Патент USA US2405106код для вставки
July 30, 1946. J. A. WIDMER ET AL 2,405,106 PHOTOGRAPHIC FILTER AND ANTIHALATION LAYERS Filed 001;. 27, 1944 FIGJ. 13 BLUE scnsmv: EMULSION 14 ' ,FILTER LAYER CONTAINING A PYRROLE WW4; ‘2 mm? / DYE AND AN ANIONIC DISPERSING AGENT GREEN SENSITIVE EMULSION RED SENSITIVE EMULSION SUPPORT I j/ E MULSION 15-/“////////'//////:<_/~SUPPORT / ANTiHALATION LAYER CONTAINING A PYRROLE DYE AND AN ANIONIC DISPERSING AGENT JULES A.WIDMER BURT H. CARROLL INVENTORS WM BY @- MJmJa€~ A TTORNE Y Patented July 30, 1946 2,405,105 .UNITED STATES PATENT OFFICE 2,405,106 PHOTOGRAPHIC FILTER AND AN TIHALA TION LAYERS Jules Arthur Widmer, Oak Ridge, Tenn, and Burt H. Carroll, Rochester, N. Y., assignors to East man Kodak Company, Rochester, N. Y., a corpo ration of New Jersey Application October 27, 1944, Serial No. 560,626 5 Claims. (Cl. 95-8) 1 This invention relates to photography and par ticularly to ?lter and antihalation layers for CH3——h—CH=CH—OH=C———-C-CH3 H photographic elements. Dyes which can be used successfully, by direct dispersion in gelatin, for the preparation of ?lter 5 layers in contact with photographic emulsions are very rare. Such dyes must have good spectral CH3—C C 3X1?/—CHa CH3 I Bis-[1,2,11,5-tetra1nethyl pyrrole-(3)]-trimethinoyanine iodide /CH3 ——C—-CH3 H ‘ C—CH==CH \Na / CZH5 and Sprague U. S. Patents 2,268,798 and 2,298,731 1'5 C-CHs /N\ CH3 absorption properties and be readily dispersible in gelatin without crystallization. In addition, such dyes should bleach readily in photographic 10 processing baths, should not diffuse in multi-layer coatings, nor either sensitize or desensitize the emulsion layers with which they are in contact. It is difficult to ?nd dyes which ful?ll all of these requirements. The pyrrole dyes of Brooker \ / OH: —N __ \ CH3 C104 2-p-dimethylamino-styryl-l-ethyLB,3~dimethyl-4,5 benzoindolenium perchlorate are satisfactory in many respects for use in ?lter and antlhalation layers but do not ful?ll all of the necessary requirements. ___(CHs)2 We have found that many of the properties of 20 the pyrrole dyes of the Brooker and Sprague C \NfCH— H— patents may be improved by dispersing the dyes C 6 H 5 \CIO 4 CH with an excess of an anionic dispersing agent. Such dispersing agents include water-soluble salts of alkyl naphthalene sulfonates, water-sol 25 uble salts of esters of sulfoaliphatic dicarboxylic acids, and tannic acid. The accompanying drawing shows sectional views of photographic ?lm constructed accord CH 3 | (311115 [l-n-heptyl-2,5-dimethyl pyrrole- (8)]-[3,3-dimctl1y1~l phcnylindoleniue- (2)1-dimethincyanine perchlorate ——<oH@>. 30 The pyrrole dyes which We propose to use are I ing to our invention. /\ l I \N%-CH_OH——C—\N/ I polymethine dyes having a conjugated methine chain joining two heterocyclic nuclei, at least one / \ C2H5 of which nuclei is a pyrrole nucleus. In addition to the dyes disclosed in the Brooker and Sprague 35 U. S. Patents 2,268,798 and 2,298,731, the follow ing are suitable: I CH3—G=C—OH3 [l-ethy1-3,3~_dimethyl_ indole-(2)]-[2,3-di1nethyl pyrrocollne-(l)]-dimeth1ncyan1ne iodide / C—CH=CH—~CH=CH—~_ 40 \N/ / \I OZHB CH3‘\N/~CH3 I (Oetyl-l-octadecyl) GzHs Cl [3-ethyl—2-benzoxazole]-[2,5-dimethyl-l-heptyl pyrrole(3)1-dimethincynanine chloride 1 45 [3-cthyl-2<benzoxaz0le}-[l-eety1+octadecyl(mixture)-2,5-dimethyl pyrrole (3)1-tetramethincyanine io dide‘ The anionic dispersing agents which may be used with the pyrrole dyes include water-soluble salts of alkyl naphthalene sulfonates, such as Alkanol B sold by E. I. du Pont de Nemours 8.: 50 Company, Nekal A sold by General Dyestu? Cor poration, N ovonacco sold by National Aniline and Chemical Company, Inc., and Aerosol OS sold by American Cyanamid and Chemical Corporation. These compounds are generally sold as the so CGHE [3,3-dimethyl-l-phenyl-indolenino (2)]-[2,5-dimethyl-l phenyl pyrrole (3)1-dimethincyanine perchlorate 55 dium salts, for example, Aerosol OS is isopropyl naphthalene sodium sulfonate. Other Water soluble salts may, however, be used. 2,405,106 4 a 0 Another class of anionic dispersing agents which We may employ is that of the water-soluble the Aerosol OT and diffusion was found to be prevented. salts of esters of sulfo aliphatic dicarboxylic acids, Example 5 A coating was made as in Example 1 but using such as Aerosol AY and Aerosol OT sold by Amer Corporation. as the dye [1-n-heptyl-2,5-dimethylpyrrole (3) l Aerosol AY is the diamyl ester of sodium sulfo~ succinic acid and Aerosol CT is the dioctyl ester of sodium sulfosuccinic acid. .water-soluble salts other than the sodium salts may be used. . [3,3-dimethyl-l-phenylindolenine (2) l-dimethin ican Cyanamid and‘ Chemical cyanine perchlorate. The coating was found to be free from diffusion. Example 6 A third type of dispersing agent which we may 10 use for the pyrrole dyes is tannic acid or tannin. The pyrrole dye and the anionic dispersing agent used according to our invention should be chosen so that in equivalent quantities they form a dii?cultly soluble precipitate which is colloidally dispersed by an excess of the anionic material. This procedure has several advantages which per mit the use of pyrrole dyes not otherwise appli» cable to ?lter layers for multi-layer photographic elements. The true solubility of the pyrrole dye 20 in water can be reduced to an extremely low value, thus preventing diffusion while retaining good dispersability in colloidal form. In addition, many dyes which in a puri?ed state crystallize readily from gelatin layers so that their disper~ sion in sufficient tinctorial strength is poor, can be incorporated in gelatin with greatly reduced tendencies to crystallize. Further advantages are improved spectral absorption and increased fast ness to heat and moisture. Fading is usually re A coating was made as in Example 1 but using as the dye [l-ethyl-3,3-dimethyl-indole (2) l l2,3-dimethyl-pyrrccoline (1) l-dimethincyanine iodide. Diffusion of the dye was found to be con siderably reduced over a similar coating not con taining the dispersing agent. Example 7 Dyed gelatin for a coating was made as in EX ample 1 but omitting the dispersing agent and using as the dye [3-ethyl-2-benzoxazolel-[1 cetyl+octadecyl (mixture) -2,5-dimethyl pyrrole (3)l-tetramethincyanine iodide. Considerable fading of the dye resulted upon holding ‘this gel at 40° C. for four hours. Similar gels made with the addition of 0.1 to 0.2 gram of Aerosol OT, Alkanol B or Nekal A before the dye was added showed no fading of the dye in four hours at 40° C. It will be evident from a consideration of the tarded by the anionic material which presumably pyrr01e dyes described above that the dyes which combines with the pyrrole dyes to give an in we use may have either a pyrrole nucleus or an indole nucleus, substituted or unsubstituted, at soluble and more stable salt. the end of a polymethine chain and that the Our invention will be further illustrated by ref 35 opposite end of the polymethine chain may be erence to the following examples: attached either to a similar or dissimilar pyrrole Example 1 or indole nucleus or to an aromatic nucleus. Where we refer to “pyrrole nucleus” it is to be To 25 cc. of a 10% gelatin solution at pH 6.3 understood that we intend to include both pyrrole diluted with 20 cc. of water, there were added 50 4-0 and indole nuclei, the indole nucleus being con milligrams of [3-ethyl-2-benzoxazole]-[2,5-di methyl - 1 - heptylpyrrole (3) l-dimethincyanine chloride dissolved in 3 to 5 cc. of methyl alcohol. To this was added 4 cc. of 5% solution of Aerosol OT in a solution containing 50% methyl alcohol sidered a substituted pyrrole and the term, pyrrole nucleus, being generic to both pyrrole and indole nuclei. The amount of pyrrole dye used in ?lter and antihalation layers according to our invention will generally vary from about 50 milligrams to which when coated on a glass or ?lm support about 150 milligrams of dye in 25 cc. of 10% dried to give a clear yellow coating. The dye in gelatin solution. The dispersing agent is used in this coating did not diffuse when immersed in of the equivalent amount of the dye so tap water, whereas the dye-forming coating made 50 excess that an excess of the dispersing agent is present up in a similar manner by omitting the Aerosol in the dispersion. OT di?used almost completely into tap water in In the accompanying drawing, We have shown and 50% water. This yielded a heavy yellow gel 30 minutes. photographic elements coated according to our invention. As shown therein, Fig. 1 illustrates A coating was made in the same manner as 55 a multi-layer photographic element having a support l0 of cellulose acetate or other suitable in Example 1 but using as the dye [3,3-dimethyl material ?ltered with successive layers H, [2 1 - phenylindolenine (2) l-[2,5-dimethyl-1-phen and I3, sensitive respectively to the red, green ylpyrrole (3)1-dimethincyanine perchlorate. A and blue spectral regions. Between layers I2 clear orange coating was obtained which on mi croscopic examination was found to be free from 60 and I3, there is coated a layer M of gelatin con taining a pyrrole dye and an anionic dispersing crystallization. A similar coating Without the agent for the dye. Aerosol OT crystallized quite badly. Example 2 Example 3 Fig, 2 illustrates a photographic element com prising a support l5 of cellulose acetate or other A coating was made as in Example 1 but using 65 suitable material having on one side thereof a sensitive emulsion layer 16 and on the other side as the dye bis-[1,2,4,5-tetramethylpyrrole (3)] trimethincyanine iodide. This coating was found to be free from diffusion and crystallization of the dye. 70 Example 4 A coating was made as in Example 1 but using an antihalation layer ll containing pyrrole dye and an anionic dispersing agent according to our invention. While we have shown the use of our invention in ?lter and antihalation layers, it is obvious that the dispersion of dye and dispersing agent may be applied in other positions in the photographic element. For example, the dispersions may be dispersion of the dye was greatly improved by 75 used in overcoating layers or in ?lter layers be as the dye 2-p-dimethylamino-styryl-1-ethyl-3,3 dimethyl-‘lj-benzoindolenium perchlorate. The 2,405,106 tween any two of the emulsion layers of a multi layer element or between the emulsion layer and the support. Supports of glass, cellulose ester, synthetic resin, paper, metal, or other suitable material may be used. The examples and modi?cations included here in are to be considered as illustrative only and our invention is to be limited only by the scope of the appended claims. We claim: 1. A photographic element comprising a sup port having thereon a light-sensitive layer and a layer containing a colloidal dispersion of (l) a class consisting of water-soluble salts of alkyl naphthalene sulfonates, water-soluble salts of esters of sulfo aliphatic dicarlooxylic acids, and tannic acid. 3. A photographic element comprising a sup port having thereon a light-sensitive layer and a layer containing a colloidal dispersion of a poly methine dye having a conjugated methine chain joining two heterocyolic nuclei, at least one of which nuclei is a pyrrole nucleus, and an amount in excess of the equivalent amount of said dye of a water-soluble salt of an alkyl naphthalene sul fonate. ' polymethine dye having a conjugated methine 4. A photographic element comprising a sup~ chain joining two heterocyclic nuclei, at least 15 port having thereon a light-sensitive layer and a one of which nuclei is a pyrrole nucleus, and (2) an amount in excess of the equivalent amount of said dye of an anionic dispersing agent selected from the class consisting of water-solublasalts of alkyl naphthalene sulfonates, water-soluble salts of esters of sulfo aliphatic dicarboxylic acids, and tannic acid. 2. A photographic element comprising a sup port having thereon a plurality of layers sensi tive to different regions of the visible spectrum and between two of said layers a layer contain ing a colloidal dispersion of (1) a polymethine dye having a conjugated methine chain joining two heterocyclic nuclei, at least one of which layer containing a colloidal dispersion of a poly methine dye having a conjugated methine chain joining two heterocyclic nuclei, at least one of which nuclei is a pyrrole nuclus, and an amount in excess of the equivalent amount of said dye of a water-soluble salt of an ester of a sulfo ali phatic dicarboxylic acid. 5. A photographic element comprising a sup port having thereon a light-sensitive layer and a layer containing a colloidal dispersion of a polymethine dye having a conjugated methine chain joining two heterocyclic nuclei, at least one of which nuclei is a pyrrole nucleus, and an amount in excess of the equivalent amount of nuclei is a pyrrole nucleus, and (2) an amount in 30 said dye of tannic acid. excess of the equivalent amount of said dye of J ULES ARTHUR WIDMER. an anionic dispersing agent selected from the BURT H. CARROLL.