HU203603B - Method for improving physical-chemical features of the photographic layers - Google Patents

Abstract

A process of adding to gelatine silver halide photographic layers a) 0.020 to 0.25 mole of a hardening or a coupling agent containing 2 glycidyl groups or epichlorohydrin and b) 10 to 100g of a cyclodextrin or a cyclodextrin polymer and/or a polyethylene imine or (ii) 0.020 to 0.25 mole of formaldehyde or glyoxal and 10 to 100 g of a polyethylenimine polymer of the general formula (VII) or (iii) 0.020 to 0.25 mole of epichlorohydrin or a coupling agent, containing 2 glycidyl groups and 10 to 100 g of gelatin-cyclodextrin copolymer and optionally a polyethylenimine calculated for 100 g of gelatin of the photographic emulsion or gelatin solution, where the gelatin/cyclodextrin ratio in the copolymer added may be varied from 10:90 to 90:10. The addition gives good development diffusion, minimum hydration and sufficient hardness.

Description

BACKGROUND OF THE INVENTION This invention relates to a process for improving the physico-chemical properties of silver halide-based photographic layers using copolymers of various compositions of gelatin.

Modem machining technologies require photo materials that allow you to quickly get to the finished product by quickly completing operations. The prerequisite for this is that the working solutions diffuse into the layer at the required rate, but not from damage. However, the layer absorbs only the amount of water that can be removed by the equipment during the drying process. Meeting these contradictory requirements is one of the basic tasks of a photo material manufacturer.

The problem cannot be solved only by changing the chemical structure of the tanning agent. It is well known, for example, that during tanning with formalin, the water uptake of the layer can be significantly reduced, but due to the high tanning, retention of diffusion results in deterioration of photographic properties. On the other hand, 2-oxy-4,6-dichloro-s-triazine provides good sensitometric properties even when the layer is sufficiently tanned, but the water uptake of the layer is increased.

In order to improve the physico-chemical properties of the layers, polymer dispersions of various compositions are called so-called. recommend latex. Such are described in 3,142,568; 3,414,912; a 3,359,108, a 3,062,674; No. 3,359,108. U.S. Patents, or U.S. Patent No. 2,218,218. Disclosure document in the Federal Republic of Germany. By using the acrylate latex recommended at several locations, the water uptake of the layer is reduced by 40% compared to that containing gelatin alone at 30% polymer content (Böttcher, H. et al., J. Signal AM 8/1980/229). in such a layer, the diffusion of the prodrug is significantly reduced.

described the use of water-soluble ionic cyclodextrin polymers have also (Szucs, M. and others to improve the photographic emulsions physical and photographic properties of..... 192 135 Hungarian and British patent specification No. 2 138 158. UK No. In particular the silver image opacity can be increased However, with e., a gelatin film containing carboxymethyl-p-cyclodextrin polymer and tanned formalin, suitable hardness and good developing diffusion, a higher hydration in relation to that containing (Szucs, M. Images and sound systems 33/1987/65) only formalin.

It is an object of the present invention to provide a layer which, with sufficient hardness, allows good caller diffusion and minimal water uptake.

The present invention is based on the recognition that a suitable composition of a gelatin-cyclodextrin copolymer is capable of meeting these needs.

A further basis of the invention is the discovery that said gelatin-cyclodextrin copolymer can not only be incorporated into the photographic layers in a finished form, but can also be prepared "in situ".

The present invention is also based on the discovery that a "copolymer of gelatin with the desired property" can be formed in the layer by "in situ" polyethyleneimine and a suitable coupling agent.

A further basis of the invention is the discovery that a terpolymer of gelatin, cyclodextrin and polyethyleneimine may also be formed in the layer with the desired properties if a suitable coupling agent is used.

The preparation of a gelatin-cyclodextrin copolymer to be used to reduce the water uptake of the layer is described in U.S. Pat. s. Hungarian Patent Application (Szucs, M. and Csapiáros J) gives examples. According to the procedure, e.g. gelatin is reacted with a cyclodextrin monomer or a water-soluble cyclodextrin polymer in the presence of an apichlorohydrin or diepoxy coupling agent. By the same principle, the gelatin cyclodextrin copolymer can be prepared in the layer.

The ability of the aldehydes, diepoxides and epichlorohydrin to react with the polyethyleneimine also allows the preparation of polyethyleneimine-containing copolymers.

Cyclodextrins are cyclic, non-reducing oligosaccharides formed from α-D-glucopyranose units with 1,4-glucosidic bonds. The α, β, and γ-cyclodextrins of 6,7 and 8 glucopyranoses are produced by enzymatic degradation of starch. They also synthesized a large number of their derivatives, ethers, esters, etc. (Szejtli, J.: Cyclodextrins and their Inclusion Complexes. Akadémiai Kiadó, Budapest, 1982). The reactivity of the primary and secondary alcoholic hydroxy groups in the cyclodextrin molecule also enables the preparation of medium-molecular weight water-soluble, ionic and nonionic polymers (according to Hungarian Patent Nos. 180,597 and 191,101).

Polyethyleneimine is a commercially available commercial product. Compounds of various average molecular weights are marketed by Badische Anilin und Sodafabrik (Germany).

In the process of the present invention, for photographic emulsion or gelatin, 0.020-0.25 mole per 100 g of gelatin emulsion or gelatin solution is coupling agent of formula (I) or (Π) or (ΙΠ) or (IV) or epichlorohydrin and 10-100 g of cyclodextrin. (CD) or a substituted cyclodextrin of formula (V) or a water soluble cyclodextrin polymer of formula (VI) or / and a polyethyleneimine of formula (VII).

According to the invention, it is also possible to apply 10-100 g of polyethyleneimine and 0.020-0.25 moles of formalin per 100 g of photographic emulsion or gelatin solution, or glyoxal or epichlorohydrin, either (I) or (Π), or the coupling agent (ΙΠ) or (TV) and polyethyleneimine (VII) (10-100 g) are added.

According to the invention, it is also possible to use 0.020-0.25 moles of epichlorohydrin per 100 g of photographic emulsion or gelatin solution, either in accordance with the general formula (I) or (,) or (ΙΠ) or (IV). The molar ratio of gelatin to cyclodextrin in the copolymer and from 10 to 100 g of gelatin-cyclodextrin copolymer may vary from 10:90 to 90:10, and optionally polyethyleneimine of formula (VH) is added.

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Aképletekben:

Q - ((¾) ^ group,

X is hydrogen, -COOH, -NR 2, -OH, -SO ₃ H group,

R is hydrogen or C1-C3 alkyl,

R ¹ in the polymer chain of the cyclodextrin molecules together an ether bond bridge which epillórhidrin coupling agent

-CH ₂ -CH-CH ₂ - [- O-CH ₂ -CH-CH ₂ -] - _x ,

ORy For example, ORy is a diethoxide coupling agent

-CH ₂ -CH-CH ₂ -O- (CH ₂ ) _m -OORy PRl ·

-CHCII ₂ -CII - (- O-CII ₂ -CH-CH ₂ O- (CH ₂ ) _in ORy ORy

-O-CH ₂ -CH-CH ₂ -] - _x ,

ORy ORy

Ry is hydrogen, carboxy (C 1 -C 5 alldl) or amino (C 1 -C 5 alkyl), x 0

R ^{2 is} hydrogen or a substituent identical to R ³ ,

R ^{3 is} -OH, -ORy, -O (CH 2) _m ORy, - (OO ^ CH ^ ORy, -NHR, -NR 1, -NH 1 CH 2 -COOH),

R ^ -R ^4, - (R ¹ -R ¹ -CD ³⁾⁾ _n -R ² or ³ z R

The same substituent as Ry,

R ⁶ - (CH 3 -COOH group,

CD is a group obtained by removing an m-hydroxyl group from an α-, β- or γ-cyclodextrin molecule,

CD ¹ is α-, β- or γ-cyclodextrin molecule a group obtained by removing three hydroxy,

^CD3 is α-, δ- or a hydroxyl group obtained by removing γ-cyclodextrin molecules (z + 2), m is 1 to 6, n is a number from 2 to 12, w is from 1 to 4 and z is 0 or at least two small , such as the number of original OH groups on the CD, k 650, p 0, or at least two less than the number of original OH groups on the CD.

In addition to the α-, δ- or γ-cyclodextrin monomers, substituted derivatives thereof, such as, e.g. carboxymethyl, diethylaminoethyl, dimethyl, trimethyl, hydroxypropyl, sulfopropyl, sulfobutyl, and the like. water-soluble cyclodextrin polymers having an average molecular weight of 2,000 to 10,000 daltons and 30 to 701% CD, such as e.g. unsubstituted α-, δ- or γ-cidodextrin polymer, or carboxymethyl, diethylaminoethyl, carboxypropyl-γ-amino, and the like. cyclodextrin polymers containing one or more groups.

The polyethylene imines which may be used may be unsubstituted or may have, e.g. carboxypropyl polyethyleneimine. Their molecular weights may vary within wide limits; medium molecular weight (M 3 - 3.10 ⁴ -4.10 ⁴ ) polymers

As coupling agents, they can be used in addition to epichlorohydrin, e.g. diglycidyl ether (I. m-1), butanediol diglycidyl ether (Π, m-4), diglycidyl diethylamine (ΙΠ, m-1) or triglycidophosphorous oxide (IV, m-1).

In the process of the invention, the copolymer. Hl. Its components for in situ preparation (CD, FEI coupling agent) are added before the casting solutions are applied to the carrier, after addition of the usual additives (optical sensitizer, plasticizer, wetting agent, colorant dispersion, stabilizer, etc.).

No additional tanning agent is required when using the process of the invention.

The photo material carrier can be hanta hats. plastic coated (RC) paper or film. The process of the invention is particularly effective in the latter two cases.

The effect of the copolymers on the properties of the gelatin-containing layer can be monitored by determining three characteristics: hardness and water uptake of the layer and diffusion in the developing layer.

The hardness is determined by dipping the strip of the test substance in a 500 ml beaker at room temperature in 0.08 M / L sodium carbonate solution, immersing the liquid in a thermometer and heating the vessel at 1-2 V / min. The melting point is defined as the temperature at which the layer is wet from the substrate. Hardness is characterized by increasing the melting point of At _mp - t _mp - t ' _mp , where - t' _{mp of} the coupling agent is the wetting temperature of the non-coupling layer at the equilibrium state of the layer hardness (when At 1 no longer changes).

The water uptake is determined by immersing a 36 cm ² photographic material in a 25 ° C sodium carbonate solution (0.08 M / L) for 16 minutes (equilibration of the water uptake), then removing the surface by filter paper and determining weight gain. The water uptake is calculated using the formula Q-g-go (g ,,) and is given for the layer for which At, ™ 50 (except for the non-coupling layers, where Atmp-0). In the formula g is the weight of the wet layer grams obtained by subtracting the weight of the wet base from the wet (layer + base) weight; g "- the dry weight in grams obtained by subtracting the dry weight from the dry (layer + base) weight .

The developer diffusion is plotted on the linear portion of the curve with the same H illumination and t time eluted, D * optical density per unit silver content of the undeveloped layer, D * -D / C _Ag , where C ^ is the silver content of the undeveloped layer in g / m ² . The decrease in D * may be due, if appropriate, to a slowdown in caller diffusion.

The gelatin copolymer exhibits the desired effect when Q is reduced in its presence, and λ p and D * are not less than the corresponding indices of the non-copolymer-containing layer.

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

HU 203 603 Β

- provides meadows with good physico-chemical and mechanical properties,

- reduced water uptake,

however, the diffusion properties of j do not degrade photographic properties.

The following embodiments illustrate the process of the present invention.

Example 1

For AgBr emulsion containing 100.0 g octahedral crystals (11.2 g gelatin, 0.025 mol AgBr content, L-180 nm crystal size) 2 ml of 0.05% 3,3'-diethyl-r-phenyl- benzoxazolidene) -ethylidene-2'-thiolaldantoin, 2 ml of 50% glycerol solution, 5 ml of 4% saponin solution and 1 ml of 1% phenylmercaptotetrazole solution, and an appropriate amount of coupling agent and . Addition of distilled water and sufficient distilled water to obtain 1.15 ± 0.05 g / m ^{2 of} silver on a RC casting machine.

To capture the characteristic curve needed to determine D *, photographic material is illuminated with a 2800 K color incandescent lamp through a photographic modulator and exposed to 18 'Con for 2 minutes in the following composition: 1 g of methol, 4 g of hydroquinone, 230 g of anhydrous potassium sulfite, g of potassium bromide - in 1 liter of water.

No additive.

Coupling agent: a) 10.5 mL of 8% 2-oxy-4,6-dichlorotriazine; b) 6.7 ml of 2% formalin; c) 6.5 ml of 4% glyoxal solution; d) 7.2 ml of 8% diglycidyl ether (DGE; I, m-1) solution; e) 11.2 mL of 8% butanediol diglycidether (BGE; Hm-4); (f) 14 ml of a 5% solution of diglycidylethylamine (DGEA; ΙΠ. m-1); g) 15 ml of a solution of 8 µl of triglycidylphosphoric oxide (TGF; IVjn-1).

Example 2

All were carried out as in Example 1 except that different additives and coupling agents were used: a) Acrylate latex additive (Rhoplex, Hass and Rohm), 16.8 ml of 20% dispersion; coupling agent: 6.7 ml 2% formalin; b) Additive as a); coupling agent. 7.2ml8t% DGE c) Adye / dfc · 22.3ml 15% carboxymethyl-β-cyclodextrin polymer (CM-βCDP; CD content 42t%, M ^ 2800); coupling agent. 6.7 ml 2% formalin.

Example 3

Everything was done as in Example 1 except that different additives and coupling agents were used. Additive in each case 33.6 ml of 10% α-cyclodextrin (α-CD) o > coupling agent.

a) 3.6 ml; b) 7.2 ml; c) 14.4 mL of 8% DGE.

Example 4

In the same manner as in Example 1 except that different additives and coupling agents were used, additive a) 7.5 ml; b) 14.9 ml; c) 22.4 ml; d) 44.8 ml of a 15% solution of CM-β-CDP (CD content: 56%, M-3000). Coupling agent: 7.2 ml of 8% DGE solution in each case.

Example 5

All were carried out as in Example 1 except that 22.4 ml of a 10% solution of dimethyl-β-cyclodextrin (ΟΜ-β-CD) were used in each case with different additives and coupling agents.

Coupling agent (a) 7.5 ml; b) 15 ml; c) 22.5 ml; d) 30 ml of 8% TGF solution.

Example 6

Everything is done as in Example 1, except that different additives and coupling agents are used.

Additive in each case is 14 ml of a 20% solution of hydroxypropyl-β-cyclodextrin (ΗΡ-β-CD).

Coupling agent: a) 11.2 ml; b) 22.4 ml; c) 33.6 ml; d) 44.8 ml of 8% BGE solution.

Example 7

Everything is done as in Example 1 except that different additives and coupling agents are used.

Additive in each case was a solution of 28 ml of a 20% solution of carboxypropyl-7-amino-β-cyclodextrin polymer (ΚΡΑ-βCDP; CD content 581, M M - 3900).

Coupling agent, (a) 5.6 ml; b) 11.2 ml; c) 16.8 ml; d) 22.4 ml of 8% BGE solution.

Example 8

Everything is done as in Example 1 except that different additives and coupling agents are used.

Additive in each case 28 ml of a 10% solution of 10% diethylaminoethyl-β-cyclodextrin polymer (ΟΕΑ-β-CDP; CD content 591 µM - 3100)

Coupling agent, (a) 3.5 ml; b) 7.0 mL; c) 14.0 mL; d) 21.0 mL of 10% DGEA solution.

Example 9

Everything is done as in Example 1 except that different additives and coupling agents are used.

Additive a) 8.4 ml; b) 16.8 ml; c) 22.4 ml; d) 28 ml of 20%%-β-CD solution.

Coupling agent: 7.0 ml of 10% DGEA solution in each case.

Example 10

In everything we do as in Example 1, except that we use different additives and coupling agents

Additive a) 11.2 ml; b) 22.4 ml; c) 33.6 ml of a 20% solution of di (carboxymethyl) -? - cyclodextrin (diCM-? -CD)

Coupling agent: 14.0 mL of 10% DGEA solution in each case.

Example 11

In everything we do as in Example 1, except that we use different additives and coupling agents

In each case, 16.8 ml of 20% gel-41 was added

HU 203 603 Solution of tin-cildodextrin polymer ([ZS] / [CD3-15/85).

Coupling agent, (a) 7.2 ml; b) 14.4 ml; c) 21.6 ml of 8% DGE solution.

Example 12

Everything was done as in Example 1 except that different amounts of gelatin and / or gelatin were used. various additives and coupling agents are used.

a) 8.0 g of gelatin; 40.0 ml of a 20% solution of gelatin-cyclodextrin copolymer ([ZS] / [CD] - 50/50); 5.2 mL of 8% DGE solution.

b) 8.4 g of gelatin; 36 ml of 20% gelatin cyclodextrin copolymer ([ZS] / [CD] - 50/50), 5.5 ml of 8% DGE solution.

c) 8.8 g of gelatin; 32 ml of a 20% gelatin-eicodextrin copolymer ([ZS] / [CD] - 50/50) solution; 5.7 ml of 8% DGE solution.

d) 9.2 g of gelatin; 28 ml of a 20% gelatin-cyclodextrin copolymer ([ZSJ / [CD] - 50/50) solution; 6 ml of 8% DGE solution.

Example 13

Everything was done as in Example 1 except that different amounts of gelatin and / or gelatin were used. various additives and coupling agents are used.

a) 6.2 g of gelatin; 31 mL of a 20% solution of Jdatin / Cildodextrin copolymer ([ZS] / [CD] - 85/15); 8 ml of 8% DGE solution.

b) 6.7 g of gelatin; 28 ml 20% copolymer ([ZS] / [CD] - 85/15) solution; 8.7 ml of 8% DGE solution.

c) 7.3 g of gelatin; 25 ml of a 20% copolymer ([ZS] / [CD3-85/15) solution; 9.5 ml of 8% DGE solution,

d) 7.8 g of gelatin; 22 ml 20% copolymer ([ZSJ / [CD] - 85/15) solution; 10.2 ml of 8% DGE solution.

1-13. The results of Examples 1 to 6 are shown in Table 1. The data show that, as compared to the non-additive layers, the additive is an acrylate latex or an additive. layers containing a cyclodextrin polymer introduced without a suitable coupling agent do not show better properties. In contrast, the layers containing the additive and coupling agents of the present invention absorb, with good heat resistance and a suitable photographic index, a smaller amount of water than those without the same additive additive.

Example 14 To a ml of gelatin solution (containing 12.0 g of gelatin), a) no coupling agent was added; added

b) 7.8 ml; c) 15.6 ml; d) 23.4 ml of an 8% DGE solution and made up to 150 ml with distilled water and stirred at 40 ° C for 10 minutes. Each solution is applied to an RC paper support on an experimental casting machine so that after solidification and drying the application rate shall be 11,5 ± 1 g / m ² .

Example 15 To a ml of gelatin solution (containing 12.0 g of gelatin) was added 30 ml of a 12% solution of CM-β-CDP (03 content 421%, 2800), (a) no coupling agent was added; b) 15.6 ml; c) 23.4 ml;

d) 31.2 mL of 8% DGE solution.

Table 1

1-13. data for examples (D * applies to 30 lxs fields)

Coupling_Add_Layer Characteristics

Example Neve mol / 100 g of gel. Neve gram / 100g plus gel. Q D * First the triazine 0.04 no > 50 3.12 1.02 b Formalin 0.4 »» > 50 2.59 0.85 c glyoxal 0.04 »» > 50 2.68 0.94 d DGE 0.04 "♦ > 50 1.53 0.96 e BGE 0.04 »» > 50 2.15 1 "1 f DGEA 0.04 »· > 50 3.41 1.18 g TGF- 0.04 »» > 50 2.86 1.24 Second the shape 0.04 Acrylate latex 30 > 50 2.28 0.35 b DGE 0.04 Akrura latex 30 > 50 1.51 0.37 c formalin 0.04 CM-P-CDP 30 > 50 2.73 0.90 Third the DGE 0.02 the CD 30 > 50 1.16 1.29 b 0.04 30 > 50 1.02 1.21 c 0.08 30 > 50 0.90 1.18

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Table 1 continued Data for Examples l-13 (D * refers to fields with 30 lxs of illumination)

coupling agent additive Characteristics of the layer Example Neve mol / 100g plus gel. Neve gram / 100 g of gel. ATMP Q D * 4th the DGE 0.04 CM-P-CDP 10 > 50 1.15 1.32 b 0.04 20 > 50 1.05 129 c 0.04 30 > 50 1.00 1.15 d 0.04 60 > 50 0.96 1.0 5th the TGF- 0.02 DM-ss-CD 20 > 50 1.52 1.36 b 0.04 20 > 50 1.25 1.34 c 0.06 20 > 50 1.10 1.32 d z 0.08 20 > 50 0.88 1.29 0th the BGE 0.04 HP-p-CD 25 > 50 1.36 1.08 b 0.08 25 > 50 1.15 1.05 c 0.12 25 > 50 0.96 0.96 d 0.16 25 > 50 0.88 0.94 7th the BGE 0.02 KPA pCDP 50 > 50 2.00 1:14 b 0.04 50 > 50 1.85 1.18 c 0.06 50 > 50 1.63 1.09 d 0.08 50 > 50 1.26 1.05 She. the DGEA 0.02 DEA-P-CDP 25 > 50 1.66 121 b 0.04 25 > 50 1.16 1.25 c 0.08 25 > 50 0.80 1.24 d 0.12 25 > 5o 0.75 1.24 9th the DGEA 0.04 HP-p-CD 15 > 50 1.03 1.10 b 0.04 30 > 50 0.88 1.12 c 0.04 40 > 50 0.92 1.06 d 0.04 50 > 50 1.08 1.05 10th the DGEA 0.08 di-CM-P-CD 20 > 50 1.10 0.96 b 0.08 40 > 50 1.08 0.98 c 0.08 60 > 50 1.10 1.00

11th

a b

c

12th

DBE 0.04 Gel / CDkop. 30 > 50 0.91 0.98 0.08 15/85 30 > 50 0.86 0.96 0.12 30 > 50 0.81 0.97

(λ ο

DGE 0.04 Gel / CDkop. 100 > 50 1.16 1.05 0.04 50/50 86 > 50 0.95 0.96 0.04 73 > 50 1.00 0.97 0.04 61 > 50 1.08 0.98

13th

a b

c d

DGE 0.08 Gel / CDkop. 100 > 50 1.38 1.20 0.08 85/15 84 > 50 1.30 1.18 0.08 68 > 50 1.26 1.18 0.08 56 > 50 1.30 1.21

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In the following, we proceed as in Example 14.

Example 16 To a ml of gelatin solution (containing 12.0 g of gelatin) was added a) 10 ml, b) 20 ml of 12% CM-pCDP solution, c) 32 ml; d) 48 ml of 15% CM-β-CDP solution (see Example 15 for characteristics), sit. in each case 19.5 ml of 8% DGE solution. In the following, we proceed as in Example 14.

Example 17 To a ml of gelatin solution (containing 8.0 g of gelatin) was added 30 ml of a 8% solution of polyethyleneimine (PEI; "Polymin P" product from BASF), a) no coupling agent was added. b) 7.8 ml;

c) 15.6 ml; d) 31.2 mL of 8% DGE solution. In the following, we live as in Example 14.

Example 18 To a solution of gelatin (containing 8.0 g of gelatin) is added 10 ml of 8% PEI solution, a) no coupling agent is added, b) 9.6 ml of 2% formaldehyde solution is added. In the following, we proceed as in Example 14.

Example 19 To a solution of gelatin (containing 8.0 g of gelatin) is added 20 ml of 8% PEI solution, a) no coupling agent is added, b) 7.4 ml of 5% glyoxal solution is added, and as in Example 14.

Example 20 To a ml of gelatin solution (containing 12.0 g of gelatin) was added a) 20 ml of a 12% solution of β-cyclodextrin polymer (β-CDP; CD content: 581%; M ^-3200), b) 30 ml of a 12% solution of--β-CDP (CD content: 56%; M _w - 3500), c) 30 ml of a 12% bis (carboxymethyl) β-cyclodextrin polymer (BCM-p- CDP; CD content: 50%; M _{w / w} 2950), d) 30 ml of a 12% solution of CD-β-CDP (CD content: 61 wt%; M _w 4800); in each case 15.6 ml of 8% DGE solution. In the following, the procedure of Example 14 is followed.

Example 21 A solution of gelatin solution (containing 12.0 g of gelatin) was adjusted to pH 7.0 with 40% NaOH and then a) 40 ml of 15% a-cylodextrin solution and 0.0216 mole of epichlorohydrin, b) 45 ml of 4% β-cyclodextrin solution and 0.006 mole of epichlorohydrin, c) 48 ml of 25% γ-cyclodextrin solution and 0.030 mole of epichlorohydrin, d) 40 ml of 15% dimethyl-p- cyclodextrin (ΟΜ-β-CD) solution and 0.018 moles of epildlorohydrin; hereinafter, as in Example 14.

Example 22 To a ml of gelatin solution (containing 12.0 g of gelatin) was added 30 ml of a 12% solution of HPP-CD,

a) no coupling agent is added; b) 15.6 mL of 8% DGE solution, c) 18.9 mL of 8% DGE solution, d) 24.2 mL of 8% BGE solution. In the following, we proceed as in Example 14.

Example 23 To a ml of gelatin solution (containing 10.0 g of gelatin) was added 25 ml of a 16% solution of DM-β-CD, (a) no coupling agent was added; added

b) 10.1 mL, c) 20.2 mL, d) 40.44 mL of a 10% BGE solution. In the following, we proceed as in Example 14.

Example 24 To a solution of gelatin (containing 10.0 g of gelatin) was added a) 5 ml b) 10 ml c) 20 ml d) 40 ml 20% sulfobutyl-β-cyclodextrin (SB-β-CD) ) and 16.2 mL of 10% BGE. In the following, we proceed as in Example 14.

Example 25

a) Dissolve 3.4 g of β-cyclodextrin in 100 ml of 6% gelatin solution at 40 ° C, add 24 ml of 10 volumes of PEI and 7.8 ml of 8% DGE solution.

b) Dissolve 1.8 g of β-cyclodextrin in 100 ml of 6% gelatin solution at 40 ° C, add 12 ml of 101% PEI and 7.8 ml of 8% DGE solution.

c) Dissolve 2.4 g of β-cyclodextrin in 100 ml of 6% gelatin solution at 40 ° C, add 36 ml of 10% PEI solution and 7.8 ml of 8% DGE solution.

d) Swell in 100 ml of a 1.2% β-cyclodextrin solution, then dissolve 6 g of gelatin, then add 40 ml of 12% PEI solution and 7.8 ml of 8% DGE solution at 40 ° C.

In each case, make up to 150 ml and proceed as in Example 14.

Example 26

After swelling in 101 ml of a 3% solution of CM-β-CDP (CD content 48%, M +/- 6100), 6 g of gelatin were dissolved and 30 ml of a 10% PEI solution were added at 40 ° C. (a) no additive or additive is added; b) 2.35 ml, c) 4.7 ml, d) 9.4 ml of 8% DGEA solution are added. Hereinafter we shall proceed as

Example 14.

Example 27 To 40 ml of gelatin solution (containing 6 g of gelatin) was added 40 ml of a 15% solution of gelatin / cyclodextrin copolymer ([ZS] / [CD] - 10/90), (a) no coupling agent was added; add b) 3.2 ml, c) 6.4 ml,

d) 12.8 mL, e) 25.6 mL of a 10% TGF solution. In the following, we proceed as in Example 14.

14-27. The results for Examples 1 to 8 are shown in Table 2. It is apparent from the data that the cyclodextrin derivatives added to the gelatin and the polyethyleneimine can be used to produce layers having substantially reduced water uptake with appropriate mechanical properties. Layers containing separately synthesized gelatin / cyclodextrin polymer also exhibit similar properties.

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Table 2

A14-27. data for examples

coupling agent additive Characteristics of the layer Example Neve mol / 100 g of gel. Neve gram / 100 g of gel. Δ ^ ιηρ Q 14th the DGE 0 no - 0 7.75 b 0.04 > 50 4.12 c 0.08 > 50 2.53 d 0.12 > 50 1.36 15th the DGE 0 CM-3-CDP 30 0 $ 44 b 0.08 30 > 50 1.19 c 0.12 30 > 50 0.85 d 0.16 30 > 50 0.79 16th the DGE 0.10 CM-P-CDP 10 > 50 1.12 b 0.10 20 > 50 0.95 c 0.10 40 > 50 0.76 d 0.10 60 > 50 0.69 17th the DGE 0 PEI 30 0 3.02 b 0.04 30 > 50 1.20 c 0.08 30 > 50 0.50 d 0.16 30 > 50 0.37 18th the formalin 0 PEI 10 0 5.15 b 0.08 10 > 50 1.10 19th the Glloxal 0 PEI 20 0 4.70 b 0.08 20 > 50 1.80 20th the DGE 0.08 β-CDP 30 > 50 0.93 b 0.08 DEA-P-CDP 30 > 50 1.09 c 0.08 BCM-3-CDP 30 > 50 0.95 d 0.08 ΚΡΑ-β-CDP 30 > 50 1.03 21st the epichlorohydrin 0.18 the CD 50 38 1.42 b 0.05 β-CD 15 35 1.90 c 0.25 γ-CD 100 32 1.60 d 0.15 DM ^ -CD 50 36 1.38 22nd the DGE 0 ΗΡ-β-CD 30 > 50 6.49 b DGE 0.08 30 > 50 1.06 c DGEA 0.08 30 > 50 1.10 d BGE 0.08 30 > 50 0.55 23rd the BGE 0 ϋΜ-β-CD 40 > 50 5.33 b 0.05 40 > 50 1.45 c 0.10 40 > 50 0.89 d 0.20 40 > 50 0.78 24th the BGE 0.10 SB-p-CD 10 > 50 4.86 b 0.10 20 > 50 1.50 c 0.10 40 > 50 1.32 d 0.10 80 > 50 1.26

HU 203 603 Β

Continuing Table A14-27. data for examples

coupling agent additive Characteristics of the layer Example Neve mol / 100 g of gel. Neve gram / 100 g of gel. Q 25th the DGE 0.80 40% PEI / 60% β-CD 100 > 50 0.35 b 0.08 50 > 50 0.68 c 0.08 60% PEI / 40% β-CD 30 > 50 0.72 d 0.08 80% PEI / 20% β-CD 10 > 50 0.78 26th the DGEA 0 50% PEI / 50% ΟΜ-β-CDP 30 0 4.35 b 0.02 30 > 50 1.86 c 0.04 30 > 50 1.39 d 0.08 30 > 50 1.26 27 the TGF- 0 Gel / CDkop. 100 0 5.30 b 0.02 10/90 100 > 50 1.86 c 0.04 100 > 50 1.50 d 0.08 100 > 50 1.32 e 0.16 100 > 50 1.06

Claims (5)

A process for improving the physico-chemical properties of silver halide based photographic layers by adding a coupling agent and a monomer and / or polymer to an emulsion of gelatin 30 and additives, characterized in that the photographic emulsion or gelatin emulsion or gelatin solution per 100 g of gelatin (a) 36 0.020-0.25 moles of coupling agent of formula (I) or (Π) or (E) or (TV), and 10,100 g of cyclodextrin or substituted cyclodextrin or water-soluble cyclodextrin polymer or / and polyethyleneimine; b) 0.020-0.25 moles of formalin or glyoxalized or epichlorohydrin or coupling agent of formula (I) or (Π) or (E) or (IV) and 10-100 g of polyethylene imine or c) 0.020-0.25 moles of epichlorohydrin or coupling agent of formula (I) or (Π) or (E) or (TV) and 10-100 g of gelatin-cyclodextrin copolymer in a copolymer having a gelatin-cyclodextrin molar ratio of 1090 to 50 90 : May be within the range of 10, and optionally pdethylenimine of formula (VII) may be added, Q-jCH ^ - group, X is hydrogen, or -COOH, -NR ^ -OH, -SO ₃ H, 55 R is hydrogen or C ₁ -C ₅ alkyl, R ^{1 is} the ether linker linking the cyclodextrin molecules in the polymer chain, which in the case of epillorhydrin coupler -CH ₂ -CH-CH ₂ - [- O-CH ₂ -CHCH ₂ -] - _x , 60 For example, ORy ORy for the diethoxy coupling agent is -CH ₂ -CH-CH ₂ -O- (CH ₂ ) _m -OORy PRy -CHCH ₂ -CH - [- O-CH ₂ -CH-CH ₂ O- (CH ₂ ) _m ORy ORy -O-CH ₂ -CH-CII ₂ -] - _x , ORy ORy Ry is hydrogen, carboxy (C 1 -C 5) alkyl or amino (C 1 -C 5) alkyl; R ^{2 is} hydrogen or a substituent identical to R ³ , R ³ -OH, -OR ,, -O _{(CH2: lm} ORY - <OCH ₂ CH _{2) m} OR _y, -NHR, -NR ,, -NH (CH,) _m -COOH. R ⁴ -R'R * - ^ - aP-R ^ -R ^ or zR ³ The same substituent as Ry, R ° (CH ^-COOH group, CD is a group obtained by removing an m-hydroxyl group from an α-, β- or γ-cyclodextrin molecule, CD ¹ is α-, β- or γ-cyclodextrin molecule a hydroxyl group obtained by removal of 3 and CD ³ represents α-, δ- or a hydroxyl group obtained by removing γ-cyclodextrin molecules (z + 2), m is n is 1 to 6 A number from 2 to 12, w a number from 1 to 4, z 0 or at least two less than the number of original OH groups on the CD, k 650, p 0 or at least two less than the number of original OH groups on the CD. A process according to claim 1, characterized in that: EN 203603 Β using diglycidyl ether as a coupling agent. 3. The process according to claim 1, wherein the coupling agent is butanediol diglycidyl ether. The process of claim 1, wherein the coupling agent is diglycidyl diethyline. 5. A process according to claim 1 wherein the coupling agent is triglycidyl phosphorous oxide.