US3764337A

US3764337A - Color photographic materials containing dihydroxyspirochroman compounds as stabilizers

Info

Publication number: US3764337A
Application number: US00213540A
Authority: US
Inventors: A Arai; Y Oishi
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1970-12-29
Filing date: 1971-12-29
Publication date: 1973-10-09
Anticipated expiration: 1990-10-09
Also published as: CA998872A; DE2166076A1; GB1381499A; DE2165371A1; FR2121087A5; BE777487A; DE2165371C2

Abstract

COLOR PHOTOGRAPHIC MATERIALS CONTAINING AS STABILIZERS COMPOUNDS REPRESENTED BY THE FORMULA I

4,4,4'',4''-TETRA(CH3-),6,6''-DI(HO-),7,7''-DI(R1-),8,8''-

DI(R2-)-3,4,3'',4''-TETRAHYDRO-2,2''-SPIROBI(2H-1-BENZOPYRAN)

WHEREIN R1 IS AN ALKYL GROUP HAVING 18 OR LESS CARBON ATOMS, AN ALKENYL GROUP, AN ARYL GROUP, AN ALKOXY GROUP, AN ALKENOXY GROUP, AN ARYLOXY GROUP, AN ACYLAMINOALKYL GROUP OR AN ACYLAMINOARALKYL GROUP, AND R2 IS A HYDROGEN ATOM, A HALOGEN ATOM, AN ALKYL GROUP, AN ALKENYL GROUP OR AN ALKOXY GROUP.

Description

Oct. 9, 1973 AT$UAK| ARM ET AL 3,764,337

COLOR PHOTOGRAPHIC MATERIALS CONTAINING I DIHYDROXYSPIROCHROMAN COMPOUNDS AS STABILIZERS Filed Dec. 29, 1971 2 Sheets-Sheet '1 WAVELENGTH (p) 5.5 25 8.0 8.5909510 II |2l3 I4I5I6 2 I00 O 3 80 Z 60 g E 0 CL 4000 3200 2400 I900 I700 I500 I300 II00 900 700 3500 2800 2000 I800 I600 I400 I200 I000 800 s00 WAVENUMBER (cm) F; I INFRARED SPECTRUM OFVCOMPOUNDI (KBr DISK) a s 4' 2 0 PPM NUCLEAR MAGNETIC RESONANCE SPECTRUM 0F COMPOUND I (IN 00 0000 SOLUTION) FIG. I

United States Patent Office US. Cl. 96-100 7 Claims ABSTRACT OF THE DISCLOSURE Color photographic materials containing as stabilizers compounds represented by the Formula I R: R1 CH3 CH3 HO 'O I CH3 C 3 1 2 wherein R is an alkyl group having 18 or less carbon atoms, an alkenyl group, an aryl group, an alkoxy group, an alkenoxy group, an aryloxy group, an acylaminoalkyl group or an acylaminoaralkyl group, and R is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group or an alkoxy group.

The present invention relates to new dihydroxyspirochroman compounds as stabilizers. An object of the invention is to obtain dihydroxyspirochroman compounds which are suitable as the color image stabilizer (often referred to as a dye stabilizer) of color photographic materials.

FIGS. l-S show spectrum data concerning Compounds I and XVI.

The dihydroxyspirochroman compounds of the present invention are represented by the following Formula I:

wherein R is an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenoxy group, an aryloxy group, an acylamino group or an acylamino aralkyl group, each of which having one to 18 carbon atoms, R is a hydrogen atom, a halogen atom, an alkyl group an alkenyl group or an alkoxy group.

As the specific examples thereof, the following can be mentioned.

(Compound I) CH1 CH3 I OH; CH: C

6,6'-dihydroxy-7,7'-dimethyl-4,4,4,4'-tetramethyl-bis-2,2'-

spirochroman 3,764,337 Patented Oct. 9, 1973 4Ho(t) CH: CH:

6,6'-dihydroxy-7,7'-di-t-butyl-4,4,4',4'-tetramethyl-bis-2,2'-

spirochroman CH: C

CH5 OH:

CnHMt) 6,6-dihydroxy-7,7-di-t-amyl-4,4,4,4'-tetramethyl-bis-2,2'-

spirochroman CH3 CH3 CH3 CH 6,6'-dihydroxy-7,7 '-di-n-octyl-4,4,4',4'-tetramethyl-bis- 2,2-spirochroman v C1lH31(D) CH; CH:

HO O

- CH: CH:

(5151mm) 6,6'-dihydroxy-7,7-di-n-pentadecyl-4,4,4',4'-tetramethylbis-2,2'-spirochroman CH: CH;

O-- OH CH3 C 3 6,6'-dihydroxy-7,7-diphenyl-4,4,4',4'-tetramethyl-bis- 2,2'-spirochroman cm0H=cm CH: CH:

6,6-dihydroxy-7,7'-diallyl-4,4,4',4' tetramethyl-bis-2,2'- spirochroman (VIII) 6,6-dihydroxy-7,7'-dimethoxy-4,4,4',4' tetramethyl-bis- 2,2'-spirochroman 3 v 4 1 OCgHs (XVI) H.

H5020 Cm- 6,6-dihydroxy-7,7'-diethoxy 4,4,4',4' tetramethyl-bis- 2,2"splmchroman 6,6'-dihydroxy-7,7'-di-p-tolyl 4,4,4',4' tetramethyl-bis- 2,2'-spirochroman The above-mentioned dihydroxyspirochromans are new compounds and are prepared by the condensation CH, CH; of hydroquinone derivatives with acetone.

EXAMPLE OF SYNTHESIS 1 0 6,6-dihydroXy-7,7-dirnethyl-4,4,4,4-tetramethyl bis- CH; CH; 2,2-spirochromane A 5-liter three-necked flask provided with a stirrer and a reflux condenser Was charged with 620 g. (5.0 mols) of methyl hydroquinone, 1500 cc. of glacial acetic acid, 580 i g. (10.0 mols) of acetone, and 850 cc. of concentrated tetramethyl'bls hydrochloric acid sequentially. The resulting mixture was 'spu'ochroman heated under reflux in an oil bath under stirring. In 30 OCH=CH=CHI minutes, the reaction mixture turned black brown. The CH3 CH3 mixture was then continuously refluxed for 7 to 8 hours,

and then allowed to stand at room temperature. After a lapse of 5 days, the precipiated crystals were separated by 110 0 filtration, washed with water, and recrystallized from Q CH3 ethanol to form 170 g. of Compound I in the form of CHFCHCH colorless needle-like crystals. These crystals contained 1 6,6'-dihydroxy-7,7'-diallyloxy 4,4,4',4' tetramethyl-bismol of ethanol as crystal solvent. The crystals melt at 2,2'-spirochroman 145-149" C. to release ethanol, again solidifies, and then (XII) CH;

CHg-HNHC O CH;

CH: CH: CI-IgOOHNHSJHa 6,6 dihydroxy 7,7 di-B-acetylaminopropylt,4,4',4'- 4 melt at 203 to 206 C. When the crystals were recrystaltetramethyl-bis-2,2-spirochroman lized from hydrous ethanol, there was obtained a Com- CHQCH: NHCOCH; CH3 CH3 I O -OH Q CH: CH: CHtCONHQ-CHMJH:

6,6 dihydroxy 7,7' di-fi-(p-acetylaminophenyl)ethylpound I having a melting point of 203 to 206 C. free 4,4,4',4'-tetramethyl-bis-2,2-spirochroman from crystal solvent. (XIV) CH3 Cm Elemental analysis.Found (percent): C, 74.85; H,

CH3 CH3 1 l 7.59. Calculated (percent): C, 75.00; H, 7. 61.

The infrared absorption spectrum of the Compound I as measured by the KBr tablet method is shown in FIG. 1. HO The nuclear magnetic resonance spectrum of this compound as measured in heavy-hydrogenated acetone using E TMS as an internal standard is shown in FIG. 2. The observed chemical shift and area intensity of the signal gifigilgdroxy-4A ,4 ,7,7 ,8,8 octamethyl-bis-2,2 -sp1rosupport the above Structure. (XV) Cl Cm 1.28, l.54 p.p.m. (6H; of 4,4 gem. dimethyl groups, two

CH: CH equivalent methyl groups);

0H 2.08 p.p.m. (10H; methyl group at the 7,7-position, and

methylene groups at the 3,3'-position); Ho 6.31 p.p.m. (2H; hydrogen at 5,5'-position);

CH3 Cm 6.77 p.p.m. (2H; hydrogen at 8,8-position); and CH3 1 7.39 p.p.m. (2H; hydroxy group at 6,6'-position). 8,8'-dichloro-6,6'-dihydroxy-3,4,4',4,7,7'-hexamethyl-2,2'- The mass spectrum of the Compound I as measured spirochroman by the direct introduction methnd C.. 70 ev., 200

ua., IM 4 kv.) is shown in FIG. 3. Specifically, the parent ion peak (M+) 368 (C H O =368) was observed. The fragment ion peaks at m/e 353 (M CH rn/e 204, m/e 189 (m/e 204CH and rn/e 165 (m/e 353-m/e 189+H) were observed.

EXAMPLE OF SYNTHESIS 2 A mixture consisting of 60 g. (0.3 mol) of 2-p-tolylhydroquinone, 200 cc. of glacial acetic acid, 53 g. (0.9 mol) of acetone and 85 cc. of concentrated hydrochloric acid was refluxed for hours, and cooled to room temperature, followed by allowing to stand for 12 hours. The mixture was then slowly, poured into a great quantity of ice water to form a grey-white solid. The solid was fractionated, washed with cold water, dried, dissolved in ethanol, treated with activated carbon, and then allowed to stand to give light yellow crystals. When the crystals were recrystallized from ethanol, Compound XVI having a melting point of 293 to 296 C. in the form of fine crystalline powders was obtained in a yield of 14 g.

Elemental analysis.Found (percent): C, 80.63; H, 7.00. Calculated (percent): C, 80.75; H, 6.92.

The infrared absorption spectrum of the Compound XVI as measured by the KB'r tablet method is shown in FIG. 4. The mass spectrum of this compound measured by the direct introduction method (130 C., 70 ev., 200 ua., IM 4 kv.) is shown in FIG. 5. The parent ion peak (M+) 520 (C I-I O =520) was observed. Also, the fragment ion peaks at m/e 505 (M+CH m/e 280, m/e 265 (m/e 280CH and m/e 241 (m/e 505-m/e 265+H) were observed.

Other spirochromans are prepared by the same way.

Compound: Hydroquinone derivatives to be used in synthesis II Butylhydroxyquinone.

III t-Amylhydroxyquinone.

IV n-Octylhydroxyquinone.

V n-Pentadecylhydroxyquinone.

VI Phenylhydroxyquinone.

VII Allylhydroxyquinone.

VIII Methoxyhydroxyquinone.

IX Ethoxyhydroxyquinone.

X Phenoxyhydroxyquinone.

XI Aryloxyhydroxyquinone.

XII ,B-Acetylaminopropyl hydroxyquinone.

XIII B-AcetylaminophenyDethyl hydroxyquinone.

XIV 2,3-dimethyl hydroxyquinone.

XV 2-methyl 3-chloro hydroxyquinone.

The dihydroxyspirochroman compounds of the present invention are very effective as the color image stabilizer for color photographic materials.

The present invention relates to color photographic materials containing the dihydroxyspirochroman compounds represented by the above-mentioned Formula I as the color image stabilizer and particularly to color photographic materials that provide a color image which, even if exposed to light, is difficult of fading.

In order to transform a distribution of light into the corresponding distribution of dyes with use of silver halide as a photo-sensitive material, grains of silver halide exposed to light using a primary aromatic amine are developed and dyes are formed from the resulting oxidation product of said amine by means of a coupling reaction.

The active compound participating in the coupling reac-;-

tion in this instance is called a coupler. The dyes formed belong to the classes of indophenols, indoanilines, azomethines, indamines and azines. There are two methods of supplying couplers, one is to supply from the developer solution a coupler which is capable of diffusing into the inside of the layer of emulsion and another method is to add a diffusion-fast coupler to the emulsion during the process of manufacture of the photographic material. The

photographic material to be used for the former is called external type and that for the latter is called incorporated type.

The color photographic material to be used for color photography by the subtractive color process has usually those emulsion elements on the same support which sensitize themselves selectively to the lights of blue, green and red. These emulsion elements provide respective color images of yellow, magenta and cyan in the color development using a primary aromatic amine as a developing agent.

As the couplers providing a magenta color image are known S-pyrazolones, pyrazolobenzimidazoles, indazolones and 2-cyano-acetyl-cumarones. Of them S-pyrazolones are the most widely used.

The magenta color image obtained from 5-pyrazolones fades, if exposed to a strong light over a prolonged period of time. This fading of the magenta color image due to light has been impedient to the use in case color photographs require to be preserved in a stable way without any change over a long period of time.

Some expedients have been so far tried with a view to making the magenta color image obtained from S-pyrazolones fast to lights. They are, for example, means of incorporating ultra-violet absorbents into color photographic materials to protect the color image from the ultra-violet rays, for making the dye itself fast to light by making a proper selection of the structure of the coupler or of using color dye stabilizers to prevent the decomposition of the dyes to be caused by light.

As the dye stabilizers for the color image of the color photography, there have been proposed some compounds having phenolic hydroxyl radicals.

(i) In the specification of each of the US. Pats. No. 2,336,327, No. 2,360,290, No. 2,403,721, No. 2,418,613, No. 2,704,713, No. 2,728,659, No. 2,732,300 and No. 2,735,765 is mentioned the addition of alkyl hydroquinones of the following description to a layer of photographic emulsion and some of them are said to have effects for the stabilization of the color image.

2,5-di-n-octylhydroquinone.

HsC

2-methyl-5-octadecyl-hydroquinone.

CHa- 3 CH CH 2,5,7,8-tetramethyl 2 (4-,8',12'-trimethyltridecyl)-6- hydroxychroman.

7 (iii) The specification of US. Pat. No. 3,432,300 discloses the use of the hydroxychroman derivative of the following formula as color image stabilizer.

CH3 CH3 2,2-4-trimethyl 7-t-octyl-6-hydroxychroman.

(iv) In German patent publication No. 2,008,376 it is mentioned to the effect that the color image is rendered fast to light by use of the following S-hydroxychroman derivatives:

hydroxy-Z-(N-n-butyl-anilino) 3 methyl-fi-t-octylcoumaran.

(t) CQHQ 0 CH3 Z-(N-anilino)-6-t-butoxy-5-hydroxy 3 3,4 trimethyl coumaran.

These known compounds, however, were far from satisfactory, in that they had any one of the defects of limiting the effect of light fastness to the color image obtained from the S-pyrazolone coupler, decreasing the color developing density of the coupler with the resulting decrease in photographic sensitivity and assuming colors during the processing to contaminate the color photograph.

An object of the present invention is to provide color photographs of a small degree of fading and particularly of good light-fastness.

Another object of the present invention is to provide color photographic materials which are capable of giving stable color image of a small degree of fading.

The compounds of the present invention is to provide new dye stabilizers which make magenta color image obtained from the S-pyrazolone coupler fast to light.

Still another object of the present invention to provide color photographic materials containing new color image stabilizers which make the magenta color image fast to light.

These objects of the present invention can be attained by impregnating the newly discovered phenolic hydroxyl radical-containing spiro compounds indicated by the general Formula I as color image stabilizer in the emulsion elements which provide magenta dye from the 5-pyrazolone coupler of the color photographic material. And all of Compound I-XV exemplified as the example of the dihydroxy spirochroman compounds represented by the Formula I described are excellent stabilizing agents for magenta color images, having the characteristics of the following description in comparison with the conventionally used ones mentioned previously.

(1) The dihydroxyspirochroman compounds decrease greatly the degree to which the magenta color image obtained from a pyrazolone coupler is faded upon exposure to light. In comparison with the dye stabilizer known in the past, they can show an equivalent efiect in smaller quantities.

(2) The dihydroxyspirochroman compounds to be used in the present invention are very stable in themselves and do not lend themselves to the color forming reaction or do not give rise to coloring during the color development with use of aromatic primary amino compounds and also in a bleach bath containing a strong oxidizing agent such as ferricyamide or oichromate. They, even when left in the color photograph after processing, do not cause any taint.

(3) The dihydroxyspirochroman compounds to be used in the present invention inhibit the undesirable change of the S-pyrazolone couplers to light or heat.

(4) The dihydroxyspirochroman compounds to be used in the present invention are readily soluble in organic sol vents and can be incorporated readily and stably into the color photographic material.

(5) These dihydroxyspirochroman compounds can be synthesized readily in one step from cheap starting materials which are easily available.

(6) These compounds do not exert any adverse elfect on the photographic emulsion in which they are incorporated and do not interfere with the color formation of the pyrazolone coupler.

On the other hand, the magenta coupler to be used in the present invention can be selected from a Wide range of structures. Of those structures, the S-pyrazolone compounds that yield a particularly excellent result when used with the dihydroxyspirochroman compounds of the structural Formula I mentioned earlier belong to the groups represented by the following structural Formulas II and III.

In the foregoing formulae, R is an aryl group or a substituted aryl group. As the substituent group for the aryl group there is useful an alkyl group, aryl group, alkoxyl group, aryloxy group, alkylthio group, arylthio group, halogen atom, trifiuoromethyl group, cyano group, acyl group, sulfonyl group, acylamino group, sulfonamino group, ureido group, amino group, carboxyl group, alkoxycarbonyl group or carbamyl group, and particularly a phenyl group substituted by these substituent groups is excellent as R R is an alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, aryl group, substituted aryl group, amino group, substituted amino group, acylamino group, substituted ureido group, sulfonamide group or alkoxy group, and R is a lower alkyl group or aryl group.

X represents those radicals which can be split ofi by the oxidation product of the primary aromatic amino developing agent, for instance, a hydrogen atom, halogen atom, cyano group, arylthio group, aryloxy group, arylazo group, heteroazo group and acyloxy group.

l R4 Structural Formula III radical of 830 carbon atoms. This hydrophobic radical tends to enhance the afiinity between the coupler molecules as well as between the coupler molecules and the coupler-solvent molecules and keeps the coupler in the interior and in the vicinity of the solvent particles keeping the close contact with each other. This hydrophobic radical further affords aflinity for the coupler solvent to the dyes derived from it and also tends to strengthen the effect of the coupler solvent. This hydrophobic radical is contained in R or R being linked with the coupler radical either directly or indirectly through a di-valent organic radical having an amino bond, ether bond, ester bond, urea bond or sulfonamide bond.

The useful hydrophobic radical for the present invention is selected from straight-chain or branched alkyl groups, alkenyl groups, alkoxyalkyl groups, alkoxyaryl groups, aryl groups, aryloxyalkyl groups, aryloxyaryl groups, and acylaminoalkyl groups. Specific examples of the hydrophobic radical include:

(vlll) Y CIHB tert- 04H 0 43H- tert- 0 4H (X) nC1 H|1-C N-CHzCHr- In putting the present invention into practice, a dispersion product in which a dihydroxyspirochroman compound has been emulsified may be added to 'a photographic emulsion of silver halide separated containing a diffusion-fast pyrazolone coupler, or the diffusion pyrazolone coupler and dihydroxyspirochroman compound are dissolved in one and the same solvent to form a mixed solution which is then dispersed in an aqueous medium, and the resultant dispersion is added to the photographic emulsion.

The amount of the dihydroxyspirochroman compound to be used in the present invention varies with the purpose for which the color photographic material is to be used, the type of the 5-pyrazolone coupler and also the structure of the dihydroxyspirochroman compound to be used, but the amount in the range of 0.05 mol-5.0 moles per mol of the 5-pyrazolone coupler is effective and particularly that of 0.1 mol2.0 mols is preferable.

Specific examples of the S-pyrazolone compounds to be used in the present invention with particularly satisfactory results are as follows:

Melting Coupler point, C.

A Cl 82-4 /N=CC11 u 01 N\ (3-0 H: 01 II O B /N=CC11 as 121 /N=C C OiaHn C-C H2 7 /N=C 0 C18H|1 01 N\ I C-CH: 01

/N=CNH NH0 0 CHaO- CrHnUZ) (1H (t) I C a in C1 ll F CsHnUJ) 172 amgmmg (QM c-cm The dihydroxyspirochroman compounds represented by Structural Formula I display, as said before, a marked elfect on stabilization for the azomethine dyes derived from the incorporated couplers having a -pyrazolone ring and sometimes show an effect on stabilization also for the color images derived from magenta forming couplers of other structures, for instance, from pyrazolobenzimidazoles, indazolones or 2-cyanoacetylchromans.

Furthermore, the dihydroxyspirochroman compounds to be used in the present invention sometimes exhibit the effect of improving the light-fastness also for the color images induced from the yellow color forming couplers consisting of acylacetoanilides and cyan forming couplers consisting of phenols or alpha naphthols.

The dihydroxyspirochroman compounds to be used in the present invention dissolve readily in many organic solvents. These comopunds are dispersed finely in an aque ous medium after being dissolved in an organic solvent. The emulsion so obtained is then added to the photographic emulsion. One embodiment of the present invention is to mingle the dihydroxyspirochroman compounds With oil-soluble S-pyrazolone couplers and then to disperse the mixture in the said medium or to add the dye stabilizer and the coupler separately in the form of a solution or a dispersion to the emulsion.

A Wide range of organic solvents are used for the purpose of adding the coupler and the dye stabilizer to be used in the present invention to the photographic emulsion, but particularly suitable for this purpose are those described in the following:

(1) Substantially Water-insoluble and non-volatile solvents having a boiling point of not lower than 200 C. at normal atmospheric pressure. For instance, di-n-butyl phthalate, tri-o-cresyl phosphate, tri-n-hexyl phosphate, N, N-diethyl caprylamide, di-n-butylsuccinate, p-nonylphenol and chlorinated parafiins.

(2) Partially water-soluble and volatile solvents having a boiling point of not higher than 120 C. at normal atmospheric pressure. This kind of solvent is virtually all removed during the process of manufacture of the photographic material. 'For instance, ethyl acetate, cyclohexyl alcohol and cyclohexanone can be named.

(3) Solvents miscible with water. This type of solvent is removed during the process of manufacture of the photographic material by means of rinsing or dialysis. For instance, methanol, ethanol, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, dimethyl sulfoxide, dimethylformamide, hexamethyl phosphoryl amide and methyl Cellosolve can be mentioned.

These dihydroxyspirochroman compounds dispersed in an aqueous medium for photographic use are not soluble in water and further are not soluble either in other processing solutions including developing agents of a high pH value for use in the photoprocessing, and it never happens that they are lost by flow during the processing or that they are diffused into other layers of the photographic material.

In order to put the present invention to practice, only one dihydroxyspirochroman compound shown by the general Formula I may be used singly, or more than one compound of the same structural formula may be used in combination. Further, the use of the said compound in conjunction with dye stabilizer other than those represented by the general Formula I can even more increase the dye stabilizing effect of the present invention.

For example, alkyl hydroquinones disclosed in the specification of U.S. Patents No. 2,336,327, No. 2,403,721 and No. 2,728,659 are the compounds that are suitable to be used conjointly with dihydroxyspirochromans expressed by general Formula I. As a consequence, not only the magenta color image formed from the pyrazolone coupler is rendered markedly fast to light, but also the pyrazolone coupler remaining in the color photographic material after processing can be effectively prevented from yellowing or staining upon exposure to heat or light. Among the specific examples of such compounds are 2,5-di-t-octylhydroquinone, 2,5-di-n-octylhydroquinone, Z-methyl-S-t-octylhydroquinone and 2-methyl-5-n-octylhydroquinone.

The use of an acid buffer solution as the final bath for the processing of the photographic material of the present invention is preferred to further improve the preservability of the image. This is exemplified in the specification of patent application No. 82,769-1970.

For color processing of the photographic material containing the dihydroxyspirochroman compounds of the present invention, there can be used conventional known general methods. Substituted p-phenylenediamines are used for color development to make a color image and a silver image and the silver is oxidized to silver salt in the subsequent bleach bath. This is then followed by removing the remaining silver halide and other silver salts by dissolving in a fixing bath to thereby retain only the color image.

When the magenta color image obtained from a diffusion-fast 5-pyrazolone is processed in a bleach bath containing a strong oxidizing agent such as a bichromate and ferricyanide, it becomes liable to fade upon exposure to light. On account of this, the magenta color image processed in a bleach bath containing a weak oxidizing agent and a strong silver complex forming agent, for instance, thiosulphate and a mixture of ethylene diamine tetraacetic acid with a ferric salt, is fast to light, and the use of such a bleach bath of weakly oxidizing nature is particularly useful for the practice of the present invention.

As the p-phenylenediarnine derivative to be used for the processing of the color photographic material of the present invention, many compounds that have been previously known can be used. Specific examples include N,N-diethyl-p-phenylenediamine,

N,N-diethyl-3-methyl-4-amino-aniline,

N-ethyl-N- (fi-hydroxyethyl -p-phenylenediamine,

N-ethyl-N-( ,B-hydroxyethyl -3-methyl-4-aminoaniline,

N-ethyl-N-(fi-methylsulfonamide ethyl)-3-methyl-4- amino-aniline,

N,N-diethyl-3-(p-methylsulfonamide ethyl)-4-aminoaniline, etc.

The color photographic material of the present invention proves advantageous if it is processed with aldehydes like formaldehyde either during or after the color development processing. This not only serves to harden the hydrophilic film of the color photographic material, but improves the heat resistant property of the color image as well.

It is advantageous to have the color photographic material of the present invention processed in a stabilizing bath in the final stage of the color development processing. This bath contains an acid substance, a substance soluble in water having the action to stabilize the color image, an ultra-violet absorbent and a fluorescent whitening agent. As the color image stabilizing agent to 'be added into the stabilization bath, hydroquinone or its substituted derivatives, urea or its substituted derivatives and p-alkoxyphenol or its substituted derivatives are useful.

It is of advantage that the color photographic material of the present invention should contain a substance which does not practically absorb visible rays, but strongly absorbs ultra-violet rays. Such an ultra-violet ray absorbing material protects the color image and the residual coupler from the action of ultra-violet rays after the color development processing and further presents the color photograph from yellowing, staining or fading. The dihydroxyspirochroman compound to 'be used in this invention particularly effectively prevents the color image protected by the ultra-violet absorbent from fading due to light. As the ultra-violet absorbent particularly suitable for use in the practice of the present invention in the specific form, stilbene derivatives (see, for instance, pat. pub. No. 9,585-1970 or pat. pub. No. 9,586l970), Z-arylimino- 3 arylmethylenethiazolidone or 2 arylimino 3-alkylheteromethylenethiazolidone (see pat. pub. No. 29,627-1969) and 2 benztriazolyl 4 alkylphcnols (such as those specified in the specification of pat. appln. NO. 19,299-1968) are particularly useful.

The present invention applies to various types of color photographic materials. Namely, it is used for color negative films, color positive pictures, color photographic paper, color reversal and color films for enlargement display (for instance, Fuji Color G Print).

The support of the color photographic material of the present invention can be made from various materials and in various forms.

Plates made of glass or plastics, soft flexible sheets or paper of cellulose acetate, polyethylene terephthalate or poystyrene or resin-coated paper can be used.

The photographic emulsion to be used to put the present invention to practice is that in which silver halide is dispersed in fine grains in the hydrophilic colloid, and a suitable silver halide is silver chloride, silver bromochloride, silver bromide or silver iodobromide. Suitable hydrophilic colloids include Water soluble polymers such as gelatin, polyvinyl alcohol, polyvinyl pyrolidone, polyacrylamide, polyacrylamide subjected to the Hofiman re action and co-polymers of acrylic acid, acrylamide and N-vinylimidazole.

In the following, the present invention will be explained specifically and in detail on the basis of the working examples.

EXAMPLE 1 17 grams of 1 (2,6 dichloro 4' methoxy)- phenyl 3 [3" (oz-(2 4"'-di-t-amylphenoxy)butylamide)benzamide] 5 pyrazolone (examplified compound O) as the magenta coupler, dye stabilizers (types and quantities shown in the following table) and the solution obtained by heating 34 grams of tricresylphosphate and 30 milliliters of ethyl acetate were mixed with an aqueous solution at 50 C. containing 1.0 gram of sodium dodecylbenzeuesulfonate and 25 grams of gelatin, and

Stop-fixing bathProcessing 2:

Ammonium thiosulphate120.0 grams Sodium metabisulphite20.0 grams Glacial acetic acidl0.0 grams Water to make 1 liter pH 4.5.

Bleaching bath-Processing 4:

Potassium nitrate-25.0 grams Potassium ferricyanide--20.0 grams Potassium bromide-8.0 grams Boric acid-5 .0 grams Borax-2.5 grams Water to make 1 liter pH 7.2.

Hardening and fixing bath-Processing 6:

Ammonium thiosulphate120.0 grams Sodium sulphite5 .0 grams Boric acid2.5 grams Formalin, 38%-40.0 milliliters Water to make 1 liter pH 9.5.

These developed samples were exposed to light from a fluorescent lamp of the daylight type for 10 days through a filter (Fuji Film Filter UV-400) which absorbed practically all ultraviolet rays of a wave length shorter than 400 microns. The luminosity of the irradiated light at that time was 10,000 luxes. The change in the green density (fading of the magenta dye image) and the blue density (yellowing in the highlight areas) were measured both before and after exposure to light. The results obtained are shown in the following table.

TABLE 1.CHANGES OF DEVELOPED SAMPLES WITH THE IRRADIATION OF LIGHT Degree of fading Contamination of the magenta in the highlight dye image 1 areas 2 Dye sensitizers Period of light irradiation Quantity Samples Type (g.) 5 days 10 days 10 days Comparison N at added 0 0. 35 0. 67 0. 10 1 Compound I of the present invention 3. 0.09 0. 18 0. 08 2 Compound II of tall same Com an on Known om oun 60.? do 0 p 6.8 0.10 0. 20 0.09

Decrease of green light density, initial density=1.0.

2 Increase of blue light density.

3 2,2,4-trin1ethyl-7-t-octyl-fi-hydroxychroman.

Color development processing: Minutes (1) Color developer 7 (2) Stop-fixing bath 2 (3) Washing 2 (4) Bleaching solution 2 (5) Washing 2 (6) Hardening and fixing bath 2 (7) Washing 2 (8) Drying 2 It will be found from the results indicated in the foregoing table that the compounds of the present invention are all capable of strongly preventing the magenta dye image from fading and that their improving surpasses that of dye stabilizers so far known. Still more, the compounds of the present invention can effectively prevent the unused residual coupler in the image dye formation from yellowing or staining upon exposure to light or heat and accordingly it is evident that they can improve the dye image stabilities and lengthen the duration time of the color photograph.

EXAMPLE 2 On a paper support having a polyethylene layer on a surface, which was rendered hydrophilic, were coated in a first layer (with a dry film thickness of four microns) a blue-sensitive emulsion layer containing ot-(4-methoxybenzoyl)-[2'-chloro 5 (2",4" di-sec-amylphenoxyacetamide)] acetanilide as the yellow coupler and in a second layer (one micron) an intermediate layer consisting of gelatin.

set forth in Example 2, the following hydroquinone derivatives were further added in addition to the coupler, solvent and dye stabilizer. In all other points the example was practiced as it was and the results given in the following table were obtained.

TABLE 3.COJOINT IMPROVING EFFECTS BY DIHggBEgigISgoCfiROMAN DERIVATIVES AND HYDROQUINONE (Light irradiation time: 20 days) Dye stabilizer Hydroquinone derivative Degree of fading of the Staining of Quantity Quantity magenta dye highlight Sample Type (g.) ype (g image 1 area 2 5 Compound I of the present invention 6. 4. 2,5-di-t-octylhydroquinone. 3. 2 0. l4 0. 6 Compound II of the same 6. 4 d0 3. 2 0. 14 0. 11 7... Compound I of the same 6. 4. 2,6-di-n0ctylhydroquinone" 3. 2 0. 12 0. l2 8 Compound II of the same 6.4 .do 3. 2 0. l3 0. 13

1 Decrease of green light density with initial density used as 1.0.

2 Increase of blue light density. phosphate, 50 milliliters of acetate and the following dye stabilizers were added to 700 milliliters of aqueous solution containing 45 grams of gelatin and 3.0 grams of sodium dodecyl-sulphate and stirred. The solutions were given a violent mechanical stirring in a high speed mixer for 30 minutes. As a result, the coupler and the dye stabilizer were finely dispersed in the solvent. All of the emulsified dispersion solution was added to one kilogram of a green sensitive photographic emulsion containing 0.27 mol of silver iodobromide and 70 grams of gelatin. After 50 milliliters of an acetone solution of 3% triethylene phosphamide was added as the hardening agent, the photographic emulsion was coated as the third layer of the above color photographic paper to a dry film thickness of three microns.

On the foregoing layer as put, as a fourth layer, a gelatin layer containing Z-benzotriazo-4-sec-butyl-6-tbutylphenol as an ultraviolet absorbent to a dry film thickness of two microns. A red-sensitive emulsion layer containing 1-hydr0xy-4-chloro-2-dodecylnaphthamide as the cyan coupler to a dry film thickness of three microns and one micron thick gelatin layer as a protective layer were then applied to complete the color photographic paper.

The color photographic paper was exposed stepwise to green light and subjected to the color development processing in a way similar to that of Example 1 to obtain a magenta dye image which had a gradationally varying degree of color density.

The developed samples were directly exposed to light of a luminosity of 10,000 luxes from a fluorescent lamp of the day light type, and the results reported in the following table were obtained.

If these results are compared with those of Table 2, it will be clear that when the compounds of the present invention, namely dihydroxyspirochroman compounds, are used in combination with alkyl hydroquinone they effectively prevent the fading of the magenta dye image and concurrently the contamination of the highlight area.

EXAMPLE 4 On a film base consisting of cellulose triacetate were placed as a first layer a red sensitive emulsion layer containing the sodium salt of l-hydroxy-4-sulfo-2-octadecylnaphthoamide as a cyan forming coupler to a dry film thickness of five microns and as a second layer a 1.5 micron thick gelatin intermediate layer, one after another.

The solution obtained by dissolving the dye stabilizers and hydroquinone derivatives shown in Table 4 in 10 milliliters of tri-o-cresylphosphate and 1.0 milliliter of ethyl acetate at 50 C. was added to 200 milliliters of an aqueous solution containing 15 grams of gelatin, 0.5 gram of sodium p-dodecylbenzene sulphonate and 0.5 gram of sodium bisulphite, and stirred. By a violent mechanical stirring by means of a high speed mixer for 30 minutes, they were finely dispersed. The emulsified dispersion solution was added to one kilogram of a green sensitive emulsion containing 0.27 mol of silver iodobromide and 70 grams of gelatin. It was then added to an aqueous solution containing 21.8 grams of l-phenyl- 3[ (a oleylsuccinamide)benzamide] 5 pyrazolone exemplified compound A) and 1.5 grams of sodium hydroxide, and the pH value of the emulsion was adjusted to 6.0 with an aqueous solution of 5% acetic acid. To this solution were added 20 milliliters of an aqueous TABLE 2.FADING OF MAGENTA DYE IMAGES AND STAINING OF THE HIGHLIGHT AREA; IRRADIATION OF LIGHT TO DEVELOPED SAMPLES Dye stabilizer dye image 1 highlight area" Period of time of light irradiation Quantity Sample Type (g.) 10 days 20 days 20 days Comparative.--. Not added 0 0. 31 0. 45 0. 25 3 Compound I of the present invention- 6. 4 0. 09 0. 17 0. 14. 4. Compound H of the same..- 6. 4 0. 08 0. 17 0. 14 Comparative Known compound a 12. 8 0. 10 0. 20 0. 17

l Decrease of green light density with initial density used as 1.0.

2 This is the absolute value of the blue density measured by blue filter.

5 Increase of blue light density.

As is apparent from the foregoing results, the comsolution of 4% sodium salt of l-hydroxy-3,5-dichloro-5- pounds of the present invention are both capable of strongly preventing the magenta dye image from fading and their improving effects are stronger than those of the conventionally known dye stabilizer. It was further ascertained that the compounds of the present invention efiiectively prevent the highlight area of the color print from yellowing upon exposure to light.

EXAMPLE 3 In preparing the coupler emulsified dispersion solution triazine as the hardening agent, which was then applied to the above color film base as the third layer to a dry film thickness of five microns.

On the third layer of the film were further placed a gelatin layer containing a yellow colloid to a dry film thickness of two microns, a blue sensitive layer containing the 2Na salt of o:-(4-oleyl-succinamidobenzoyl)-2'-meth oxy-S-carboxy-acetoanilide as the yellow coupler as a fifth layer to a thickness of six microns and a gelatin to be added to the green sensitive emulsion in the manner containing a high molecular weight ultra-violet absorbent having the following structure to a thickness of 2.5 microns to complete the color film.

NaOaS 2- aNa (m represents a large positive whole number.)

This film was exposed stepwise to green light and then processed in the color developing solution of the following composition at 20 C. for 18 minutes.

Color developing solution:

Grams N,N-diethyl-p-phenylenediamine sulphate 2.8 Sodium sulphite 2.5

Sodium carbonate 65.0 Hydroxylamine hydrochloride 1.0 Potassium bromide 1.2 Water-1,000 milliliters.

This was followed by washing at 17 C. for two minutes, processing in the bleaching and fixing solution of the following composition at 20 C. for five minutes and finally by washing in running water at 17 C. for minutes, to obtain a magenta image.

Potassium bromide Potassium thiocyanate Waterone liter.

The color developed samples were exposed to light of a luminosity of 50,000 luxes from a xenon lamp (which was passed through a heat-absorbing filter) for three days. The results given in the following table were obtained.

taining 0.5 gram of sodium cetylsulphate and 5.0 grams of gelatin. They were given a violent mechanical stirring in a homoblender to disperse them.

Dispersion solutions of dye stabilizers: The solutions obtained by dissolving the dye stabilizers described in Table 5 in a mixed solvent consisting of two milliliters of di-n-butyl phthalate and five milliliters of ethyl acetate were added to 30 milliliters of an aqueous solution containing 0.1 gram of sodium cetylsulphate and 2.0 grams of gelatin. They were dispersed by violent mechanical stirring in a homo-blender.

These film samples were sensitometrically exposed and processed as set forth in Example 1 to form magenta dye images and subjected, behind an ultra-violet absorbing filter, to light irradiation of a luminosity of 10,000 luxes from a fluorescent lamp for 10 days to determine the fading of the dye images. The results given in Table 5 were obtained.

As indicated in the following table, the dihydroxyspirochroman compounds to be used in the present invention make the azomethine dye image induced from 5- pyrazolone couplers having various substituent groups fast to light.

TABLE 5.FADING OF MAGENTA DYE IMAGES FADING OF MAGENTA DYE IMAGES UPON EXPOSURE TO LIGHT Magenta coupler Dye stabilizer Degree Quantity Quantity of Sample Type (g.) Type (g.) fading 1 4. 52 Not added. 0 0. 27 4. 52 L.-- 0.5 0. 09 4. 52 0. 5 0.10 4. 52 0. 5 0.12 5. 80 0 0.70 5. 80 0. 6 0. 25 5. 80 I 0. 6 0.19 5. 11 0 O. 5. 11 0. 5 0. 10 5. 11 0. 5 0. O8 6. 15 0 51 6. 15 0. 6 0. 15 6.15 0.6 0. 18

1 Decrease of green light density with initial density used as 1.0

TABLE 4.FADING OF MAGENTA DYE IMAGES AND STAINING OF HIGHLIGHT AREA WITH THE IRRADIATION OF LIGHT Dye stabilizer Hydroquinone derivative Degree of Contaminafading of tion of Quantity Quantity the magenta highlight Sample Type (g.) Type (g.) dye image 1 area 1 Com arative Not added 0 Not added 0 0.55 0.15 9""? Compound I of the present invention- 2. 2 2,5-di-t-octylhydroqu1n0ue 0 0. 12 0, 09 10 Compound I of the same 2. 1. 1 0.09 0. 05 11 Compound II of the same 0 0.11 0. 10 12 do 1. 1 0. O7 0. 07

l Decrease of green light density with initial density used as 1.1. I Increase of blue light density.

dro quinone.

EXAMPLE 5 To 200 grams of an emulsion containing 0.27 mol of silver iodobromide and 70 grams of gelatin in one kilogram thereof were added the following magenta coupler dispersed solutions and dye stabilizer dispersed solutions. After the further addition of three milliliters of an acetone solution of 3% triethylene phosphamide thereto, they were coated on a polyethylene terephthalate film base to a dry film thickness of five microns. Coupler dispersed solutions: The couplers mentioned in Table 5 were dissolved by reflux in 10 milliliters of tri-n-hexylphosphate and 15 milliliters of ethyl acetate. The solution obtained was added to 70 milliliters of an aqueous solution con- CH3 CH3 CH3 CH I l R1 R2 wherein R is an alkyl group, alkenyl group, aryl group, alkoxy group, alkenoxy group, aryloxy group, acylaminoalkyl group or acylaminoaral-kyl group having not more than 18 carbon atoms, and R is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group or an alkoxy group.

2. A color photographic material as in claim 1, wherein said color image stabilizing agent is selected from the group consisting of 6,6'-dihydroxy-7,7-dimethyl-4,4,4',4'-tetramethylbis-2,2'-spirochroman, 6,6'-dihydroxy-7,7'-di-t-butyl-4,4,4',4'-tetramethylbis-2,2-spirochroman, 6,6'-dihydroxy-7,7-di-t-amyl-4,4,4',4-tetramethylbis-2,2'-spirochroman, 6,6'-di-hydroxy-7,7'-di-n-0ctyl-4,4,4',4'-tetramethylbis-2,2'-spirochroman, 6,6'-dihydroxy-7,7-di-n-pentadecyl-4,4,4',4'-tetramethyl-bis-2,2'-spirochroman, 6,6-dihydroxy-7,7'-di-phenyl4,4,4,4-tetramethylbis-2,2-spirochroman, 6,6'-dihydroXy-7,7diallyl-4,4,4', '-tetramethyl-bis- 2,2-spirochroman, 6,6-dihydroxy-7,7'-dimethoxy-4,4,4',4'-tetramethylbis-2,2'-spirochroman, 6,6'-dihydroxy-7,7'-diethoxy-4,4,4', '-tetramethyl-bis- 2,2-spirochroman, 6,6'-dihydroxy-7,7'-diphenoxy-4,4,4', -tetramethy1 bis-2,2'-spirochroman, 6,6'-dihydroxy-7,7'-diallyloxy-4,4,4',4'-tetramethylbis-2,2'-spirochroman, 6,6'-dihydroxy-7,7'-di-,8-acetylaminopropyl-4,4,4',4-

tetrarnethy1-bis-2,2'-spirochroman, 6,6'-dihydroxy-7,7'-di- 3-(p-acetylaminophenyl)ethyl- 4,4,4,4'-tetramethyl-bis-2,2'-spirochroman, 6,6-dihydroxy-4,4,4,4',7,7,8,8'-octamethylbis-2,2-

spirochroman, and 6,6'-dihydroxy-7,7'-di-p-tolyl-4,4,4',4-tetramethy1-bis- 2,2'-spirochroman.

3. A color photographic material as in claim 1 wherein the amount of said color image stabilizing agent is 0.05 to 5 mols per mole of the 5-pyrazolone coupler.

4. A color photographic material as in claim 2 wherein the amount of said color image stabilizing agent is 0.1 to 2 mols per mol of the 5-pyrazolone coupler.

5. A color photographic material as in claim 1 wherein said silver halide is selected from silver chloride, silver bromochloride, silver bromide, and silver iodobromo chloride.

6. A color photographic material as in claim 1 wherein an alkyl hydroquinone selected from 2,5-di-t-octylhydroquinone, 2,S-di-n-octylhydroquinone, Z-methyl-S-t-octylhydroquinone and Z-methyl-S-n-octylhydroquinone is further included.

7. A color photographic material as in claim 1 wherein stilbene derivatives, 2-arylimino-3-arylmethylene-thiazoline, 2-arylimino-3-alkyl-S-heteromethylene-thiazoline and 2-benzotriazolyl-4-alkylphenol are further included as an ultraviolet absorbing agent.

References Cited UNITED STATES PATENTS 3,432,300 3/1969 Lestina et a1 96-56 3,519,429 7/ 1970 Lestina 96-100 3,574,627 4/1971 Stern et a1. 96-56 3,698,909 10/ 1972 Lestina et al 96-56 I. TRAVIS BROWN, Primary Examiner US. Cl. X.R.