|Publication number||US3247127 A|
|Publication date||Apr 19, 1966|
|Filing date||Mar 27, 1961|
|Priority date||Apr 14, 1960|
|Also published as||US3440051|
|Publication number||US 3247127 A, US 3247127A, US-A-3247127, US3247127 A, US3247127A|
|Original Assignee||Eastman Kodak Co|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (6), Referenced by (40), Classifications (19)|
|External Links: USPTO, USPTO Assignment, Espacenet|
April 19, 1966 LIGHT-ABSORBING WATER-PERMEABLE COLLOID J. BAILEY 3,247,127
LAYER CONTAINING AN OXONOL DYE Filed March 27, 1961 6 E LATIN CONTAINING BIS [I-CARBOXWWETHYb HEXAHYDRO -3 "n- OCTYL-2,4-,6*TRIOXO 5- P'YRIMIDINE) PENTAMETH IN OXONOL Fig.1
LIEHT SENSITIVE SILVER HALIDE EMULSION LIGHT SENSITIVE SILVER HALIDE EMULSION /*GELATIN commons BIS E-BUTYL-S-CARBOXY' METHYLHEMHYDRO-ZfiB-TRIOXO s- F'YRIMIDINE) PENTAMETHINOXONQL SUPF-ORT LIGHT SENSITIVE K. SILVER HALIDE EMULSION SUPPORT GELATIN CONTAINING e|s[|-eum-3- CAR BOXYMETHYLHEXAHYDRO 2 3,6-
TRIOXO 5"PYR|MIDINE) PENTAMETHINONOXOL Joseph/Bailey IN VEN TOR.
BY 4. W/M
ATIDRNEY (A AGEN'J United States Patent 3,247,127 LIGHT-ABSORBING WATER-PERMEABLE COL- LOID LAYER CONTAINING AN OXONOL DYE Joseph Bailey, Wealdstone, Harrow, England, assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey Filed Mar. 27, 1961, Ser. No. 98,709 Claims priority, application Great Britain, Apr. 14, 1960, 13,379/ 60 9 Claims. (Cl. 252300) This invention relates to new dyes and more particularly to photographic elements containing these dyes in light-screening layers.
It is known that photographic elements require for many purposes to have light-screening substances incorporated therein. Such a light-screening substance may be in a layer overlying a light-sensitive emulsion or overlying two or more light-sensitive emulsions; or it may be in a light-sensitive emulsion for the purpose of modifying a light record in such emulsion or for protecting an overlying light-sensitive emulsion or emulsions from the action of light of wavelengths absorbed by such lightscreening substance; or it may be in a layer not containing a light-sensitive substance but arranged between two light-sensitive emulsions; or it may be in a layer serving as a backing on an element having one or more light-sensitive emulsions (for example to reduce halation) In particular, light-screening substances are often required (a) in overcoatings upon photographic elements to protect the light-sensitive emulsion or emulsions from the action of light which it is not desired to record, e.g., ultraviolet light in the case of still or moving pictures, especially color pictures, (b) in layers arranged between differentially color sensitized emulsions, e.g., to protect red and green sensitive emulsions from the action of blue light, and (c) in backings forming the socalled antihalation layers on either side of a transparent support carrying the light-sensitive emulsion or emulsions.
In most cases and especially where the element contains a color sensitized emulsion or color sensitized emulsions, it is particularly desirable to employ lightscreening substances which do not affect the general sensitivity or the color sensitivity of light-sensitive emulsions with which they may come into contact. It is also particularly desirable to employ light-screening substances which do not substantially diffuse from the layers or coatings in which they are incorporated, either during the manufacture of the element or on storing it or in photographically processing it. Finally it is generally necessary to employ light-screening substances which can readily be rendered ineifective, i.e., decolorized or. destroyed and removed prior to or during or after photographic processing. For many purpose it is particularly convenient to employ light-screening substances which are rendered ineffective by one of the photographic baths employed in processing the element after exposure, such as a photographic developing bath or fixing bath. The decoloration or destruction of the light-screening dye will hereinafter be referred to as bleaching.
Numerous substances have been employed as lightscreening materials for the purposes indicated above. Among the dyes used are the oxonol dyes. Oxonol dyes known in the past have not absorbed light of the wavelength desired. Previously known oxonol dye-mordant combinations, however, which are sufiiciently nonwandering to use in layers in contact with emulsion layers,
are bleached only with difiiculty or not at all during normal processing of the film. Those known combinations which bleach more easily are not sufficiently nonwandering so the dye migrates to the emulsion layers with a consequent deleterious elfect upon the sensitometric properties of the film. In some instances where the lightscreening dye has been mordanted to make it sufficiently nonwandering, the dye does not bleach satisfactorily in the processing baths and it has been necessary to remove the light-screening layer itself from the photographic element to eliminate the unwanted residual dye.
It is therefore an object of my invention to provide a new class of symmetrical oxonol dyes which have their maximum absorption of light at the wavelength desired.
Another object is to provide new symmetrical acid oxonol dyes which are readily mordanted in light-screening layers so that they will not diffuse into adjacent emulsion layers and dyes which are readily bleached by conventional processing solutions without removing the lightscreening layer containing them.
Another object is to provide a new class of light-screen ing filter layers which are valuable for use in photographic elements as interlayers between two sensitive silver halide emulsion layers, between the support and a sensitive silver halide emulsion layer, as a layer over a sensitive silver halide layer or as an antihalation layer behind the support.
Another object is to provide a method for preparing new symmetrical oxonol dyes.
Still other objects will become apparent from the following specification and claims.
I have found that the above objects are accomplished by using symmetrical oxonol dyes represented by the following formula:
wherein Z represents the nonmetallic atoms necessary to complete a l-carboxyalkyl-3hydrocarbon substituted hexahydro-2,4,6-trioxo-5-pyrimidine nucleus and n is an integer of: from 1 to 3.
Particularly advantageous dyes of my invention may be represented by the following formula:
wherein R is a carboxyalkyl group in which the carboxy substituent is attached to an alkyl group having from 1 to 2 carbon atoms such as methyl and ethyl; R is a member selected from the class consisting of an alkyl group having from 1 to 8 carbon atoms, such as methyl, benzyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, hexyl, octyl, cyclohexyl, etc., an aryl group, such as phenyl, Z-methylphenyl, Z-methoxyphenyl, 2,4-dimethylphenyl, etc.; n is an integer of from 1 to 3; X is a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl, etc., such that not more than one X is an alkyl group.
My dyes are valuable for use in photographic lightsensitive materials employing one or more sensitive silver halide layers. The dyes can be used to make light-screening layers including antihalation layers with or without dyes of other classes and can be incorporated readily in colloidal binders used for forming such layers. They are especially useful in gelatin layers lying adjacent to silver halide layers, since the dyes can be mordanted with organic polymeric substances to form excellent nonwandering characteristics in gelatin While the dyes can be readily bleached without the need for removing the layers containing them. Bleaching of the dyes occurs when the layer is treated with alkaline solutions containing sodium sulfite such as photographic developing solutions.
My dyes can be m-ordanted in layers coated in contact with light-sensitive silver halide emulsion layers since the dyes have very good stability at the pH of most sensitive silver halide emulsions (about 6.3) and have little or no undesirable effect on the silver halide. Consequently, the dyes may be used as light-screening dyes in layers coated directly on top of sensitive silver halide emulsion layers or between two sensitive silver halide emulsion layers or between the support and a sensitive silver halide emulsion layer or on the back of the support as an antihalation layer.
Representative dyes of my invention and their preparation are illustrated by the following examples which are not intended to limit my invention.
Example 1 .Bis 1 -n-butyl-3-carb0xymethy lhexa'lzydro- 2,4,6-trix0-5-pyrimidine pentamethinoxonol HO 0 C C Hz 1-n-butyl-3-carboxymethylbarbituric acid (3.6 grams) glutaconic aldehyde dianilide hydrochloride (2.13 grams), ethanol (30 cc.) and triethylamine (8.4 cc.) were heated on the steam bath for 20 minutes. The dye solution was chilled and acidified with concentrated hydrochloric acid (12 cc.) and the solution was poured into water (750 cc.). The precipitated dye was collected, washed with Water and dried. The product which weighed 3 grams (73%) melted at 88 C.
The dye in water had an absorption maximum at 590 m Analysis fOr C25H30N4010:
| C l N Cald 55. 0% 5. 10. 2% Found. 55. 3% 6. 2% 10. 05%
Example 2Bis(1 -carb0xymethylhexahydro-3-n-0ctyl- 2,4,6 tri0x0-5-pyrimidine) pentamethinoxo nol Analysis for C 3H N4O10I Cald Found Example 3 .Bis(1 -carb0xymetlzyl-3-cycl0hexylhexa'hyrim-2,4, 6 -triox0-5 pyrimidine pentamefh inoxonol HOOC-(IJHZ H(|) ?H2-COOH NCO CN OC\ /C=CHOH=CHCH=CHO\ CO N-oo CtHn CoHn Prepared similarly to Example 1 using a proportional amount of 1-carboxyrnethyl-3-cyclohexylbarbituric acid instead of 1-n-butyl-3-car-boxymethylbarbituric acid. The dye was obtained in yield, it melted at and had an absorption maximum in ethanol at 592 m Analysis for C19H3N401QI Calcd-N, Found- N, 9.2%.
Example 4 .Bz's( 1 -carb0xymethy lhexalzydr0-3-phenyl- 2,4,6-fri0x0-5-pyrimidine pent'amethinoxonol This dye was prepared similarly to Example 1 using a proportional amount of 1-carboxymethyl-3-phenylbarbituric acid instead of 1-n-butyl-3-carboxyrnethylbarbituric acid. The dye was obtained in 63% yield, it melted at and had an absorption maximum in ethanol at 591 m Analysis for C H N O Cald 9. 6% Found Example 5.Bis(1-carb0xymetlzylhexahydr0-3-n-octyl- 2,4,6-trioxo-5-pyrimidine) -3-methylpentamethinoxonol This dye was prepared similarly to Example 2 using 1- anilino-S-anilo-3-methyl-1,3-pentadiene HBr in place of glutaconicaldehyde dianilide HCl. The dye was obtained in 86% yield, it had an absorption maximum in ethanol at 614 m Example 6 .Bis (.1 -carb0xymethy lhexahydr0-3-n-0cty 2,4,6 -tri0x0-5 pyrimidine) trime thinoxonol HOOCLCHZ HO CH2.COOH NC 0 as CO C=CHCH=CHC CO NC O BC-N CaHir $51117 5 Analysis for C H44N O Z C H N Cald 58. 9% 7. 8. 9% Found 60. 0% 7. 15% 9.
Example 7.Bis(1-n-butyl-3-carb0xymethylhexahydro- 2,4,6-trioxo-5-pyrimidine) trimethinoxo-nol Prepared similarly to Example 6 using a proportional amount of l-n-butyl-3-carboxymethylbarbituric acid in place of 1-carboxymethyl-3-n-octylbarbituric acid. The dye was obtained in 60% yield, melted at 66 and had an absorption maximum ethanol at 493 mp.
Analysis for C H N O H 0:
Cald 51. 3% 5. 6% 10. 4% Found- 51. 0% 5. 9% 10. 1%
Example 8.Bis(1-carb0xymethyl-3-cycl0hexyllzexahydr0-2,4,6-trioxo-S-pyrimidine) trimethz'noxono-l Prepared similarly to Example 6 using a proportional amount of l-carboxyrnethyl-Ii-cyclohexylbarbituric acid in place of 1-carboxymethyl-3-n-octylbarbituric acid. The dye was obtained in 63% yield, melted at 170 and had an absorption maximum in ethanol at 494 m Analysis for C27H32N4010: CaldN, 9.
Example 9.--Bis(l -carboxymethy lhexahydro-S-n-octyl- 2,4,6-triox0-5-pyrimidine) methinoxonol l-carboxymethyl-B-n-octylbarbituric acid (6 g.), ethyl orthofor-mate (3 cc.), pyridine (15 cc.) were heated under reflux for 30 minutes. The reaction mixture was cooled, diluted with water (100 cc.), acidified with concentrated hydrochloric acid, cooled and the product collected by filtration. It was dried and recrystallized from ethyl acetate. The dye weighed 2.5 g. (41%), melted at 173 C. and had an absorption'maximum in methanol at 415 m Analysis for C2gH42N4010:
C H N iliif.IIIIIIIIIIIIIIIIIIII 5533;; 32353 31 i3;
The following are further examples of compounds according to the present invention.
Found Example J0.Bis(1-tertiarybutyl-S-carboxymethflhexahydro-2,4,6-tri0x0-5-pyrimidine) penfamethinoxonol Example 1 1 .--Bis(1 -carb0xymethyl-3-n-hexy lhexahydr0 2,4,6-tri0x0-5pyrimidine) pen-tamethinoxonol Example 12 .Bis(1-benzyl-3-carb0xymethylhexahydro- 2,4,6-triox0-5-pyrimidine pentamethinoxonol Example 13.Bis( 1-carboxymethyllzexahydr0-3-0-metlzoxyphenyl-2,4,6-tri0x0-5-pyrimidine) pentamethinoxonol Example 14.Bz's(1-tertimybutyl-3-carboxymethylhexahydr0-2,4,6-tri0x0-5-pyrim idl'ne) trimet'hinoxonol Example 15.Bz's(I-z:arboxymezhyl-3-n-hexylhexalzyalro 2,4,6-trioxo-5-pyrimidine) trimeth inoxonol Example 16.Bis( 1 -benzyl-3-carb0xymetlzylhexalzydro- 2,4,6-trioxo-S-pyrimidine) trimethinoxon'ol Example 17.Bis(1-carb0xymethylhexahydr0-3-0-methoxyphenyl-2,4,6-trioxo-S-pyrimidine) trimethinoxonol Example 18.Bis(1 -n-butyl-3-carb oxymethylhexalzydro- 2,4,6 -tri0x0-5 -pyrimidine) methinoxonol Example 1 9.Bis(1-tertiarybutyl-3-carb0xymethylhexahydro-2,4,6-trioxo-S-pyrimidine) methinoxonol The intermediates used in preparing my dyes were synthesized according to the following procedures which are typical and will illustrate the methods used to prepare intermediates for other dyes of my invention.
N ETHOXYCARBON'Y LMETHYLN -N-OCTYLUREA C2H5OOC'CH2'NH'CONHC3H17 Ethoxycarbonylmethyl isocyanate (Ann. 1948, 5 62, 76) (17.5 grams) in benzene (25 cc.) was treated with noctylamine (17.5 grams) in benzene (25 cc.). There was a temperature rise on mixing and the solution was maintained at room temperature overnight. The solvent was pound using a proportional amount of n-butylamine in place of n-octylamine. It yield) was obtained as very low melting colourless needles.
Analysis for C H N O Cald-N, 13.9%. N, 13.3%.
N-ETHOXYCARBONYLMETHYL-N-PHENYLUREA C2H5OOC CH2 NH C5H5 It was obtained similarly to the above using a propor tional amount of aniline in place of n-octylamine. It
(72% yield) was obtained as colourless needles, M.P. 108109 C.
N-CYCLOHEXYL-N-ETHOXYCARBONYLUREA C H OOC-CH 'NH-CONH 0 H It was obtained similarly to the above using a proportional amount of cyclohexylamine in place of n-octylaminep It (70% yield) was obtained as long colourless needles, M.P. 121122.
Other intermediates according to the invention include:
Found-- N-tertiarybutyl-N-ethoxycarbonylrnethylurea N-ethoxycarbonylmethyl-N-n-hexylurea N-benzyl-N'-ethoxycarbonylmethylurea N-ethoxycarbonylmethyl-N'-o-methoxyphenylurea Analysis for C H25O5N2:
1 O i H N Oald 58. 9% 8. 8. 6% Found. 57. 8. 1% 8. 35%
l-n-BUTYL-3 ETHOXYCARBONYLMETHYL- BARBITURIC ACID Prepared similarly to the above intermediate. It was obtained in 52% yield as a colourless viscous oil, B.P. 161163/O.2 mm.
1 ETHOXYCARBONYLMETHYL-3-PHENYL- BARBITURJC ACID Prepared similarly to the above intermediate. It was obtained in 63% yield as a pale yellow viscous oil, B.P. 216218/O.5 mm.
l-CYCLOHEXYL-S-ETH OXYCARBONYLMETHYL- BARBITURIC ACID I Cs n Prepared similarly to the above intermediate. It was obtained in 83% yield as a pale yellow viscous oil, B1. l78-l8()/0.2 mm.
Other intermediates according to the invention include:
l-tertiarybutyl-3-ethoxycarbonylmethylbarbituric acid 1-ethoxycarbonylmethyl-3-n-hexylbarbituric acid 1-benzyl-3-ethoxycarbonylmethylbarbituric .acid
l-ethoxycarbonylmethyl 3 o methoxyphenylbarbituric acid l-CARBOXYMETHYL-3-n-OCTYLBARBITURIC ACID Noo CH2 NC6 l-ethoxyc'arbonylmethyl-3-octylbarbituric acid (16 grams) was treated with aqueous sodium hydroxide (10 cc., 40%) in water (40 cc.). The solution was heated 011 the steam bath for 4 hours. Then the reaction mixture was chilled and acidified with concentrated hydrochloric acid. The separated oil was extracted with benzene. The benzene solution was concentrated and solid product was obtained by warming the residual gum with petroleum ether (B.P. 4060). The product was collected and recrystallized from petroleum ether (B.P. -100 C.) as colourless shiny plates. The product weighed 9 grams (62%) and melted at ll7.5l18.5 C.
Analysis for C H O N Cald 5s. 4% 7. 4% 9. 4% Found. 56.3% 7. 6% 9. 2%
1-n-BUTYL-3-CARBOXYMETHYLBARBITURIC ACID HOOOEH:
N-CQ 0o CH2 N-CO To a solution of potassium hydroxide (6.65 grams) in methanol (75 cc.) was added 1-n-butyl-3-ethoxycarbonylmethylbarbituric acid (13.5 grams). The mixture was maintained overnight at room temperature when the solid potassium salt of the product precipitated. It was collected by filtration and washed with methanol. It was dissolved in water and the solution acidified with hydrochloric acid. The separated oil was extracted with benzene. The benzene solution was concentrated and the residual oil purified by dissolution in ethyl acetate and treating the solution by the dropwise addition of petroluem either (B.P. 6080) until the product began to precipitate. After chilling, the colourless crystals were collected. The product weighed 4 grams (33%) and melted at 7375 C.
Analysis for C H O N o I H l N Cald 49. 6% 5 8% 11.6% Found 50. 0% 6 0% 11.35%
1CARBOXYMETHYL3PHENYLBARBITURIC ACID H O C CH2 NCg Prepared in a similar way to l-n-butyl-S-carboxymethylbarbituric acid. It was obtained in 43% yield as colourless crystals, M.P. 100.
Analysis for C H N O i C H N Cald 55. 0% 3. 8% 10. 7% Found 54. 3% 4. 5% 10. 6%
1-CARBOXYMETHYL-3-CYCLOHEXYLBARB I- TURIC ACID Anaylsis for C H N O l G l H l N Cald 53. 7% 6. 0% 10. 4% Found. 53. 6% 5. 85% 10.7%
Other intermediates according to the invention include:
1-tertiarybutyl-3=carboxymell1ylbarbituric acid l-carboxymethyl-B-n-hexylbanbituric acid 1-bcnzyl-3-carboxyrnethylbanbituric acid l-carboxymethyl-3-o-methoxyphenylbarbituric acid The light-screening layers of my invention are prepared by coating on the photognaphic element or on its support, by methods well known in the art, a water solution of the dye, a hydrophilic colloid binder and a coating aid such as saponin. In addition to these materials it is advantageous t add a basic mordant to this solution to render the acid dye nonwandering. For most purposes it is desirable to add agents to harden the colloidal binder material so that the light-screening layer will remain intact in the photographic element during and following the processing operation. The pH of the coating solution is adjusted when necessary to a level that is compatible with the light-sensitive emulsion layer by the usual methods.
The proportions of dye, colloidal binder, mordant, hardener, coating aid used in making my light-screening layers may be varied over wide ranges and will depend upon the specific requirements of the photographic element being produced. The methods used to determine the optimum composition are well known in the art and need not be described here.
The light-sensitive layer or layers and the light-screen ing layer or layers of the photographic element may be coated on any suitable support material used in photography such as cellulose nitrate, cellulose acetate, synthetic resin, paper, etc. i
Hydrophilic colloidal materials used as binders include collodion, gum arabic, cellulose ester derivatives such as alkyl esters of carboxylated cellulose, hydroxy ethyl cellulose, carboxy methyl hyd-roxy ethyl cellulose, synthetic l 0 resins, such as the amphoteric copolymers described by Cl-avier et al. in US. Patent 2,949,442, issued August 16, 1960, polyvinyl alcohol, and others well known in the art. The above-mentioned amphoteric copolymers are made by polymerizing the monomer having the formula:
CH CR C O OH wherein R represents an atom of hydrogen or a methyl group, and a salt of a compound having the general formula:
CH =(IJ R wherein R has the above-mentioned meaning, such as an allylamine salt. These monomers can further be polymerized with a third unsaturated monomer in an amount of 0 to 20% of the total monomer used, such as an ethylene monomer that is copolymerizable with the two principal monomers. The third monomer may contain neither a basic group nor an acid group and may, for example, be vinyl acetate, vinyl chloride, acrylonitrile, methacrylonitrile, styrene, acrylates, methacrylates, acrylamide, methacrylamide, etc. Examples of these polymeric gelatin substitutes are copolymers of allylamine and methacrylic acid; copolymers of allylamine, acrylic acid and acrylamide; hydrolyzed copolyrners of allylamine, methacrylic acid and vinyl acetate; copolymers of allylamine, acrylic acid and styrene; the copolymer of allylamine, methacrylic acid and acrylonitrile; etc.
My dyes are generally added to the water-permeable colloidal binder in water solution. In some instances it may be advantageous to form an alkali metal salt of the dye by dissolving the dye in a dilute aqueous alkali metal carbonate solution, for example. Usually a coating aid, such as saponin, is added to the dyed colloidal suspension before coating it as a layer on the photographic element. The dyes are advantageously mordanted with a suitable basic mord'ant added to the colloidal suspension before coating.
Basic mordants that may be used include the basic mordants described by Minsk in US. 2382, 156, issued April 14, 1959, prepared by condensing a polyvinyloxo-compound such as a polyacrolein, a poly-'y-methylacrolein, a polyvinyl alkyl ketone, such as polyvinyl methyl ketone, polyvinyl ethyl ketone, polyvinyl propyl ketone, polyvinyl butyl ketone, etc., or certain copolymers containing acrolein, methacrolein, or said vinyl alkyl ketone components, for example, 1 to 1 molar ratio copolymers of these components with styrene or alkyl methacrylates wherein the alkyl group contains from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, or butyl methacrylates in the proportions from about .25 to 5 parts by weight of the said polymeric oXo-cornpound with one part by weight of an aminoguanidine compound such as aminoguanidine bicarbonate, aminoguanidine acetate, aminoguanidine butynate, etc.; the reaction prodnets of polyvinyl-sulfonates with C-aminopyridines of Reynolds et al. US. 2,768,078, issued October 23, 1956, prepared by reacting alkyl and aryl polyvinyl sulfonates prepared as described in our patents US. 2,531,468 and US. 2,531,469, both dated November 28, 1950, under controlled conditions with C-aminopyridines or alkyl group substituted C-aminopyridines such as 2-aminopyridine, 4-aminopyridine, the aminopicolines such as 2- amino-3-methy-lpyridine, 2-amino4-methylpyi-ridine, 2- amino-S-methylpyridine, 2-amino-6-methylpyridine and corresponding 4-aminomethyl derivatives which react in this reaction in exactly the same way, 2-arnino-6-ethylpyridine, 2-amino-6-bntylpyridine, 2-amino-6-amylpyridine, etc., the various aminolutidines such as, for example, 4-am-ino-2,6-dimethylpyridine and the various aminocollidines such as, for example, 2-amino-3-ethyl-4-methylpyridine, etc.; the dialkylaminoalkyl esters or dialky1 aminoalkylamino amides, e.g., such as those described by Carroll et al. U.S. Patent 2,675,316, issued April 13, 1954, prepared by reacting addition polymers containing carboxyl groups with a basic dialkylamino compound, for example, N-dialkyl amine ethyl esters of polymers or copolymers containing carboxyl groups; the addition type polymers containing periodically occurring quaternary groups of Sprague et al. U.S. 2,548,564, issued April 10, 1951, including quaternary ammonium salts of vinyl substituted azines such as vinylpyridine and its homologs such as vinylquinoline, vinylacridine, and vinyl derivatives of other six-membered heterocyclic ring compounds containing hydrogen atoms. These addition polymers include 2-vinylpyridine polymer metho-p-toluenesulfonate, 4-vinylpyridine polymer metho-p-toluenesulfonate.
Hardening materials that may be used to advantage include such hardening agents as formaldehyde; a halogensubstit-uted aliphatic acid such as mucobromic acid as described in White, U.S. Patent 2,080,019, issued May 11, 1937; a compound having a plurality of acid anhydride groups such as 7,8-diphenylbicyclo (2,2,2)-7-octene- 2,3,5,6-tetra-carboxylic dianhydride, or a dicarboxylic or a disulfonic acid chloride such as terephthaloyl chloride or naphthalene-1,5-disulfonyl chloride as described in Allen and Carroll, U.S. Patents 2,725,294 and 2,725,295, both issued November 29, 1955; a cyclic 1,2-diketone such as cyclopentane-LZ-dione as described in Allen and Byers, U.S. Patent 2,725,305, issued November 29, 1955; 1a bisester iof methane-sulfonic acid such as l,2-di(meth- |anesulfonoxy)-ethane as described in Allen and Laakso, U.S. Patent 2,726,162, issued December 6, 1955; 1,3-dihydroxymethylbenzimidazol-Z, one as described in July, Knott and Pollak, U.S. Patent 2,732,316, issued January 24, 1956; a dia-ldehyde or a sodium bisulfite derivative thereof, the aldehyde groups of which are separated by 2-3 carbon atoms, such as fl-methyl glutaraldehyde bis-sodium bisulfite as described in Allen and Burness, U.S. patent application Serial No. 556,031, filed December 29, 1955, and now abandoned; a bis-aziridine carboxamide such as itrimet hylene bis(1-aziridine oarboxarnide) as described in Allen and Webster, U.S. Patent 2,950,197, issued August 23, 1960; or 2,3-dihydroxydioxane as described in Jeffreys, U.S. Patent 2,870,013, issued January 20, 1959.
The photographic element utilizing my light-screening layers have light-sensitive emulsion layers containing silver chloride, silver bromide, silver chlorobromide, silver iodide, silver bromoiodide, silver chlorobromoiodide, etc., as the light-sensitive material. Any light-sensitive silver halide emulsion layers may be used in these photographic elements. The silver halide emulsion may be sensitized by any of the sensitizers commonly used to produce the desired sensitometric characteristics.
My invention is further illustrated by the following examples describing the preparation of photographic elements containing my light-screening layers.
Example 20 An aqueous solution was made up which contained 4.54 g. of gelatin, .91 g. of poly(or-methyl allyl-N-guanidylketimine), .153 g. of saponin, and .302 g. of bis(1- butyl 3 carboxymethylhexahydro 2,4,6 trioxo 5- pyrimidine) pentamethinoxonol to a total weight of 150 g. at a pH of 6.1. This solution was coated on clear cellulose acetate film support at 4.6 g. per sq. ft. The resulting coating was overcoated with a fine-grained silver chlorobromide emulsion with panchromatic sensitization at a silver coverage at 257 milligrams of silver per sq. ft. A control was coated on clear support. These film samples were exposed in an intensity scale sensitometer, then developed for 6 minutes in a developer having the composition:
G. p-Methylaminophenol sulfate 2.2 Sodium sulfite (desiccated) 72.0 Hydroquinone 8.0
G. Sodium carbonate (anhydrous) 48.0 Potassium bromide 4.0
Water to 1 liter.
fixed for 10 minutes in a fixing bath having the formula:
Sodium thios-ulfate g 240.0 Sodium sulfite (desiccated) g 15.0 Acetic acid, 28% cc 48.0 Boric acid crystals g 7.5 Potassium alum g 150.0
Water to 1 liter.
Washed and dried.
The following tables gives the halation latitude determined for these film samples as the increase over normal required in log E exposure to give a halation density of 0:1 in the center of a 0.008 inch wide unexposed line.
Halation Latitude Clear Blue Green Red Control 78 51 71 53 Film sample provided with lightscreening layer 1.67 .86 1.74 2.36
Example 21 0.5 gram of the dye of Example 2 was dissolved in 1% aqueous sodium carbonate and added to a 5% gelatin solution containing 0.5 gram polyvinylpyridinium methop-toluenesulfonate. The pH of the solution was adjusted to 6.5. This dyed gelatin solution was then coated on top of a sensitive silver halide emulsion of the kind used for Xray photography at the rate of 25.5 mg. of dye per square foot. Two such coated materials were made from exactly the same emulsion and dyed gelatin solution and measurements made on the products are shown below as A and B, along with the measurements on the same prodnet but omitting the dye from the gelatin.
The three products were exposed, developed in the developer of Example 17 for 4 minutes and fixed in a hypo solution of Example 17 in the usual way and washed. The dyed layers were completely bleached by this treatment. In the following table, the column headed Safety Factor, are relative measurements of the inverse of the effective sensitivity of the material when exposed to the red component of the light transmitted by a Wratten 68 Darkroom Safelight, which contains an amber coloured filter transmitting light in the range of 570 to 700 m with a maximum transmission at a wavelength of 595 III/1.. The Safety Factor was calculated as the antilogarithm of the inverse of the logarithm of the speed measured as the exposure required to give a density of 0.2 above the fog density. 7
Thus the Safety Factor to Wratten 6B Safelight for the photographic element protected with my light-screening layer was about twice as high as it was for the control.
The accompanying drawing containing FIGS. 1, 2 and 13 3 still further illustrates my invention. FIGS. 1, 2, and 3 represent greatly enlarged cross-sectional views of lightsensitive photographic elements containing my light-absorbing water-permeable colloid layers.
FIG. 1 shows light-screening layer 10 consisting of gelatin containing bis(l-carboxymethylhexahydro-3-noctyl-2,4,6-trioxo-S-pyrimidine)pentamethinoxonol mordanted with polyvinylpyridinium metho-p-toluenesulfonate coated over light-sensitive silver halide emulsion layer 11 which is coated on support 12.
FIG. 2 shows light-sensitive silver halide emulsion layer 13 coated over light-screening layer 14 consisting of gelatin containing bis(1-butyl-3-carboxymethylhexahydro-2,4, 6-trioxo-5-pyrimidine)pentamethinoxonol mordanted with a-methyl allyl-N-guanidylketimine coated over support 15.
FIG. 3 shows light-sensitive silver halide emulsion layer 16 coated on support 17 bearing antihalation backing layer 18 consisting of gelatin containing bis(1-butyl-3-carboxymethylhexahydro-2,4,6-trioxopyrimidine)pentamethinoxonol mordanted with a-methyl allyl-N-guanidylketimine.
The symmetrical, acid oxonol dyes of my invention are valuable for preparing light-screening layers .for making light-sensitive photographic elements containing silver halide emulsion layers. The light-screening layers containing my dyes are used to advantage either over the light-sensitive silver halide emulsion layers, between the light-sensitive silver halide emulsion layer and the support, between two difierent light-sensitive layers, or as an antihalation backing layer. My dyes are characterized by having maximum light absorption at desirable wavelengths. They are further characterized by being readily mordanted with basic mordants so that they will not wander into light-sensitive silver halide emulsion layers coated directly in contact with them and yet they are readily bleached in the light-screening layer by conventional processing solutions which contain. sodium sulfite. Furthermore, my dyes are characterized by having very good stability at the pH of most sensitive silver halide emulsions (about 6.3) and have little or no undesirable eifect on the sensitivity of the silver halide emulsion layer even when they are used in direct contact with them.
The invention has been described in detail with particular reference to preferred embodiments thereof but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.
1. A light-absorbing water-permeable colloid layer containing a light-absorbing dye as a light-screening sub stance having the formula:
wherein R is a carboxyalkyl group in which the alkyl group has from 1 to 2 carbon atoms; R is a member se- 1 4 lected from the class consisting of an alkyl group having from 1 to 8 carbon atoms and an aryl group; n is an integer of from 1 to 3; X is a member selected from the class consisting of a hydrogen atom and an alkyl group having from 1 to 4 carbon atoms such that not more than one X is an alkyl group, in an amount sufiicient to impart light screening properties to the said colloid layer.
2. The light-absorbing layer of claim 1 containing a basic mordant for the said dye.
3. The light-absorbing layer of claim 1 containing poly- (ct-methyl allyl-N-guanidylketirnine) as a basic mordant for said dye.
4. The light-absorbing layer of claim 1 containing polyvinylpyridinium metho-p-toluenesulfonate as a basic mordant for said dye.
5. A light-absorbing water-permeable gelatin layer containing the light-absorbing dye bis(1-n-butyl-3-carboxy methylhexahydro-2,4,6-trioxo-5 pyrimidiue)pentamethinoxonol as a light-screening substance, in an amount sufficient to impart light screening properties to the said gelatin layer.
6. A light-absorbing water-permeable gelatin layer containing the light-absorbing dye bis(l-carboxymethylhexahydro-3 n octyl-2,4,6-trioxo-5-pyrimidine)pentamethinoxonol as light-screening substance, in an amount sufficient to impart light screening properties to the said gelatin layer.
7. A light-absorbing water-permeable gelatin layer containing the light-absorbing dye bis(l-carboxymethylhexahydro 3 phenyl-2,4,6-trioxo-5-pyrimidine)pentamethinoxonol as a light-screening substance, in an amount suflicient to impart light screening properties to the said gelatin layer.
8. A light-absorbing water-permeable gelatin layer containing the light-absorbing dye bis(1-n-butyl-3-carboxymethylhexahydro 2,4,6 trioxo-S-pyn'midnefirimethinoxonol as a light-screening substance, in an amount sulficient to impart light screening properties to the said gelatin layer.
9. A light-absorbing water-permeable gelatin layer containing the light-absorbing dye bis(1-carboxymethyl-3- cyclohexylhexahydro 2,4, 6- trioxo 5 pyrimidine)trimethinoxonol as a light-screening substance, in an amount sufiicient to impart light screening properties to the said gelatin layer.
References Cited by the Examiner UNITED STATES PATENTS 2,345,193 3/1944 Gaspar 260-2402 2,533,206 12/1950 Dent et a1. 260240.2 2,533,472 12/1950 Keyes et a1. 9684 2,534,654 12/1950 Barnes 252300 2,611,698 9/1952 Jennen 9684 2,614,940 10/1952 Freyermuth et a1. 252300 JULIUS GREENWALD, Primary Examiner. PHILIP E. MANGAN, Examiner.
W. C. GILLIS, JR., R. D. LOVERING,
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US2345193 *||May 6, 1939||Mar 28, 1944||Chromogen Inc||Organic dye|
|US2533206 *||Feb 24, 1949||Dec 12, 1950||Eastman Kodak Co||Process for preparing oxonol dyes|
|US2533472 *||Jan 17, 1947||Dec 12, 1950||Eastman Kodak Co||Unsymmetrical oxonol filter and antihalation dyes|
|US2534654 *||Jan 11, 1946||Dec 19, 1950||Polaroid Corp||Ultraviolet absorbing filter|
|US2611698 *||Aug 4, 1947||Sep 23, 1952||Gevaert Photo Prod Nv||Colored photographic layer|
|US2614940 *||Dec 31, 1948||Oct 21, 1952||Gen Aniline & Film Corp||Ultraviolet light absorbing film|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US3480436 *||Aug 29, 1966||Nov 25, 1969||Eastman Kodak Co||Antihalation compositions containing pentamethine oxonol dyes in aromatic alcohols|
|US3511660 *||Oct 18, 1966||May 12, 1970||Eastman Kodak Co||Antihalation backing for photographic silver halide recording elements|
|US3652284 *||Nov 4, 1968||Mar 28, 1972||Eastman Kodak Co||Photographic silver halide emulsion containing a methine dye|
|US3653905 *||May 13, 1969||Apr 4, 1972||Agfa Gevaert Nv||Oxonol dyes in filter and anti-halation layers|
|US4078933 *||Mar 15, 1977||Mar 14, 1978||Fuji Photo Film Co., Ltd.||Silver halide photographic light-sensitive element containing dye|
|US4587195 *||Apr 10, 1985||May 6, 1986||Konishiroku Photo Industry Co., Ltd.||Method of processing silver halide photographic light-sensitive material|
|US4746598 *||Feb 26, 1987||May 24, 1988||Konishiroku Photo Industry Co., Ltd.||Processing of color photographic material utilizing a stabilizing solution after fixing|
|US4770984 *||Jul 8, 1987||Sep 13, 1988||Agfa-Gevaert, N.V.||Color photographic film element with blue and yellow antihalation layers|
|US4895786 *||May 11, 1989||Jan 23, 1990||Konishiroku Photo Industry Co., Ltd.||Process for stabilizing photosensitive materials to replace exhaustive washing|
|US5035986 *||Jan 30, 1989||Jul 30, 1991||Fuji Photo Film Co., Ltd.||Silver halide color photographic material|
|US5139930 *||Feb 3, 1992||Aug 18, 1992||Konishiroku Photo Industry Co., Ltd.||Silver halide photographic light-sensitive material|
|US5204236 *||Feb 27, 1992||Apr 20, 1993||Konica Corporation||Silver halide photographic materials|
|US5314796 *||Mar 26, 1993||May 24, 1994||Konica Corporation||Silver halide color photographic light sensitive material|
|US5354646 *||Mar 7, 1994||Oct 11, 1994||Konishiroku Photo Industry Co., Ltd.||Method capable of rapidly processing a silver halide color photographic light-sensitive material|
|US5451494 *||Jul 22, 1994||Sep 19, 1995||Eastman Kodak Company||Photographic elements containing acyl substituted oxonol dyes|
|US5459265 *||Mar 23, 1994||Oct 17, 1995||Fuji Photo Film Co., Ltd.||Silver halide photographic light-sensitive material|
|US5561028 *||Jun 2, 1995||Oct 1, 1996||Mitsubishi Paper Mills Limited||Silver halide photographic photosensitive material|
|US5922523 *||Nov 30, 1995||Jul 13, 1999||Eastman Kodak Company||Filter dyes for photographic elements|
|US5928849 *||Jul 31, 1996||Jul 27, 1999||Eastman Kodak Company||Black and white photographic element|
|US5965333 *||Mar 10, 1998||Oct 12, 1999||Eastman Kodak Company||Thermal recording element|
|US6183944||Nov 30, 1995||Feb 6, 2001||Eastman Kodak Company||Aggregated dyes for radiation-sensitive elements|
|US6291149||Dec 7, 2000||Sep 18, 2001||Eastman Kodak Company||Aggregated dyes for radiation-sensitive elements|
|US6300046||Dec 7, 2000||Oct 9, 2001||Eastman Kodak Company||Aggregated dyes for radiation-sensitive elements|
|US6306567||Dec 7, 2000||Oct 23, 2001||Eastman Kodak Company||Aggregated dyes for radiation-sensitive elements|
|US6342339||Dec 7, 2000||Jan 29, 2002||Eastman Kodak Company||Aggregated dyes for radiation-sensitive elements|
|US8012383 *||Dec 12, 2002||Sep 6, 2011||Sumitomo Chemical Company, Limited||Method for producing polarizing film|
|US20060244163 *||Dec 12, 2002||Nov 2, 2006||Koji Matsumoto||Method for producing polarizing film|
|EP0200502A2||Apr 25, 1986||Nov 5, 1986||Konica Corporation||Light-sensitive silver halide color photographic material|
|EP0202616A2||May 15, 1986||Nov 26, 1986||Konica Corporation||Method for color-developing a silver halide photographic light-sensitive material|
|EP0313051A1||Oct 20, 1988||Apr 26, 1989||Fuji Photo Film Co., Ltd.||Silver halide photographic material|
|EP0822444A1 *||Jul 21, 1997||Feb 4, 1998||Eastman Kodak Company||Black and white photographic element|
|EP1035428A2||Mar 1, 2000||Sep 13, 2000||Fuji Photo Film Co., Ltd.||Optical logic device and optical memory device|
|EP1155002A1 *||Feb 4, 2000||Nov 21, 2001||TransTech Pharma Inc.||Method of synthesizing barbituric acid derivatives and their use for the synthesis of chemical libraries|
|EP1701347A2||Nov 28, 2003||Sep 13, 2006||Fuji Photo Film Co., Ltd.||Optical information-recording Medium, novel oxonol compound and method of recording information|
|EP1975698A1||Mar 25, 2008||Oct 1, 2008||FUJIFILM Corporation||Method and apparatus for producing conductive material|
|EP2009977A2||May 7, 2008||Dec 31, 2008||FUJIFILM Corporation||Electromagnetic shielding film and optical filter|
|WO2007055273A1||Nov 9, 2006||May 18, 2007||Fujifilm Corporation||Cation compound, dye compound and use thereof, and optical information recording medium|
|WO2007114196A1||Mar 28, 2007||Oct 11, 2007||Fujifilm Corporation||Conductive film, method for producing same, and light-transmitting electromagnetic shielding film|
|WO2008038764A1||Sep 28, 2007||Apr 3, 2008||Fujifilm Corporation||Spontaneous emission display, spontaneous emission display manufacturing method, transparent conductive film, electroluminescence device, solar cell transparent electrode, and electronic paper transparent electrode|
|WO2008075771A1||Dec 21, 2007||Jun 26, 2008||Fujifilm Corporation||Conductive film and method for manufacturing the same|
|U.S. Classification||252/582, 544/302, 544/300, 430/522, 430/507, 430/518|
|International Classification||G03C1/83, C07C275/26, C09B23/02, C07C275/28, C07C273/18, C07C275/16|
|Cooperative Classification||G03C1/832, C07C273/1827, C07C2101/14, C09B23/02|
|European Classification||G03C1/83C, C09B23/02, C07C273/18B2B|