US3574627A - Color photographic elements - Google Patents

Abstract

NONDIFFUSIBLE HYDROXYLATED TRINUCLEAR STABILIZER COMPOUNDS INCLUDING THE 2,2 - (B-ISOPROPYL)-TETRAMETHYLENE6-CHROMANOLS, THE 2-2-(B,B-DIMETHYL)-PENTAMETHYLENE-6CHROMANOLS AND THE 5A,6,7,8,9,9A - HEXAHYDRO-2-DIBENZOFURANOLS ARE ADVANTAGEOUSLY INCORPORATED IN HYDROPHILIC COLLOID LAYERS OF PHOTOGRAPHIC ELEMENTS IN WHICH COLOR PHOTOGRAPHIC DYE IMAGES ARE TO BE STORED FOR VIEWING. THE STABILIZER COMPOUNDS PROTECT DYE IMAGES AGAINST THE FADING EFFECTS OF PROLONGED EXPOSURE TO LIGHT.

Description

United States Patent 3,574,627 COLQR PHOTOGRAPHIC ELEMENTS Max H. Stern and Gregory J. Lestina, Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N.Y. No Drawing. Filed Feb. 6, 1969, Ser. No. 797,276 Int. Cl. G03c 1/90, 7/00 US. Cl. 96-100 20 Clalms ABSTRACT OF THE DISCLOSURE Nondiffusible hydroxylated trinuclear stabilizer compounds including the 2,2 (fit-isopropyl)-tetramethylene- 6-chromanols, the 2,2-([3,;3-dimethyl)-pentamethylene-6- chromanols and the 5a,6,7,8,9,9a hexahydro-Z-dibenzofuranols are advantageously incorporated in hydrophilic colloid layers of photographic elements in which color photographic dye images are to be stored for viewing. The stabilizer compounds protect dye images against the fading effects of prolonged exposure to light.

This invention relates to photography, photographic materials including color photographic materials containing dye image stabilizing agents, and methods for improving the stabilities of dyes in photographic materials.

The formation of dye images by the chromogenic development of silver halide photographic materials, involving the coupling reaction of oxidized primary aromatic amino developing agents with coupling compounds to form indophenol, indamine, azomethine, phenoxazine, phenazine, and similar dyes, is well known. In this system, the subtractive color process of color formation is ordinarily used and the image dyes customarily formed are cyan, magenta, and yellow, which are the colors that are complementary to the primary colors, red, green and blue, respectively. Usually phenolic couplers (i.e., phenols and naphthols) are used to form the cyan dye image; pyrazolone or cyanoacetyl couplers are used to form the magenta dye image; and acylacetamide or dibenzoylmethane couplers are used to form the yellow dye image.

In these color photographic systems, the color-forming coupler may be applied in a developer solution or incorporated in the light-sensitive photographic emulsion layer or in another dye-image-forming layer, so that, during development, it is available to react with oxidized color developing agent formed as the result of latent image development.

The dye images formed in such processes are not indefinitely stable to ultraviolet radiation so that under rigorous viewing or display conditions involving, for example, long periods of exposure to sunlight, or other ultraviolet radiant illumination, the dyes may fade, resulting in deterioration in the quality of the picture.

Increases in the stability of indophenol, indoaniline, and azomethine dyes to ultraviolet radiation have been achieved by the use of a variety of agents which can be added to the emulsion in processing, or more conveniently, in manufacture. Lestina and Reckhow describe the use of dinuclear 6-hydroxy chroman stabilizers in photographic elements in US. Ser. No. 452,889, filed May 3, 1965, now Pat. No. 3,432,300. The need remains for still other stabilizers that will further enhance the resistance of these dyes to actinic light.

It is therefore an object of our invention to provide novel photographic elements containing dyes and/ or dyeforming compounds, and hydroxylated tricyclic stabilizer compounds to increase the stability of the dyes against ultraviolet and visible light radiation.

Another object of our invention is to provide novel image dye stabilizing agents which do not form highly colored oxidation products in the processing baths, e.g., bleach baths, etc., used in color photographic processing.

Another object of our invention is to provide novel color photographic image-forming layers comprising hydrophilic colloid film-forming binders containing finely particulate dispersions of solutions of our hydroxylated trinuclear stabilizing agents.

It is a further object to provide such layers also containing couplers.

A further object is to provide novel dispersions of our hydroxylated trinuclear stabilizing agents which can be incorporated in silver halide emulsion layers without adverse emulsion effects.

It is a still further object of our invention to provide processed color photographic layers containing dye images in association with the hydroxylated trinuclear stabilizing agents of our invention.

These and other objects will be apparent from a consideration of the following specification and claims.

These and still other objects are accomplished according to our invention by addition to layers intended for the storage of color photographic dye images, of dye stabilizing quantities of a nondiffusible hydroxylated trinuclear stabilizer compound including a 2,2 (fr-isopropyl)-tetramethylene 6 chromanol, a 2,2-(B,B-dimethyl)- pentamethylene-6-chromanol, and a 5a,6,7,8,9,9a hexahydro-Z-dibenzofuranol.

Particularly advantageous dye-stabilizing agents for the practice of our invention are included in the nondiffusible hydroxylated trinuclear stabilizers having the formulas:

I Be

wherein R and R each represents hydrogen, a lower alkyl group, preferably alkyl of 1 to 4 carbon atoms (e.g., methyl, ethyl, propyl, isopropyl, butyl, t-butyl, etc.) or a lower alkoxy group preferably having from 1 to 4 carbon atoms (e.g., methoxy, ethoxy, butoxy, t-butoxy, etc.); R represents hydrogen, an alkyl group preferably an alkyl group having from 1 to 18 carbon atoms including an acyclic alkyl group having from 1 to 18 carbon atoms, e.g., methyl, butyl, octadecyl, t-butyl, t-octyl, isopropyl, cyclopentylmethyl, 2 cyclopentylethyl, 4 cyclopentylbutyl, cyclopentyloctadecyl, 2 cyclopentyl-1,1-dirnethylethyl, cyclohexylmethyl, 2-cyclohexylethyl, 3-cyclohexylpropyl, 4 cyclohexylbutyl, w-cyclohexyloctadecyl, etc., a cyclic alkyl group, e.g., a cycloalkyl group, such as, a cyclopentyl group (e.g., cyclopentyl, l-methylcyclopentyl, l-ethylcyclopentyl, 1 propylcyclopentyl, 1-butylcyclopentyl, etc.), a cyclohexyl group (e.g., cyclohexyl group, l-methylcyclohexyl, 1 ethylcyclohexyl, l-propylcyclohexyl, l-butylcyclohexyl, etc.) or an alkoxy group in which the alkyl moiety is any of the alkyl groups defined for R, such that when R is hydrogen R is preferably a branched chain lower alkyl group; R and R are hydrogen and isopropyl such that when R is hydrogen, R is isopropyl and when R is hydrogen, R is isopropyl. Typical illustrative compounds are listed below.

Compound No. Name 2 2r(ti-isopropyl)-tetramethylene-7-t-octyl-6'chromanol.

III

wherein R R and R are as defined previously, R R R and R each represent hydrogen, methyl, isopropyl, lower hydroxyalkyl having from 1 to 3 carbon atoms (e.g., hydroxymethyl, Z-hydroxyethyl, 3-hydroxypropyl, etc.), carboxyalkyl having from 2 to 4 carbon atoms (e.g., carboxymethyl, '2 carboxyethyl, 3 carboxypropyl, etc.), and alkoxyalkyl having from 2 to 4 carbon atoms (e.g., propoxymethyl, ethoxyethyl, methoxypropyl, etc.), such that when R is hydrogen, R is hydrogen, and R and R are methyl isopropyl, hydroxyalkyl, carboxyalkyl and alkoxyalkyl such that one of R and R is isopropyl, and such that when R, is hydrogen, R is hydrogen and R and R are methyl, isopropyl, hydroxyalkyl, carboxyalkyl, alkoxyalkyl such that one of R and R is isopropyl.

Typical examples of stabilizers of Formula III include the following:

(a) 5 a,6,7,8,9,9a-hexahydro-5 a-isopropyl-8-methyl-3-toctyl) -2-dibenzofuranol (b) 5a,6,7,8,9,9a-hexahydro-5a-methyl-8-isopropyl-3- (tbutyl -2-dibenzofuranol (c) 5 a,6,7,8,9,9a-hexahydro-7-isopropyl-9a-methyl-3- (tbutyl) -'2-dibenzofuranol (d) 5a,6,7,8,9,9a-hexahydro-7-methyl-9a-isopropy1-3-(tbutyl -2-dibenzofuranol (e) 5a,6,7,8,9,9a-hexahydro-5a- 2-hydroxyethyl) -8- isopropyl-3-(t-butyl -2-dibenzofuranol (f) 5 a,-6,7,8,9,9a-hexahydro-7-isopropyl-9a-( 2-hydroxyethyl) -3- (t-butyl) -2-dibenzofuranol (g) 5 a,6,7,8,9,9a-hexahydro-Sa-isopropyl-8-carboxymethyl-3-(t-buty1)-2-dibenzofurano1 (h) 5a,6,7,8,9,9a-hexahydro-Sa-methyl-8-isopropyl-3- (toctyl) -2'dibenzofuranol.

The 1-, d-optical isomers of our stabilizers as well as various mixtures of these are equally effective as .stabilizing agents according to our invention.

Our stabilizing agents are advantageously used to improve the stability of the indophenol, indoaniline and azomethine dyes, such as, those produced by chromogenic development, the azo dyes produced in well-known diazotype elements, and dyes produced in well-known silverdye-bleach elements and the dyes used in dye transfer, dye imbibition and dye diffusion transfer systems. Our stabilizing agents are advantageously incorporated in the layer in which the dye image will be stored after image formation; this is either the layer in 'which a nondiffusible dye image is formed or the layer to which a diffusible dye image is transferred, such as, the image-receiving layer of a receiving sheet in a dye-transfer system, a dyeimbibition system or a dye-diffusion transfer system. The

2,2-(fl-isopropyl)-tetramethylene-7-t-butyl-tlchromanol.

..... 2,2-(fl,fl-dimethyl)-pentamethylene-7-is0propyl-6-chromanol.

2,2- (B,fl-dlmethyl)-pentamethylene-7-t-butyl-dchromanol. 2,2-09,B-dimethylg-pentamethylene-7-t-butyl-B-methyl-(ichromanol.

-pentamethylene-7-cyclohexyl-Gchromanol.

2,2-(fi,fl-dimethyl)-pentamethylene-7-cyelopentyl-(S-ehromanol.

2,2-(5,,8-dlmethyl)-pentamethylene-7-(l-methylcyclopentyl)-6-chromanol.

2,2(B,fl-dimethyl)-pentamethylene-7-cyclohexylmethyl-6-chromanol.

2,2-(BJS-dlmethyD-pentamethylene7-n-octyl-6-chromanol.

2,2(fi,fl-dl1nethyl)-pentamethylenefl-boctyl-6-chromanol.

specific method used to form the indophenol, indoaniline, azomethine, or azo dye is not important since any of the well-known image-forming elements and processes are used advantageously.

Our stabilizers are particularly efiicacious in protecting dyes produced by chromogenic development of any of the well-known 5-pyrazolone couplers used in photography for magenta dye formation. Typical magenta dyes are those produced by color development of couplers described in U.S. patents, such as 2,600,788, 2,725,292, 2,908,573, 3,006,759, 3,062,653, 3,152,896, 3,311,476 and Young U.S. application Ser. No. 458,455, filed May 24, 1965, which couplers are herein incorporated by reference.

Cyan dye-forming couplers of such U.S. patents as 2,474,293, 2,725,292, 2,895,826, 2,908,573 produce cyan dyes upon chromogenic development that are advantageously stabilized against light exposure by our stabilizing compounds.

Yellow dye-forming couplers of U.S. Pat. 2,908,573 produce yellow dyes that are made less subject to the fading effects of prolonged exposure to light by the presence of our stabilizing compounds.

Our stabilizing agents are incorporated alone or together with a color-forming coupler in a dye image-forming layer of a color photographic element. A useful method of dispersing our stabilizing compounds is that described for dispersing couplers in Mannes et al. U.S. Pat. 2,304,939, issued Dec. 15, 1942; Jelley et al. U.S. Pat. 2,322,027, issued June 15, 1943, etc., in which highboiling organic solvents are used to dissolve the material. Other applicable methods are described in Vittum et al. U.S. Pat. 2,801,170, and Fierke et al. U.S. Pat. 2,801,171, both issued July 30, 1957, and Julian U.S. Pat. 2,949,360. issued Aug. 16, 1960, in which low-boiling or water-soluble organic solvents are used with high-boiling solvent.

In these methods of dispersion our stabilizing agents can be contained in the same dispersion with nondifiusing couplers, or in a separate dispersion, and the couplers can optionally be dispersed directly in the emulsion. Highboiling solvents useful is dispersing the hydroxylated tri cyclic stabilizer compounds of our invention include di-nbutylphthalate, benzylphthalate, triphenyl phosphate, trio-cresyl phosphate, diphenyl mono-p-tert-butylphenyl phosphate, monophenyl di-p-tert-butylphenyl phosphate, diphenyl mono-o-chlorophenyl phosphate, monophenyl dio-chlorophenyl phosphate, tri-p-tert-butylphenyl mono- (S-tert-butyl 2 phenylphenyl)phosphate, 2,4-di-n-amylphenol, 2,4-di-t-amylphenol, N,N-diethylaurarnide, etc.

The low-boiling or water-soluble organic solvents which can be used to advantage with the high-boiling solvents are disclosed in patents, such as Fierke et al., U.S. Pat. 2,801,171, and Vittum et al., U.S. Pat. 2,801,170, both issued July 30, 1957, and Julian U.S. Pat. 2,949,360, issued Aug. 16, 1960, etc.

The organic solvents include:

1) Low-boiling, substantially Water-insoluble organic solvents, such as, methyl, ethyl, propyl, and butyl acetates, isopropyl acetate, ethyl propionate, sec-butyl alcohol, ethyl formate, butyl formate, nitromethane, nitroethane, carbon tetrachloride, chloroform, etc., and

(2) Water-soluble organic solvents, such as methyl isobutyl ketone, B-ethoxyethyl acetate, tetrahydrofurfuryl adipate, Carbitol acetate (diethyleneglycol monoacetate), methoxytriglycol acetate, methyl Cellosolve acetate, acetonyl acetone, diacetone alcohol, butyl Carbitol, butyl Cellosolve, methyl Carbitol, methyl Cellosolve, ethylene gycol, diethylene gycol, dipropylene glyco, acetone, methanol, ethanol, acetonitrile, dimethylformamide, dioxane, etc.

Combinations of two or more of the new and improved dye-stabilizing agents of our invention may be used. These agents may also be used in combination with other addenda in the same dispersion, for example, other stabilizing agents, antistain agents, e.g., ballasted hydroquinones, phenolic antioxidants, etc. The selection of the specific stabilizer compound and the concentration used in each layer of a multilayer film can be varied over a wide range, and will depend on the improvement in resistance to fading required for each of the image dyes in the respective layers.

Any of the well-known primary aromatic amino colorforming silver halide developing agents such as the phenylenediamines, e.-g., N,N-diethyl-p-phenylenediamine hydrochloride, N-monomethyl p phenylenediarnine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N-laurylamino)toluene, N-ethyl-N-fl- (methylsulfonamido)ethyl 3 methyl-4-aminoaniline sulfate, N-ethyl-N-(B-methylsulfonamidoethyl) 4 aminoaniline, 4-(N-ethyl-N- s-hydroxyethyl)aminoaniline, etc., the p-aminophenols and their substitution products where the amino group is unsubstituted, e.g., 2,6-dichloro-4- aminophenol, 2-bromo-p-aminophenol, 2,6-diiodo-4-aminophenol, 4-aminophenol, etc., may be used to develop photographic coatings containing our stabilizers. Various other materials may be included in the developer solutions depending upon the particular requirements, for example, image-forming couplers, competing couplers, antifoggants, hardeners, an alkali metal sulfite, bisulfite, alkaline buffer salts, bromide, iodide, etc., and the thickening agents used in viscous developer compositions. A typical developer solution is given in Example 2, but does not limit the invention.

Our stabilizers are incorporated in hydrophilic colloid layers intended for the storage of photographic dye images, such as, a receiving sheet for receiving a difiusible transferred dye image or a dye-image forming layer containing a light-sensitive material such as silver halide (e.g., silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chlorobromoiodide, silver bromoiodide, etc.), a light-sensitive diazo compound (as in diazo-type material), etc.

Hydrophilic colloids used to advantage in the image layers include any of the hydrophilic colloids used in image-forming layers and in receiving layers, such as gelatin, and gelatin derivatives, casein and other proteinaceous colloids, hydrophilic cellulosic derivatives, e.g. carboxymethyl cellulose, alginates, synthetic resins, e.g., polyvinyl alcohol, copoly(ethylacrylate, acrylic acid) polyvinyl pyrrolidone, etc. Some colloids used to advantage are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in US. Pat. 2,286,215, a far hydrolyzed cellulose ester, such as cellulose acetate hydrolyzed to an acetyl content of 19-26%, as described in US. Pat. 2,327,808, a water-soluble ethanolamine cellulose acetate as described in U.S. Pat. 2,322,085, a polyacrylamide having a combined acrylamide content of 30-60% and a specific viscosity of 025- on an imidized polyacrylamide of like acrylarnide content and viscosity as de scribed in US. Pat. 2,541,474, zein as described in US. Pat. 2,563,791, a vinyl alcohol polymer containing urethane carboxylic acid groups of the type described in US. Pat. 2,768,154, or containing cyano-acetyl groups, such as the vinyl alcohol-vinyl cyano-acetate copolyrner as described in US. Pat. 2,808,331, or a polymeric material which results from polymerizing a protein or a saturated acylated protein with a monomer having a vinyl group as described in US. Pat. 2,852,382.

The emulsions used in the photographic element of our invention can be chemically or optically sensitized.

Our stabilizing compounds are also used to advantage with mordants in dye-image receiving sheets for dye diffusion transfer processes such as are described in French Pat. 75,676, dlivr June 19, 1961. Mordant receiving sheets in which our compounds can be used to advantage are described in French Patent 1,361,293, dlivr Apr. 6, 1964. When the diffusible-image dyes are mordanted in such receiving sheets containing our stabilizer compounds, they exhibit marked improvement in light stability.

Usually emulsions containing our stabilizer compounds are coated on photographic supports in the form of multilayer color photographic elements wherein at least three differently sensitized emulsion layers are coated over one another on the support. Usually the support is coated in succession with a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer either with or Without a Carey Lea filter layer between the blue-sensitive and green-sensitive layers. The three differently color sensitized layers may be arranged in any other order over one another that is desirable; however, the Carey Lea filter layer (i.e., yellow colloidal silver) would not be put over the blue-sensitive layer. Preferably, these light-sensitive layers are arranged on the same side of the support.

In general, our stabilizing agents are used in quantities ranging from 0.25 mole to 20 moles of stabilizer per 1 mole of coupler used (or per 1 mole of dye produced). The preferred range is from 1 mole to 5 moles of stabilizer per mole of coupler (or per mole of dye produced). The following examples are included for a further understanding of our invention.

EXAMPLE 1 Four single layer gelatinous coatings containing a preformed magenta dye are made on cellulose acetate film support. The coatings have the following compositions:

TABLE I Tricresyl phosphatemg./ft.

Stabilizer indicated in Table II-10- mole/ft. Gelatin-733 trng./ft.

Tri-isopropylnaphthalene sulfonate33 mg./ft. Saponin-25 mg./ft.

The magenta dye is prepared by reacting the coupler, 1 (2 chloro 4, 6 dimethylphenyl) 3 {3 [a (3- pentadecylphenoxy)butyramido1benzamido} 5 pyrazolone (described as coupler No. 6 in US. Pat. 3,062,653), dissolved in tricresyl phosphate with the oxidized form of color-developing agent, N ethyl B methanesulfonamidoethyl 3 methyl 4 aminoaniline sulfate. The four coatings are subjected to a light fading test for three weeks SANS (i.e., 500 ft. candles simulated average north sky light from a filtered xenon arc). The stabilizer and the loss in magenta dye density (from an area of the dye image having an original magenta dye density pfblabout 1.2) data are summarized in the following The results show that our stabilizer compounds N0. 2 and b produce about an 86% improvement in the stability of the preformed magenta dye in coatings Nos. 3 and 4 compared to coating No. l (the control) when subjected to the 3 weeks SANS test. Prior art compound 7 X is 2,2 dimethyl 4 isopropyl 6 hydroxy 7- t-octylchroman of French Pat. 1,478,141, dlivr Mar. 13, 1967.

Similar results are obtained when Example 1 is repeated using magenta dyes produced from the magenta 8 EXAMPLE 3 Example 2. is repeated using magenta dye-forming -pyrazolone couplers 1 through 12 of US. Pat. 2,600,788 in place of the coupler used in Example 2. The results are coupler and the oxidized form of other Well-known color 5 slmllar to those obtamed m Examp 1e developing agents including those disclosed herein previ- EXAMPLE 4 ously. Similar results are obtained when Example 1 1s Example 2 is repeated using magenta d f i repeafied 115mg any Q the well'known magenta S-pyrazolone couplers 6 through 9' of US. Pat. 2,908,573 formmg couplers Wlth OXldlZed form any of w 10 in place of the coupler used in Example 2. The results wrell knoltglin color-developmg agents described herem are Similar to those obtained in Example ev1ous p EXAMPLE 2 EXAMPLE 5 Three single layer gelatinous silver halide emulsion Exjample 2 is repeated using colored magenta coatings containing the magenta dye-forming coupler, g% f fi 7 a E 1 (2 chloro 4,6 dimethylphenyl) 3 {3 [0c (3- a m P ace 0 e coup er use pentadecylphenoxy)butyramido]benzatmido} 5 pyr amgle 2. 1In this examglie the dye oflthe 00111113161 remamcilng olone are made on a paper support. The gelatinous e C0 or Processe ayer as as magenta Ye silver halide emulsion is prepared as described by Trivelli formed by Poupler that colfpled Wlth X1d1Z ed color and Smith in The Photographic Journal, page 330, May 20 veloper during color processing are both stabilized against 1939. The coatings have the following compositions: rg g effects of Prolonged exposure to light in e a 111g test. TABLE III Similarly the valuable stabilizing effect of our stabiliz- C0upler (identified above)-5O mg./ft, mg agents can be demonstrated for still other dyes par- Tricresyl 50 /ft 2 ticularly the dyes formed by chromogenic development of Stabilizer (as indicated in Table 'IV)-equimolar to y of The known -PY couplerscoupler EXAMPLE 6 Gelatin-440 mg./ft. Tri-isopropylnaphthalene sulfonate-20 m-g./ft. Example 2 1s rapeaffiid usmg our Stablhzer Compound 9 nag/ft; in place of our stabilizer compound 2 and using the 3 weeks SANS test. The results are summarized in Table V The coatings are dried and given /2 second exposure on below; a 1B intensity scale sensitometer, followed by color TABLE v processing at 75 as follows:

mi... tates: C0101- development 6 Coating No. Stabilizer density 105s Stop-fix 3 g ----&N: Wash 2 omp un 0.9 .48 Ferricyanide bleach 4 Wash 3 40 in this example our compound No. 9 produces a 53% Hardening fix "d 3 improvement 1n the stability of the magenta dye image W ash 8 upon the prolonged exposure to light. Bufier (stabilizer) 1 3 EXAMPLE 7 The color developer is a conventional color developer Example 2 is repeated using stabilizer compounds (a) solution containing benzyl alcohol, sodium sulfite, the and (b) in place of stabilizer compound No. 2. The recolor developing agent, N ethyl [3 methanesulfonsults are summarized below: atmidoethyl 3 methyl 4 arninoaniline sulfate and an alkali to give a pH of about 10. A conventional stop-fix 1 week SANS 3weeks SANS bath containing sodium th osulfate, sodium sulfite, acetlc Coating Stabilizer ii g gffigg; i acid, bor1c acid and potassium alum is used for the stopfix p and for the hardening fix t p in the process 5331331311333: finltaata'tiij 3% 3'21 A conventional alkali metal ferricyanide-bromide bleach 3 Compound b-1111: 0114 0:43 bath is used, and a conventional aqueous citric acid stabilizer bath having a pH of 3.5 is used in the process. The EXAMPLE 3 magenta dye density is measured in each processed coat- Example 2 is repeated usin g stabilizer compound h in mg before and 1 W SANS and 3 Weeks SANS place of stabilizer compound No. 2. The results are sumfading test as described in Example 1. The results are marized below: summarized in the following table.

1 week SAdNS 3 Weeks SANS TABLE IV Coating No. Stabilizer iiiiisit? 10 t i e n s iig iii;

lweek SANS 3weeks SANS 1 None 0 62 0 92 t d d Coating No. Stabilizer itiiriit? 10%? 132% 2 Cmpmndh 14 1 N t 1 0.5 2.. P33?.o;2.20undX 0.11 3.21 65 P E 9 3 Compound No. 2 (of 0.08 0.24

invention). A gelatinous silver halide emulsion is prepared as described by Trivelli and Smith in The Photographic Journal, page 330, May 1939. One portion of this emulsion The results show that our stabilizer No. 2 produces an is coa ed as a control identified as coating No. 1 on a 86% improvement in the stability of the magenta dye cellulose acetate film support. Coating No. 2 is made of images formed by color development in coating No. 3 another portion of the emulsion to which our stabilizing compared to coating No. 1 (the control) when subjected Compound No. 2 is added so that it is coated at a rate to the 1 week SANS test and a improvement in the of 10 mole (of stabilizer) per ft. Coating No. 3 is stability of the magenta dye when subjected to the 3 made of another portion of the emulsion to which our weeks SANS test. 75 stabilizing compound N0. 9 is added so that it is coated at the same rate as stabilizing compound No. 2. The coatings are given a sensitometric exposure and color developed in a conventional magenta color developing solution containing the color developing agent, 4-amino-N-ethyl- N-(fl-methanesulfonamidoethyl)m-toluidine sesquisulfate monohydrate, an alkali, an alkali metal sulfite and the magenta dye-formin g coupler, 1-(2,4,6-trichlorophenyl) -3- (2,4-dichloroanilino)-5-pyrazolone (coupler No. 6 of US. Pat. 3,152,896). The color developed coatings are then water washed, bleached in a conventional alkali metal ferricyanide-bromide bleach, fixed in a conventional alkali metal thiosulfate fixing bath washed and dried. Our stabilizer compounds 2 and 9 in coatings 2 and 3 impart valuable protection to the magenta dye images as is illus trated by 1 and 3 weeks SANS tests as described in Example 2.

Similar results are obtained when Example 9 is repeated with other dye-stabilizing compounds of our invention and with other primary aromatic amine color developing agents and other magenta dye-forming couplers including couplers l, 2, 3, 4, 5, 7 and 8 of US. Pat. 3,152,896 as well as other diifusible magenta dyeforming couplers well known in the art.

Our stabilizer compounds are advantageously incorporated in the receiving layer of image receiving sheets to stabilize the dye images transferred thereto. For example, image transfer dyes made from compounds I through XLVI of US. Pat, 3,227,551 and transferred to receiving layers containing our stabilizer compounds have improved stability to prolonged exposure to light. Similarly, dye images produced from dye developers such as those described in US. Pat. 3,404,002 and transferred to receiving layers containing our stabilizer compounds are found to fade less upon prolonged exposure to light than the same images transferred to a receiving layer containing none of our stabilizers.

Similarly, the azo dye images produced in silver dyebleach elements containing our stabilizers are substantially more stable to prolonged exposure to light than images that are not so protected. Thus our stabilizers are advantageously incorporated in silver dye-bleach materials, such as those described in US. Pats. 2,418,624, 2,420,630, 2,420,631, etc.

Our stabilizing compounds are also advantageously incorporated in the azo dye image-forming layer of any of the diazo-type elements that are used for duplicating images. Thus our stabilizer compound is incorporated into the polymeric matrix layer containing the diazo salt(s) and coupler(s) where it advantageously protects the azo dye image produced upon development of the light image exposed layer.

In general, the stabilizer compounds of our invention are prepared by reacting a compound of the formula:

wherein R R and R are as defined previously, with a C terpene in the presence of an acid catalyst such as zinc chloride, boron trifluoride etherate, etc., in an appropriate solvent, for example, a halogenated hydrocarbon (e.g., chloroform, dichloroethane, carbontetrachloride, etc.) preferably at a temperature in the range from about to 20 C.

Compounds of Formulas I and II are advantageously prepared by reacting a compound of Formula IV with V. CH3 CH oHi Ct...

Compound 2, for example, is advantageously made by heating t-butylhydroquinone with myrcene in acetic acid with zinc chloride catalyst at '50 to 60 C. for about 4 hours. Compound No. 2 as a crystalline product is obtained having a M.P. of l45l47 C.

Compound No. 9 is advantageously made by the method described for compound No. 2 but using an equimolar amount of t-octylhydroquinone in place of tbutylhydroquinone. Compound No. 9' as a crystalline product is obtained having a M.P. of 15ll53 C.

Compounds 1, 3, 4, 5, 6, 7, 8, l0 and 11 are advantageously prepared by the methods indicated above for compound No. 2 excepting that the t-butylhydroquinone is replaced by the appropriate hydroquinone derivative as indicated in the following table:

Compound No.: Compound of Formula IV used 1 Isopropylhydroquinone.

3 2-t-butyl-3-methylhydroquinone. 4 Cyclohexylhydroquinone.

5 Cyclopentylhydroquinone.

6 l-methylcyclopentylhydroquinone. 7 Cyclohexylmethyl.

8 n-Octylhydroquinone.

10 n-Decylhydroquinone.

11 Octadecylhydroquinone.

Compound No. 12 is isolated from the reaction mixture used to make compound No. 1. Compound No. 13 is isolated from the reaction mixture used to make compound No. 2 and compound No. 14 is isolated from the reaction mixture used to make compound No. 9.

The 5a,6,7,8,9,9a-hexahydro-2-dibenzofuranols of Formula III are advantageously prepared by reacting the appropriate compound of Formula IV with an acyclic C terpene, such as, linalool in acetic acid containing a catalyst such as zinc chloride preferably under reflux. Substantially higher yields of compounds of Formula III are advantageously obtained by reacting the appropriate compound of Formula IV with the appropriate C cyclic terpene or derivative thereof, such as, limonene, a-pinene, u-phellandrene, etc., at a temperature of from about 5 to about 20 C. with an acid catalyst, such as, boron trifluoride-etherate preferably in a halogenated hydrocarbon-ether solvent mixture, e.g., a mixture of diethyl ether with 1,2-dichloroethane or chloroform or carbontetrachloride.

Compound a is produced by condensation of t-octylhydroquinone and linalool in refluxing acetic acid containing zinc chloride. The purified product has a melting point of C.

In a preferred synthesis the compounds of Formula III are advantageously prepared in good yields by treating solutions of the appropriate hydroquinone of Formula IV and the appropriate cyclic terpene in a 4:2:1 mixture of chloroform, carbontetrachloride and ether cooled to 5- 10 C. with boron trifluoride etherate and storing at 5 to 20 C. until the condensation is completed usually from about 2 to 10 days. The products are then isolated by appropriate methods such as chromatography after washing the organic layer with dilute (1 N) sodium hydroxide and with Water to neutrality.

Compounds a and h are advantageously prepared by condensing t-octylhydroquinone with d-limonene using the procedure described above.

Compounds b, c and d are advantageously prepared by this method in which t-butylhydroquinone is condensed 11 with d-limonene. These compounds are isolated in different fractions using chromatography.

Compounds e and f are prepared by treating a solution of 0.1 mole of Nopol (trade name for 6,6-dimethylbicyclo-[3,1,l]-hept-2-ene 2 ethanol) and 0.1 mole of t-butylhydroquinone in 175 ml. of 6:1 chloroform-ether with 4 ml. of, boron trifiuoride-etherate at 20 C. for 10 days. The crude product is purified by molecular distillation, followed by recrystallation from acetonitrile to give a crystalline product with a melting point of l90l92 C.

Compound g is advantageously prepared by condenshept-Z-ene-Z-acetic acid in chloroform-carbontetrachloride hept-2-ene-2-acetic acid in chloroform carbontetrachloride-ether containing boron trifiuoride-etherate held at 5 at 20 C.

Our hydrophilic colloid layers containing dye images, such as, indophenol dye images, indoaniline dye images, azomethine dye images and azo dye images and a stabilizing amount of a nondiifusible hydroxylated tricyclic stabilizer compound, such as, a 2,2-(B-isopropyl)-tetramethylene-G-chromanol, and a 2,2-(j3,fl-dimethyl)pentamethylene-G-chromanol provide a valuable technical advance in color image reproduction because these images are substantially more stable than the same images in layers containing no stabilizer or a prior art stabilizer.

The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be eifected within the spirit and scope of the invention.

We claim:

1. A hydrophilic colloid layer containing a color photographic dye image, said layer containing at least one nonditfusible, hydroxylated tricyclic stabilizer compound for said dye, said stabilizer compound being selected from the class consisting of a 2,2-(fi-isopropyl)-tetramethylene- 6-chromanol, a 2,2 (5,5 dimethyl)-pentamethylene-6- chromanol, and a 5a,6,7,8,9,9a-hexahydro 2 benzofuranol.

2. A hydrophilic colloid layer containing a color photographic dye image, said layer containing at least one nondififusible hydroxylated tricyclic stabilizer compound selected from the class consisting of those having the formulas:

| I HO HO and R- R3 CQCHs 1 12 wherein R represents a member selected from the class consisting of hydrogen, an alkyl group and an alkoxy group: R and R each represents a member selected from the class consisting of hydrogen, a lower alkyl group and a lower alkoxy group; and R and R each represent a member selected from the classs consisting of hydrogen and isopropyl, such that when R is hydrogen, R is isopropyl and when R is hydrogen, R is isopropyl.

3. A hydrophilic colloid layer containing a color photographic dye image, said layer containing at least one nondiflusible hydroxylated tricyclic stabilizer compound selected from the class consisting of those having the formula:

consisting of hydrogen, an alkyl group, and an alkoxy group; R and R each represents a. member selected from the class consisting of hydrogen, a lower alkyl group and a lower alkoxy group; R R R and R each represent a member selected from the class consisting of hydrogen, methyl, lower hydroxyalkyl having from 1 to 3 carbon atoms, carboxyalkyl having from 2 to 4 carbon atoms and alkoxyalkyl having from 2 to 5 carbon atoms, such that when R is hydrogen, R is hydrogen, and R and R are methyl, isopropyl, hydroxyalkyl, carboxyalkyl and alkoxyalkyl such that one of R and R is isopropyl, and such that when R; is hydrogen, R is hydrogen and R and R are methyl, isopropyl, hydroxyalkyl, carboxyalkyl, alkoxyalkyl such that one of R and R is isopropyl.

4. A dye image-forming silver halide emulsion layer comprising a film-forming hydrophilic colloid containing at least one nondifiusible hydroxylated tricyclic stabilizer compound for stabilizing said dye image against the ef fects of prolonged exposure to light, said compound being selected from the class consisting of a 2,2-(B-isopropyl)- tetramethylene-6-chromanol, a 2,2-(6,,8-dimethyl)-pentamethylene-6-chromanol and a 5a,6,7,8,9,9a-hexahydro-2- benzofuranol.

5. A dye image-forming silver halide emulsion layer comprising a film-forming hydrophilic colloid containing at least one nondifiusible hydroxylated tricyclic stabilizer compound for stabilizing said dye image against the effects of prolonged exposure to light, said compound being selected from the class consisting of those having the formulas:

Ru l) R- O and R- 0 Rs I ti I M ---R2 CH3 CH3 wherein R represents a member selected from the class consisting of hydrogen, an alkyl group and an alkoxy group; R and R each represents a member selected from the class consisting of hydrogen, a lower alkyl group and a lower alkoxy group; and R and R each represent a member selected from the class consisting of hydrogen and isopropyl, such that when R is hydrogen, R is isopropyl and when R is hydrogen, R is isopropyl.

6. A dye image-forming silver halide emulsion layer comprising a film-forming hydrophilic colloid containing at least one nondifiusing hydroxylated tricycle stabilizer compound for stabilizing said dye image against the effects of prolonged exposure to light, said compound being selected from the class consisting of those having the formula:

wherein R represents a member selected from the class consisting of hydrogen, an alkyl group, and an alkoxy group; R and R each represents a member selected from the class consisting of hydrogen, a lower alkyl group and a lower alkoxy group; R R R and R each represent a member selected from the class consisting of hydrogen, methyl, lower hydroxyalkyl having from 1 to 3 carbon atoms, carboxyalkyl having from 2 to 4 carbon atoms and alkoxy-alkyl having from 2 to 4 carbon atoms, such that when R is hydrogen, R is hydrogen, and R and R are methyl, isopropyl, hydroxyalkyl, carboxyalkyl and alkoxyalkyl such that one of R and R is isopropyl, and such 13 that when R is hydrogen, R is hydrogen and R and R are methyl, isopropyl, hydroxyalkyl, carboxyalkyl, alkoxyalkyl such that one of R and R is isopropyl.

7. A dye image-forming silver halide emulsion layer of claim 4 containing an incorporated magenta dye-forming coupler.

8. A dye image-forming silver halide emulsion layer of claim 4 in which the hydrophilic colloid is gelatin.

9. A dye-image-forming silver halide emulsion layer comprising a film-forming hydrophilic colloid containing at least one nondiflusible hydroxylated tricyclic stabilizer compound for stabilizing said dye image against the eifects of prolonged exposure to light, said compound being selected from the class having the formula:

wherein R represents an alkyl group; and [R and R represents a member selected from the class consisting of hydrogen and a straight chain lower alkyl group.

10. A dye image-forming silver halide emulsion layer of claim 9 in which R in the structural formula of the stabilizer compound represents t-butyl.

11. A dye image-forming silver halide emulsion layer of claim 9 in which R in the structural formula of the stabilizer compound represents t-octyl.

12. A dye image-forming silver halide emulsion layer comprising a film-forming hydrophilic colloid containing at least one nonditfusible hydroxylated tricyclic stabilizer compound for stabilizing said dye image against the effects of prolonged exposure to light, said compound being selected from the class having the formula:

wherein R represents an alkyl group; R and R each represents a member selected from the class consisting of hydrogen and a straight chain lower alkyl group; and R and R each represent a member selected from the class consisting of hydrogen and isopropyl, such that when R is hydrogen, R is isopropyl, and when R is hydrogen, R is isopropyl.

13. A light-sensitive gelatino silver halide emulsion layer containing 2,2- (5,}8-dimethyl) pentamethylene-7-t-butyl- 6-chromanol.

14. A light-sensitive gelatino silver halide emulsion layer containing 2,2- (,8,fi-dimethyl)pentamethylene-7-t-octyl-6-chromanol.

15. A light-sensitive gelatino silver halide emulsion layer containing 2,2 (fl-ispropyl)-tetramethy1ene-7-t-butyl-6-chromanol.

16. A light-sensitive gelatino silver halide emulsion layer containing 5a,6,7,8,9,9a-hexahydro 5a isopropyl-S- methyl'3-(t-octyl)-2-dibenzofuranol.

17. A light-sensitive gelatino silver halide emulsion layer containing 5a,6,7,8,9,9a hexahydro-5a-methyl-8-isopropyl-3 (t-butyl) -2- dibenzofuranol.

18. A light-sensitive gelatino silver halide emulsion layer containing 5a,6,7,8,9,9a-hexahydro-5a-methyl-8-isopropyl- 3- (t-octyl -2-dibenzofuranol.

19. In an element for color photography designed for dye image storage, said element comprising a support layer and at least one hydrophilic colloid layer for said dye image, the improvement comprising the use of a hydrophilic colloid layer containing a dye stabilizing amount of a nondilr'usible dye stabilizer selected from the class consisting of a 2,2-(fi-isopropyl)-tetramethylene-6-chro manol, a 2,2-(fi,{3-dimethyl)pentamethylene-6-chromanol, and a 5a,6,7,8,9,9a-hexahydro-Z-benzofuranol.

20. In an element for color photography designed for dye image storage, said element comprising a support layer and at least one hydrophilic colloid layer for said dye image, the improvement comprising the use of a hydro- 7 philic colloid layer containing a dye stabilizing amount of a nonditfusible dye stabilizer selected from those having the formula:

IO: R1

References Cited UNITED STATES PATENTS 2,461,484 2/1949 Thompson 96-84 3,016,306 .1/1962 Mader et al. 96--84 2,461,485 2/ 1949 Thompson 9684 3,432,300 3/.1969 Lestina et al 96-56 NORMAN G. TORCHIN, Primary Examiner E. C. KIMLIN, Assistant Examiner US. Cl. X.lR. 96'91 52 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 57h, 627 Dated April 1 3, 1 971 lnventofl Max H. Stern and Gregory J. Lestina It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

. l Column 11 line L .5 second formula should read Column 11 line 59 "classs" should read "class";

Column 12, line 51 "tricycle" should read "tricyolic" and Signed and ealed this 19th day of October 1 971 (SEAL) Atteat .J EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Acting Commissioner of Patents