the polymeric derivatives of bacic acid described in British Patent No. 1,124,284 are similar.

For the partial replacement of gelatin, many patents have suggested, for example, poly (acrylamide), acrylamide / acrylic copolymer, polyvinylpyridine, but few have been found among the proposed compounds for industrial use (GF Duffin, Photographic Emulsion Chemistry, London 30, 1966).

In addition to the limited application of latexes in the photosensitive layer due to compatibility issues and inhibition of diffusion of the working solution components, and because of the high degree of interaction with gelatin, most of the recommended water-soluble polymers are generally limited in their use. recommended to perform a function.

Polyvinylpyrrolidone, disclosed in U.S. Patent 3,541,289, exhibits significant retention of crystal growth at high molecular weight, high viscosity enhancement activity, lower molecular weight (M = 25-30,000) in very low dosage, high volume antioxidant, for example, 15-20% by weight of gelatin), although it has an opacifying effect, but reduces sensitivity.

The present invention is based on the discovery that using a water-soluble cyclodextrin polymer of appropriate chemical structure with a relatively low average molecular weight results in the simultaneous improvement of several properties without the above-mentioned disadvantages.

Cyclodextrin is a cyclic, non-reducing oligosaccharide composed of 6, 7 or 8 glucopyranose units and is produced by 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 α-, seven-membered β- and eight-membered γ-cyclodextrin rings allows the preparation of high molecular weight derivatives (cyclodextrin polymers).

The literature distinguishes between water-soluble and insoluble but water-swellable cyclodextrin polymers. The latter have higher molecular weight and are insoluble in any solvent because of their crosslinked structure.

Water-soluble cyclodextrin polymers are prepared in two ways: by making and polymerizing an unsaturated monomer from cyclodextrin (J. Polym. Sci. Lett. British Patent Nos. 1,244,909; and Hungarian Patent Application 1961/80. Both processes yield products of average average molecular weight which are highly soluble in water and form 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 0-cyclodextrin, by the higher solubility of the polymer. (Macromolexules, 9,705, (1976), Proceedingsof Int. Symp. On Cyclodextrins 345, 1981).

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

The preparation of water-soluble cyclodextrin polymers is described in Hungarian Patent No. 180,597, and the preparation of water-soluble cyclodextrin polymers substituted with ionic groups is disclosed in U.S. Patent No. 1,191,101. According to the present invention, water-soluble cyclodextrin polymers substituted by ionic groups are used.

In the water-soluble cyclodextrin polymers used in the present invention which are substituted by ionic groups, in particular cyclodextrin derivatives containing a structural unit of formula (I) and formed by linking 2 to 10 cyclodextrin rings, the ionic groups may be present on and bonded to the cyclodextrin rings. side chains or both on cyclodextrin rings and on related bridges and side chains. In the formula

CD is a residue derived by removing p + s or l * r + t hydroxyl groups from the α-, β- or γ-cyclodextrin molecule,

R and R 'are independently -CH ₃ -, -CHOH-CH ₂ -, -CH ₂ -O- (CH ₂ ) ₂ -o-ch ₂ -choh-ch ₂ -, -CH ₂ -O-CHOH-CH. ₂ - or -CH ₂ -O- (CH 2) 4 O -CH ₂ -CHOH-CH 3 -,

X is -OR ¹ , or Ό-R ^2, or -NR ⁴ R ^{5 in} which

^R1 is hydrogen or, if different from zero r represents an α-, β represents a group derived · or γ-cyclodextrin molecule by removing a hydroxy,

R ² is hydrogen, -PO (OH) ₃ or

-SO 3 OH, -R ³ - (COOH), -R ³ -SO ₂ OH -R ³ -NR ⁴ R? a group of the formula: or a group derived by removing a hydroxyl group from a ·, β · or γ-cyclodextrin,

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-derived group whose carbon atom closer to the polymer chain s may be optionally substituted with oxo,

R ⁴ and R ⁵ are each independently hydrogen or C 1-4 alkyl, m and n are each independently an integer from 1 to 10, r is an integer from 23 to 23, p is an integer from 24 to 24, s and t are independently 0 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 from side to side within a unit, and if

CD is a group derived from α-cyclodextrin, then p + s <18 and r + t <17, and if

CD is a group derived from 0-cyclodextrin, then p + s <21 and r + t <20, and if

CD is a group derived from γ-cyclodextrin, then p + s <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 inclusion complexes, having a cyclodextrin content of between 30 and 70% and having an average molecular weight of between 2000 and 15000. .

The photographic emulsion of the present invention is prepared by precipitating the silver halide in an aqueous solution of gelatin and a water-soluble cyclodextrin polymer, physically aging the crystals formed and then adding the usual additives to the resulting emulsion by adding chemical maturation.

The emulsion of the present invention may also be prepared by subjecting the crystalline silver halide crystals precipitated in the presence of gelatin and the water-soluble cyclodextrin polymer to physical aging and removing any excess ions by any suitable means such as flocculation, washing, undergo chemical maturation and then add the usual additives.

Alternatively, the water-soluble cyclodextrin polymer may be added to the emulsion during and / or at the time of maturation and / or mixing with other additives.

The process of the present invention may also be carried out by removing from the emulsion an amount of gelatin equal to or less than the amount of water-soluble cyclodextrin polymer used.

The emulsion of the present invention can be chemically sensitized by known methods, such as labile sulfur compounds or gold complexes (T.H. James, Theory of The Photographic Process, IV Edition, Mac Miilen, New York, 1977, pp. 152-5).

Known additives can be used for the emulsion of the invention.

_; Examples of color sensitizers are 1-ethyl-3'-phenyl-2-cino-5-rhodanine (dye-I), 3 3'-diethyl-1'-phenyl-benzoxazolidene (ethylidene-2'-thiohydantione) (dye-II). ), 33 '· diethyl-6,6'-dinaphthyl-9-phenylthiocarbocyanine (dye III), benzothiazolyl phenyl-2-thiohidant can be used as tetramine tert-carbocyanine (dye-III) (P. Glafkides, Photographic Chemistry, Volume II, pages 832-856, Fountain Press, London, 1960.

Examples of stabilizers are 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindole (TAI), 1-phenyl-5-mercaptotetrazole (FMT), mercaptobenzthiazole (MBT), mercaptobenzoxazole, 2-mercaptopyrimidines ( GF Duffin, Photographic Emulsion Chemistry, pages 138-141, Focal Press, London, 1966).

For example, tanning agents such as formalin, glutaraldehyde, glyoxal, 2,4-dichloro-6-oxy-s-traiine may be added (T.H. James, p. 82).

Suitable wetting agents include, for example, alkenyl succinic polyglyceride, dodexylphenyl polyglycol cholesterol, saponin (B.M. Derjagin, S.M. Levi, Film Coating Theory, page 162, Focal Press, London, 1966).

If the emulsion of the invention is used to produce color photographic layers, yellow and / or purple and / or blue-green hydrophilic or oil-soluble colorants may be added thereto. Examples of yellow coloring agents are diketomethylene derivatives, purple coloring agents 5-pyrazolone derivatives, blue-green coloring agents naphthol or phenol derivatives (G.F. Duffin, pp. 197-200).

In the process of the present invention, the water-soluble cyclodextrin polymer is used in an amount of from 2% to 80%, preferably from 5% to 50%, by weight of the gelatin, in the form of an aqueous solution or a solid.

The main advantages of the process according to the invention are as follows:

1) With a single polymer, several properties of the photographic emulsion can be improved simultaneously, thus

a) Increase the coverage, thus saving silver.

b) increase in sensitivity can be achieved,

c) improving the freezing ability of the emulsion.

2) Partial replacement of gelatin can be achieved using the polymer.

3) Enables you to improve the tonal stability of warm-toned photo papers.

4) The polymer used for the process can be obtained from inexpensive domestic raw materials.

The process of the present invention is illustrated by the following embodiments (values in% unless otherwise stated are by weight):

Example 1

10 g of gelatin are swollen in 400 ml of water and 0.065 moles of KBr and 0.095 moles of NaCl are added after dissolution. After dissolution of the salts at 60C, silver halide was precipitated with 60 ml of 2 M AgNO ₃ solution. After 15 minutes of heat treatment, 40 g of matured gelatin was added and the heat was continued for another 65 minutes. The resulting emulsion was cooled to 40 ° C and aliquoted with the usual additives (based on 1 mole of silver halide - 75 ml of 0.05% dye solution, 100 ml of 50% glycerol solution, ml of 4% saponin solution, 20 ml of 5% formalin, 35 ml of 1% FMT) and then applied to a paper carrier with a silver content of 10 ² g / dm ² . (/ A / emulsion).

The emulsion was also prepared by adding 10 g of gelatin in 400 ml of 2.5 wt% poly (carboxymethyl-0-cyclo-31

192.135 dextrin) (Compound No. 1, iodometrically determined cyclodextrin content (Acta Chim. Hung., 100, 265 (1979)): 56.4% by weight, determined by titration with 0.02 N sodium hydroxide content: 9.2% by weight, corresponding to 4.1 equivalents of carboxyl group per unit of cyclodextrin, average molecular weight, 2200 (based on molecular weight distribution determined by gel chromatography), as described below for emulsion (A) / B / emulsion)

The emulsion is then prepared as described for emulsion (B), but using a 30g of maturing gelatin composition of appropriate composition. (/ C / emulsion)

The emulsion is then prepared as described for emulsion (A) using 30 g of a suitable maturation gelatin composition, and upon completion of the heat treatment, 100 ml of 10% poly (dimethylamino) methyl- (3-cyclodextrin) - A solution (Compound No. 2, cyclodextrin content of 54.3 wt%, nitrogen content of 1.45 wt%, representing 2.1 equivalents of dimethylamino group per cyclodextrin. Average molecular weight: 4300) (/ D / emulsion) was added. ).

The characteristics of the resulting photosensitive layers are shown in Table I. (The sensitograms were exposed to a 2800 K color incandescent lamp, developed at 18 ° C for 2 minutes in the following solution: 1 g of methol (= N-methyl-p-aminophenyl x 1/2 H ₃ SO ₄ ), 4 g of hydroquinone, 20 g of anhydrous sodium sulfite, 10 g of anhydrous sodium carbonate, 1 g of potassium bromide in 1 liter of water).

The photographic properties are determined from the characteristic curve of the optical density D as a function of the logarithm of the H illuminance. The average gradient is expressed by the formula lgHj-lgHj, where Di = D_ ♦ 0.05, D ₂ = D ^^ - 0.10, Hj and H _{2 are} the illuminations generating the Dj and Dj densities, D _{Q is} the unlit

Optical Density of Ί5 Sites after Recall, D _χ - The highest optical density of the characteristic curve that does not change systematically with further increase of illumination.

The photosensitivity is expressed by the formula \ [hThi.

The relative sensitivity is the ratio of the percent sensitivity of the control to that of the test substance.

Table I The emulsion The Treatment The Relative The average Veil lake cyclo- mode sensitive gradient D _max 18 ° C to 30 ° C dextrin hypo ness 2 '10' limer ada- Golas

/THE/ no F I 100 110 2.20 2.17 1.99 1.98 0.05 0.05 0.33 0.29 A / B / swoop F 126 2.18 2.00 0.05 0.28 I 131 2.20 1.98 0.04 0.27 / C / swoop F 122 2.24 1.96 0.05 0.27 I 129 2.21 1.98 0.06 0.28 / D / at the end of ripening F 105 2.15 2.04 0.04 0.26 I 102 2.12 2.00 0.05 0.25

(Note: F = fresh untreated sample, I = 50 ° C after a day incubation).

The data show that the cyclodextrin polymer used at the time of precipitation has a sensitivity-enhancing effect (B) and retains this property even when treated as a gelatin substitute and the same amount of gelatin is removed from the emulsion (C). When added to the system as a gelatin substitute (D) at the end of maturation, the same results are obtained with the 60 control emulsion. Similar results are obtained when an α-cyclodextrin polymer containing a carboxymethyl group as described in Hungarian Patent Application No. 191101 (cyclodextrin content: 57.3% by weight, carboxyl content: 7.3% by weight) is obtained as a cyclodextrin polymer. represents 2.8 equivalents of carboxy-41-moiety per unit of cyclodextrin (average molecular weight: 2350), 3.

Cyclodextrin polymer containing a carboxymethyl group according to its example (content of cyclodextrin: 54.2% by weight, content of carboxylate: 3.8% by weight, corresponding to 2.0 equivalents of carboxyl group per unit of cyclodextrin. Average molecular weight: 2560), Example 1b contains a β-cyclodextrin polymer having a dimethylamino group of Example 1 (54.3% by weight, 1.45% by weight of nitrogen, representing 2.1 equivalents of dimethylammonium per unit of cyclodextrin. Average molecular weight: 4300). 6, containing a sulfopropyloxy group of Example 6, having a cyclodextrin content of 49.5% by weight and a sulfur content of 1.6% by weight, corresponding to 1.25 equivalents of sulfopropyloxy group per cyclodextrin. : 4860) or the acidic phosphoric ester of the 0-cyclodextrin polymer of Example 13 (containing 52% by weight of chemically bound (3-cyclodextrin), 1.5% by weight of phosphorus, which is 1.15 equivalents of phosphorus represents a group of wood having an average molecular weight of 4800)

Example 2

Dissolve in 300 ml of a 1.5% phthaloyl gelatin solution

0.25 mol of potassium bromide and 0.01 mol ΚΙ was added followed by stirring at 65 ° C. After stirring for 2 minutes 20 minutes 320 ml of 0.5 M AgN0 ₃ solution is added. The snow temperature was then reduced to 40 ° C and the pH was adjusted to 3.8 by dropwise addition of 2 N sulfuric acid. The precipitate is allowed to settle and the aqueous phase is decanted. The precipitate is then poured into 800 ml of cold water, the pH is raised to 10.0 by dropwise addition of sodium hydroxide solution, and flocculation and decantation are repeated. The precipitate is then treated with 400 ml of 12% inert gelatine at 60 ° C. solution was added, the pH was adjusted to 6.3, and after the addition of the gold thiosulfate complex, the emulsion was subjected to chemical maturation at 60 ° C.

At the end of maturation, the temperature is reduced to 40 ° C and aliquots of the emulsion are provided with the usual additives (200 ml of 0.1% dye solution IV, 160 ml of 50% glycerol solution per mole of silver halide). 80 ml of 4% saponin solution, 40 ml of 5% formalin, 300 ml of 1% solution TAI) and then applied to a cellulose triacetate support 3,8.10 ^'2 g / dm ² of silver metal content. (/ E | emulsion)

The emulsion is prepared by addition of 6 g of salicam 1 to the gelatin solution upon precipitation, and proceeding as described below for the preparation of emulsion (E) (/ F / emulsion),

The emulsion (G) was prepared by adding 2.5 g of Compound 1 to the gelatin solution and using the same as an additive in 15% by weight of gelatin.

A photosensitive layer is also prepared using the emulsion prepared according to (E), but the following water-soluble cyclodextrin polymer derivative is added in an amount of 20% by weight of the gelatine after the addition of the color-sensitizer: Compound 1, poly (sulfobutyl) 1-cyclodextrin) (Compound # 3: 49.5% by weight of cyclodextrin, 1.6% by weight of sulfur, corresponding to 1.25 equivalents of sulfopropyloxy per unit of cyclodextrin. Average molecular weight: 4860), poly (diethyl -aminoethyl-O-cyclodextrin) (Compound 4: 58% by weight of cyclodextrin, 0.8% by weight of nitrogen, corresponding to 1.22 equivalents of diethylaminoethyl in cyclodextrin, average molecular weight: 4500 ), poly (carboxymethyl -? - cyclodextrin) (Compound # 5: Cyclodextrin content: 56.2% by weight, carboxyl content: 3.4% by weight / c, which represents 1.5 equivalents of carboxyl group per unit of cyclodextrin). average Molekül mass: 4970) (1H / emulsion).

An emulsion according to (E) is then prepared using 300 ml of a 14% solution in gelatin for redispersion, and at the end of the maturation, 100 ml of a 10% solution of compound 1 is added to the emulsion, of gelatin. (/ J / emulsion)

The characteristics of the photosensitive layers obtained are shown in Table II. are shown in the table. (Sensitograms were exposed to 5500 K color light and called F-76 for 8 minutes at 20 ° C).

Again, the average gradient is determined from the characteristic curve according to formula (1). In this case, however, lg H i is the logarithm of the illumination producing the optical density Dj - D _Q + 0.1, while lgHj - lgHj »= 1.3, and D _{2 is} the density produced by the luminous flux H ₂ .

Sensitivity is calculated using the formula S = 0.8 / Hj.

J 92.135

Η. spreadsheet

The emulsion Water-soluble cyclodextrin polymer derivative Method of treatment W no F / F / No. 1 1 F compound I / H / No. 1 F compound I No. 3 F compound I 4 F compound I No. 5 F compound I IGI No. 1 F compound I hl No. 1 F compound I

Relative sensitivity The average gradient ^D o 100 0.65 0.06 95 0.62 0.06 115 0.83 0.07 118 0.84 0.07 130 0.79 0.08 136 0.75 0.08 115 0.75 0.07 110 0.75 0.08 110 0.70 0.07 105 0.70 0.08 125 0.86 0.06 130 0.84 0.07 125 0.86 0.08 128 0.85 0.08 123 0.84 0.08 120 0.80 0.07

(Note: F - fresh, untreated sample,

I = 50 ° C after 5 days incubation

The results show that the water-soluble cyclodextrin polymer derivatives, when used as an additive as well as at the time of precipitation, have the effect of increasing opacity and sensitivity. They also have similar effects as gelatin substitutes. (/ J / emulsion). The same results as in the table are obtained, even if the acid sulfuric acid ester of the γ-cyclodextrin polymer according to Example 14 of Hungarian Patent Application No. 191101 (the content of chemically bound γ-cyclodextrin is 47% by weight, which is 2.5% by weight cyclodextrin) is obtained. or 1.86 equivalents per unit phosphate group, average molecular weight: 6600, or a γ-cyclodextrin polymer containing the diethylamino group of Example 16 (55.5% cyclodextrin content, 1.3% nitrogen content, 2.07 equivalents per cyclodextrin). diethylamino, average molecular weight: 5200),

Example 3

500 AgBr (J) emulsion containing 3 mole% iodide, 45 g Ag / kg silver, 50 g gelatin, average crystal size d - 1.4 μηι, with the usual additives (1 mole silver halide 180) at 40 ° C. 50% glycerol, 90ml 4% saponin, 28ml 5% formhn, 300ml 1% TAI) and 10% aqueous solution of Compound 1 (180ml) and then added. aqueous solutions of the synthetic polymers to be compared, and then on a support of cellulose triacetate with a silver content of 3.8 g / m ² on each side. The characteristics of the photosensitive layers thus obtained are shown in Table III. are shown in Table. (Sensitograms were exposed to light at 2850 K and exposed to Unifort for 5 minutes at 20 ° C). The photographic properties are as described in Example 2. _ Don is determined. By γ we mean the tangent to the straight line 4 ° of the curve. The opacity is determined by dividing the value of the maximum density by the amount of silver produced.

192 135

Table III

Material Dosage g / kg Treatment S _re j θο ®max Lid- ability No. 1 compound 7.5 F 2.40 100 0.25 4.00 0.75 I 2.31 102 0.26 3.95 0.73 (A) polymer 10.0 F 2.33 98 0.38 3.95; 0,5 ° I 2.21 100 0.40 3.96 0.46 (B) polymer 10.0 F Not worth it- 0.56 3.50 0.34 I Kelheim She 0.70 3.60 0.26 (C) polymer 10.0 F 1.86 70 0.46 3.60 0.43 I 1.59 75 0.57 3.62 0.40 (D) polymer 10.0 F 2.10 56 0.23 3.80 0.45 I 1.91 43 0.23 3.85 0.43 No additives F 1.92 85 0.25 3.90 0.28 I 1.60 80 0.30 3.83 0.20

(A) = Poly (N-methylol methacrylamide ether) (M = 3,000), (B) = Poly (N-methacryloylpyrrolidone) (M = 26000), (C) = Polytactonic acid monomethylamide (M = 34000), (D) = Polyvinylpyrrolidone (M = 24000).

From the data, compound 1 shows the best results. Although the photographic characteristics of Polymer (A), at higher values of the veil, are close to those obtained with the former, the higher compound yields a lower coverage. Synthetic polymers (B), (C) and (D) give significantly lower opacity and poorer photographic performance than Compound # 1.

Example 4

500 g Ag / Cl, Br emulsion containing 55 mole% chloride, 15 g / kg silver, 42 g / kg gelatin, 50 mole% halide, average crystal size d = 0.210 μτη, is made up of standard additives (1 mole silver). based on halide, 85 ml of 0.05% dye-II, 8.0 ml of 50% glycerol, 40 ml of 4% saponin, 20 ml of 5% formalin, 30 ml of 1% MBT), then increasing in a 10% solution of compound 1 and acrylate latex (a

PRIMALB, Rohn and Haas particles have an average diameter of 0.25 μιη).

The photographic examinations were performed as in Example 1, but here to characterize the image tone,

The hány> χ - 400 color quotient is also determined by taking the reflection spectrum of the optical density field D = 1.0 ± 0.03 and subtracting the λ = 400 and λ values, respectively. The densities at 700 nm are plotted. For K = 1,2-1,3, greenish-brown, brown is the tone, and the ratio decreases to gray, while K = 1.0 (7 neutral tones are obtained.

The results are shown in Table IV. Table.

192 135

ARC. spreadsheet

Material Dosage, g / kg Treatment G ^S rel 18 ^ 2? . > ®max K No additives 0 F 2.18 100 0.06 1.95 1.22 l 1.92 106 0.12 1.88 1.01 1, no. compound 2.5 P 2.19 102 0.06 1.94 1.21 I 1.93 103 you 1.92 1.15 5 F 2.20 105 0.06 1.96 1.21 I 1.96 106 0.11 1.89 1.17 10 F 2.19 104 0.07 1.95 1.21 I 1.94 108 0.12 1.90 1.16 15 F 2.21 110 0.08 1.95 1.20 I 1.92 106 0.11 1.88 1.18 20 F 2.25 110 0.07 1.96 1.24 I 1.96 111 0.12 1.90 1.19 25 F 2.20 108 0.08 1.92 1.22 I 1.94 106 0.12 1.89 1.18 Akrilátlátex 5 F 2.21 100 0.07 1.96 1.22 I 1.96 98 0.14 1.90 1.02 10 F 2.02 93 0.07 1.76 1.19 I 1.79 90 0.13 1.70 1.03 15 F 1.91 85 0.07 1.69 1.17 I 1.69 80 0.15 1.61 1.02

Note: F = fresh, untreated sample, I = 50 ° C after 30 days incubation.

The results show that in the presence of the cyclodextrin polymer during the 30 days of incubation, the warm tone of the image is maintained, i.e., the color ratio is practically unchanged, whereas in the presence of the acrylate latex it is as much as in the non-additive layer. In addition, increasing the acrylate content decreases gradation and sensitivity, which is associated with slower diffusion of the developer.

Claims (1)

A method for improved physicochemical and ph tumor 4Q Ságokkal with laj Don, photosensitive silver halide precipitating optionally removing ions in excess in any suitable manner, preferably flocculation, washing in with _u Pade physical, chemical maturation, known additives, Thus, by mixing a color sensitizer, plasticizer, wetting agent, tanning agent 45 and stabilizer, the cyclodextrin base of formula (I) is present in an amount of 5-60% based on the weight of the gelatin before, during or after aging, or as a casting additive. with a cyclodextrin content of between 30 and 70% of 50 / average molecular weight between 2000 and 15000 CD is a residue derived by removing p + s or 1 + r + t hydroxyl group from α-, α- or γ-cyclodextrin, · cg R and R 'are independently -CH ₃ -, -CHOHCH 3 -, -CH ₂ -O- (CH ₁ ) 2 -O-CH ₂ CHOH-CH ₂ -, -CH ₂ O-CH ₂ -CHOH-CH ₂ -. or -Cyl ₂ O (CH ₂ ) ₄ -O-CH 3 -, X is -OR *, or OR ² or -NR ⁴ R ^{S in} which R ¹ is hydrogen or, when it is different from r = O, a group derived by removing a hydroxyl group from the α-, β- or γ-cyclodextrin molecule, R ² is H, PO (OH) 2 or -SO2OH formula R ³ - (COOH) -R ³ - SO2OH, -R ³ -NR ⁴ R ^S, a group of formula, or a α-, β- or γ- by removing a hydroxyl group from a cyclodextrin molecule, R ² 'has the same meaning as R ² other than the above derivative of cyclodextrin, R ^{3 is} a u * 1 valence C 1 -C 10 alkane derivative, the end-carbon of which is optionally substituted by an oxo group in the polymer, R ⁴ and R ⁵ each independently represent hydrogen or C 1 -C 4 alkyl, m and n each independently represent an integer from 1 to 10, r an integer from 0 to 23, p an integer from 1 to 24, s and t independently 0 is an integer from 7 to 7 and u is an integer from 1 to 5, characterized in that m, n, r, t and u can vary within a unit, side-by-side, and if CD is a group derived from α-cyclodextrin, then p + s <18 and r + t <17, and if CD is a group derived from jcyclodextrin, then p + s <21 and rrt <20, and if CD is a group derived from γ-cyclodextrin, then p + s <24 and r + t <23.