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Publication numberUS3174861 A
Publication typeGrant
Publication dateMar 23, 1965
Filing dateJul 13, 1961
Priority dateJul 16, 1960
Also published asDE1130283B
Publication numberUS 3174861 A, US 3174861A, US-A-3174861, US3174861 A, US3174861A
InventorsHans Ulrich, Walter Kleist, Wolfgang Himmelmann
Original AssigneeAgfa Ag
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Photographic elements containing bischloroacylamido hardening agents
US 3174861 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

iinite States This invention relates to the hardening of photographic layers, particularly of silver halide emulsion layers which contain as a colloidal carrier material a protein derivative, particularly gelatin.

Photographic materials are treated with photographic processing solutions which have different pH values and diiferent temperatures. It is, therefore, extremely important to use photographic products with colloidal layers which when compared with pure gelatin are more resistant to water, swell less and have a higher melting point. For this reason, the gelatin layers must be hardened without depriving them of their water permeability. A large number of publications have recommended whole series of compounds and classes of compounds as hardening agents. The following classes can be distinguished: Metal salts such as chromium, aluminum or Zirconium salts; aldehydes and halogen containing aldehydes such as formaldehyde, dialdehydes (glyoxal) and mucochloric acid; 1,2 and 1,4-diketones such as cyclohexanedione-l,2; quinone; chlorides of di basic organic acids; dianhydrides of tetracarboxylic acids; compounds with several reactive vinyl group such as vinylsulfone or acrylamide; compounds with at least two easily splitable heterocyclic rings such as ethylene oxide and ethyleneamine; and polyfunctional esters of methanesulfonic acid.

Most of these hardening agents are photographically active and for this reason cannot be used with a large variety of photographic emulsions. Besides, the metal salts increase the brittleness of the layers, whereas the aldehydes react with various types of color formers present in the color emulsion layers and cause color fog. Several of the diketones and dialdehydes color the colloidal layers and are, therefore, unsuitable. Moreover, many hardening agents tend to fog the emulsion on prolonged storage or to decrease the sensitivity. The anhydrides and the acid chlorides have the inherent disadvantage of lowering the pH of the emulsion, thus requiring an adjustment of the pH with an alkali. In many instances, the hardening agents increase the viscosity of the coating solution to an alarming degree. Other hardening agents suffer from the disadvantage that they become active only after prolonged storage. In this manner, these hardening agents change the sensitometric characteristics of the layer in an uncontrollable manner. One refers to this effect as after-hardening.

It is among the objects of the present invention to provide novel hardening agents for photographic layers, particularly gelatin and gelatin silver halide emulsion layers, thus providing products which have improved physical and photographic properties. Other objects will be apparent from the following description.

We have found that the products obtained by the re action of aliphatic, aromatic or heterocyclic diamines with a-chloroacyl chlorides serve as very useful hardening agents. When these reaction products are added to gelatin solutions or liquid gelatin silver halide emulsions, they increase the melting point of the coated layers without causing any adverse eifects such as fog, desensitization or loss of contrast. The materials obtained are stable and do not deteriorate during storage due to after- 3,i?4,8bl. Patented Mar. 23, 1955 ice In this formulae R R R and R which may be alike or different represent hydrogen or lower alkyl groups such as methyl, ethyl, or propyl; n is a positive integer ranging from 1 to 7; X and X together represent the carbon atoms necessary to complete a fully hydrogenated 5 or 6 membered heterocyclic nucleus such as a piperazine or pyrazolidine; and Y and Y together represent the atoms necessary to complete an aromatic nucleus of the benzene series which may be further substituted by a suitable group such as a carboXy group to increase the water solubility of the hardening agent.

These hardening agents can be readily prepared by reacting in an aqueous alkaline solution, an aliphatic, aromatic or heterocyclic diamine with the chloride of an ot-chlorocarboxylic acid. The separation and purification of the reaction products does not offer any difiiculties because the compounds precipitate from the solution and need only to be purified by recrystallizing the precipitate.

Among the diamines which can be used in the reaction are the following:

Hydrazine N,N'-dimethylhydrazine Methylenediamine Ethylenediamine Propylenediamine Tetramethylenediamine Pentamethylenediarnine. l-iexamethylenediamine 1,2-phenylenediamine 1,4-phenylenediamine Pip erazine Pyrazolidine Among the chlorides of a-chlorocarboxylic acids which can be used in the preparation of the novel hardening agents are: a-chloracetyl chloride, oc-ChlOlOPIOPiOIlYl chloride and ct-chlorobutyryl chloride.

These compounds are used advantageously in photographic silver halide gelatin emulsion layers, as well as in backing layers, non-curling layers, protective layers, filter layers, and other auxiliary layers which contain gelatin or other related proteins. Our hardening procedure reduces swelling, as well as the solubility of gelatin in the desired manner. A further advantage resides in the fact that the hardened layers do not become brittle. In this respect, they are superior to the trifunctional hardening agents which provide a three-dimensional bonding and result, therefore, in layers which are inherently more brittle. The hardened layers show also in the moistened state a good abrasion resistance and a surprisingly low swelling height. In general, there is very little after-hardening because maximum hardening is reached within a few days.

A great advantage of the hardeners of this invention resides in the feature that they will not react with any color formers which are present in multilayer color materials. Consequently, they can also be used in multilayer materials having incorporated in the emulsions color formers which are fast to diffusion.

Furthermore, it was observed that the compounds do not only harden the layers but improve the adhesion of the several over-coated layers in multilayer materials. The danger of separation of the layers in the wet state during the processing and drying is, therefore, reduced.

The hardening agents are added to the photographic coating preparations in the form of a solution in a suitable water-miscible organic solvent such as methanol, ethanol, dioxane, dimethylformarnide and the like prior to coating. Neither the viscosity nor the pH of the coating solutions are altered by this technique. The amounts of hardening agents added depend on the desired effect. In general, from 1.0 to 20.0 grams of hardening agents per kilogram of dry colloidal carrier material such as gelatin are sufiicient. One thereby obtains layers with high melting points. The action of the hardening starts only after the drying of the layer.

The action of the hardening agents can be explained on a hypothetical basis by assuming that the a-chlorine atom is rendered more labile by the proximity of the CO group and is readily split off; so that the remaining part of the hardener molecule reacts with the amino group of one or several gelatin molecules as indicated by the following formula:

Z Protein E Z Protein It should be understood, however, that the invention is not based on the hypothetical formulation. There are a great number of compounds which can be used as hardening agents in accordance with this invention. The following examples are illustrative:

( 1) Bis-chloroacetylhydrazine Preparatin.40 grams of hydrazine hydrate (25%) and grams of potassium hydroxide are dissolved in 50 milliliters of water. This resultant solution is cooled to 0 to C. and 30 milliliters of chloroacetyl chloride are added dropwise with stirring. At the completion of the reaction, the pH of the mixture is adjusted with sodium hydroxide to a value between 7 and 8. Stirring is continued for one-half hour. The precipitate is filtered, washed and dried. Yield of crude product is grams. The product is purified by recrystallization from methanol and has then a melting point of 165 to 167 C.

(2) Bis-chloroacetyl-N,N'-dimethylhydrazine Preparation.--In analogy to the above procedure except that dimethylhydrazine was used as the starting material; M.P. 124 C.

(3) Methylene-bis-chloroacetamide Preparati0n.Annalen, vol. 343, page 284; M.P. 174 C.

Prepar'ation.]. Biol. Chem, vol. 21, page 151; M.P. 174176 C.

(5 Bis-chloroacetyl-N,N'-dimethylethylenediamine ClCH -C ONCH2CH2NC O-CH2C1 H3 H3 Preparation.1n analogy to the procedure described in J. Biol. Chem, vol. 21, page 151, except that N,N-dimethylethylenediamine was used in place of ethylenedlamine; M.P. -132 C.

(6) Bis-chloroacetylpiperazine CHg-OH N-C OGH2C1 GH -CH Preparation.Hopper-Seyler, vol. 144, page 220; M.P. l37-138 C.

(7) Bis-chloroacetyl-tetramethylenediamine Preparati0n.-44 grams of tetramethylenediarnine are added to a solution of sodium hydroxide in 200 milliliters of water. The mixture is cooled to a temperature of 5 C., stirred and 112 grams of chloroacetyl chloride are added dropwise with stirring. The pH is adjusted to a value between 7 and 8 by adding the necessary amount of 10% sodium hydroxide solution. Stirring was continued for one-half hour and then the substance which had precipitated was filtered off and washed with water. After recrystallization from alcohol, 42 grams of the pure compound was obtained which had a melting point of 134 C.

(8) Bis-chloroacetyl-l,'2-phenylenediamine 4 carboxylic acid IIIlEP-CO-OHzCl Preparation-15.2 grams of 3,4-diaminobenzoic acid are added to a solution of 12 grams of sodium hydroxide in 200 milliliters of Water. The resultant mixture was cooled to 5 C. and 28.2 grams of chloroacetyl chloride are added dropwise with stirring. The pH of the mixture was adjusted with sodium hydroxide to a value between 9 and 10. Stirring was continued for one-half hour and then the solution was acidified with dilute sulfuric acid. The substance which precipitated was separated, washed and recrystallized from ethanol. Yield 16 grams; M.P. 231 C.

(9) Bis-a-chloropropionylpiperazine CHZ OH2 N-CO-CHCl-C'H;

Ora-CH2 Preparation-44 grams of piperazine are added to 200 milliliters of a 10% sodium hydroxide solution. The solution is cooled to 5 C. and 128 grams of Z-chloropropionyl chloride are added dropwise with stirring. The pH is adjusted to a value between 7 to 8 with dilute sodium hydroxide at the end of the addition period. The product was filtered off under suction and washed thoroughly with water. After drying it was recrystallized from a small amount of methanol. Yield 30 grams; M.P. to 162 C.

The emulsion layers and intermediate layers which are hardened with our novel hardening agents can be coated on all known supports such as glass, paper, cellulose esters or other film forming synthetic polymers. The general composition of the coating solutions used for the preparation of these layers does not need to be changed because the adhesion of these layers is not adversely influenced by the hardening. In some cases, the.

adhesion is even improved through the use of the novel hardening agents. Similarly, the sensitizing procedure or other conventional methods of preparing the emulsions can be retained without change. The hardening agents described herein can be combined with previously known hardening agents if special efl ects are desired.

The advantages of our novel hardeners are especially pronounced when they are used in color materials including color films and papers which contain color formers fast to diffusion. Such materials are prepared according to the methods described in US. Patents 2,179,- 228, 2,179,239, 2,186,849 and 2,200,187 and consist of several integral emulsion layers coated on a clear cellulose ester film base, opaque base or paper. Each of the emulsions is sensitized to one of the primary colors of light, namely blue, green, and red. Usually, the top layer is blue sensitive, the middle layer is green sensitive, and the bottom layer is red sensitive. Each of the three silver halide emulsion layers contains dye-forming compounds fast to diffusion.

During the development of the silver image by an aromatic amino developing agent, these dye-forming compounds unite with the oxidation products of the developing agent to form an azornethine or indoaniline dye. Alternatively, the emulsion layer may be free from color formers in which case the film is processed with the color formers in the color developers by the selective second exposure and color development method as described in US. Patent 1,897,866, 1,900,870, 1,928,709, and 1,980,941.

Multicolor film in which each element bears a color yielding layer comprising a hydrophilic film-forming synthetic polymer containing a plurality of hydroxyl groups and having a plurality of color components and, in addition, containing light-sensitive silver salts in described in US. Patents 2,397,864, 2,397,865, 2,397,866, and 2,397,867.

Materials in which the developed picture is a phenazonium dye image formed by development with a 1,2,4- triaminobenzene developer are described in US. Patents 2,486,440, and 2,570,116.

While the following examples describe in detail the methods for accomplishing the aforestated objects, it is to be understood that they are given merely for the purpose of illustration and are not to be construed as limiting the scope of the invention.

Example I To 1 kilogram of a silver chlorobromide emulsion which is ready for coating and contains about 65 grams of gelatin, there was added 1.5 grams of bis-chloroacetyl- N,N-di1nethylethylenediamine dissolved in methanol. The addition of this hardening mixture does not increase the viscosity and does not change the pH which is preferably kept between a range of 6.0 to 8.0. The emulsion is coated on baryta paper. After the usual drying and storing for 48 hours at a temperature of 45, it was noted that the layer had a melting point of 100 C. The hardening is not influenced by the pH in a pH range of 6.0 to 8.0 and the photographic properties of the emulsions are not changed. After development, when conventionally hardened emulsion layers are usually in a highly swelled and tacky state, the swelling is minimal of our hardened layers and is negligible; besides the layers show no tackiness and good abrasion resistance. The extent of hardening in relation to the added amounts of hardening agents is shown in the following table:

Added amount of hardening agent relative to the dry weight of the gelatin. percent O Melting point of the layer after storage for 48 hours at 45 C 37 usual manner is coated with a blue-sensitive silver bromide emulsion which contains per one liter of solution:

45 grams of silver bromide, 70 grams of gelatin, and 11 grams of a color former of the following formula:

COONa The coating solution contains as the hardening agent 1.4 grams of bis-chloroacetyl-N,N'-dimethylethylenediamine dissolved in methanol. The coated layer is dried and stored for 48 hours after which time it showed a melting point of C. After completed color processing, the layer showed good adhesion to the support and contained a stain-free yellow dye image. The photo graphic properties of this emulsion including color density, speed and contrast were the same as those of an unhardened type emulsion.

Example III The light-sensitive material prepared in accordance with Example II was overcoated with a red-sensitive silver chloride emulsion which contains per 1 liter of solution:

33 grams of silver chloride, 72 grams of gelatin, and 14 grams of a color former having the following formula:

The coating solution contained 3 grams of the hardening agent bis-chloroacetyl-ethylenediamine. After coating, drying and storage, the melting point of the layer was determined as being above 90 C. The adhesion of the two color emulsion layers was noticeably improved by our hardening agent when compared with conventional hardening agents.

Example IV A subbed cellulose acetate film support was coated with 1 kilogram of a gelatin solution which contained approximately 30 grams of gelatin together with an antihalation dye and 1 gram of the compound bis-chloroacetyl-1,2- phenylenediamine-4-carboxylic acid dissolved in ethanol. After drying and storage, the backing layer had a melting point above C. This layer showed no tendancy to swell and had a very high resistance to abrasion in its wet state.

Example V Example IV was repeated with the exception that the hardening agent used was 1 gram of bis-chloroacetyl-N, N'-dimethylhydrazine. The backing layer obtained therefrom shows very little swelling and a high abrasion resist ance in the wet state.

Example VI '7 We claim: 1. A photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing a hardening amount of a bis-chloroacylamido hardening agent selected from the group of compounds having the following general formulae:

R1OHC o-N-c'n cn-N o o-cn-Ri I 1 -Yr 01 wherein R R R and R are members selected from the group consisting of a hydrogen atom and lower alkyl groups, n represents a positive integer ranging from 1 to 7; X and X represent the carbon atoms necessary to complete a hydrogenated heterocyclic nucleus; and Y and Y represent the carbon atoms necessary to complete an aromatic nucleus of the benzene series.

2. A photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing a hardening amount of a compound having the following formula:

CH CH3 3. A photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing a hardening amount of a compound having the following formula:

4. A photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing a hardening amount of a compound having the following formula:

5. A photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing in addition to a color former fast to diffusion capable of forming upon development with a primary amine developing agent, a dye image selected from the group consisting of azomethine, indoaniline and phenazonium dye images, a hardening amount of a hardening agent selected from the group of compounds having the following general formulae:

wherein R R R and R are members selected from the group consisting of a hydrogen atom and lower alkyl groups, n represents a positive integer ranging from 1 to 7; X and X represent the carbon atoms necessary to complete a hydrogenated heterocyclic nucleus; and Y and Y represent the carbon atoms necessary to complete an aromatic nucleus of the benzene series.

6. A photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing in addition to a color former fast to diffusion capable of forming upon development with a primary amino developing agent, a dye image selected from the group consisting of azomethine, indoaniline and phenazonium dye images, a hardening amount of a hardening agent of the following formula:

7. A photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing in addition to a color former fast to diffusion capable of forming upon development with a primary amino agent, a dye image selected from the group consisting of azomethine, indoaniline and phenazonium dye images, a hardening amount of a hardening agent of the following formula:

8. A photo-sensitive element comprising a support and a gelatin silver halide emulsion coated thereon, said emulsion containing in addition to a color former fast to diffusion capable of forming upon development with a primary amino development agent, a dye image selected from the group consisting of azomethine, indoaniline and phenazonium dye images, a hardening amount of a hardening agent of the following formula:

IITH-C O-CHzCl 9. A photo-sensitive element comprising a support and coated thereon a gelatin silver halide emulsion layer and a gelatin layer, at least one of these gelatin layers containing a hardening amount of a bis-chloroacylamido hardening agent selected from the group of compounds having the following general formulae:

wherein R R R and R are members selected from the group consisting of a hydrogen atom and lower alkyl groups, n represents a positive integer ranging from 1 to 7; X and X represent the carbon atoms necessary to complete a hydrogenated heterocyclic nucleus; and Y and Y represent the carbon atoms necessary to complete an aromatic nucleus of the benzene series.

10. A photo-sensitive element comprising a support carrying a gelatin silver halide emulsion and a gelatin layer coated thereon, at least one of these gelatin layers containing a hardening amount of a compound having the following formula:

11. A photo-sensitive element comprising a support carrying a gelatin silver halide emulsion and a gelatin layer coated thereon, at least one of these gelatin layers containing a hardening amount of a compound having the following formula:

3,174,861 9 i@ 12. A photo-sensitive element comprising a support References fired by the Examiner carrying a gelatin silver halide emulsion and a gelatin UNITED STATES PATENTS layer coated thereon, at least one of these gelatin layers r containing a hardening amount of a compound having the 3/61 Levme 11 FOREIGN PATENTS following formula: 5

T 787,400 12/57 GreatBritain.

NORMAN G. TORCHIN, Primary Examiner.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2976152 *Dec 19, 1958Mar 21, 1961Gen Aniline & Film CorpPhotographic gelatin layers containing triazine hardeners
GB787400A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3881933 *Sep 17, 1973May 6, 1975Fuji Photo Film Co LtdLight-sensitive material undergoing little change of latent image formed therein
US3977881 *Jan 24, 1975Aug 31, 1976Ciba-Geigy AgAcylurea compounds
US4039520 *Mar 11, 1974Aug 2, 1977Konishiroku Photo Industry Co., Ltd.Gelatin hardening process
US5378591 *Jul 2, 1991Jan 3, 1995Eastman Kodak CompanyReversal color photographic material
US8105349Apr 18, 2005Jan 31, 2012Cook Medical Technologies LlcRemovable vena cava filter having primary struts for enhanced retrieval and delivery
Classifications
U.S. Classification430/621, 106/150.1, 430/623, 530/354, 106/155.21
International ClassificationG03C1/30
Cooperative ClassificationG03C1/30
European ClassificationG03C1/30