US2976146A

US2976146A - Novel cyan-forming couplers

Info

Publication number: US2976146A
Application number: US776699A
Authority: US
Inventors: Ilmari F Salminen; James A Van Allan
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1958-11-28
Filing date: 1958-11-28
Publication date: 1961-03-21
Anticipated expiration: 1978-03-21
Also published as: FR1242475A; GB935698A

Description

innate United SW68 Patent O" 2,976,146 NOVEL CYAN-FORMING COUPLERS Ilmari F. Salminen and James A. Van Allan, Rochester,

N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Nov. 28, 1958, Ser. No. 776,699

7 Claims. (Cl. 96-55) This invention relates to photographic color-forming or coupling compounds and their use in developer compositions for developing colored photographic images.

The use of color-forming compounds which react with the development product of primary aromatic amino developing agents to form color images on photographic development is well known and has been the subject of numerous prior patents. The dyes formed in this way usually are insoluble in water and in the ordinary photographic developing and fixing baths, although the silver images formed simultaneously with them during the photographic development may be removed from the photographic layer to leave pure dye images in the layer. The coupler compounds used in this way may be added to the developing solution or in certain cases may be incorporated in the photographic layer prior to exposure.

The coupler compounds generally used for subtractive color photography form, upon color development, yellow, magenta or cyan dyes. In order to be useful for color photography, the dyes produced upon color development must have certain desirable light transmission or spectrophotometric characteristics. Thus, ideally, the cyan or blue-green dye should absorb red light completely and transmit blue and green light completely. It should retain these transmission characteristics over a long period of time and should withstand reasonable exposure to heat and light without appreciable fading or loss of these light transmission characteristics. The other dyes should also exhibit selective absorption and transmission characteristics.

Many of the available couplers, however, have been found not to produce dyes having these characteristics to the desired degree.

Additionally, if the coupler compounds are to be incorporated in developing solutions they must be surficiently soluble and reactive so that the amounts used will produce sufficiently high dye densities in the resulting photographic image.

It is therefore an object of the present invention to provide a novel class of cyan-forming couplers for use in color photography. A further object is to provide new and improved color-forming couplers which are useful in color developer solutions containing a primary aro matic amino developing agent. A still further object is to provide new couplers which upon color development with primary aromatic amino developing agents produce cyan dye images Which combine good light transmission characteristics and good dye stability to an unusual degree. Other objects Will become apparent from the description of our invention.

These and other objects are accomplished by means as described hereinafter.

We have discovered that certain phenols and a-naphthols having a heterocyclic group in the 2-position give indoaniline dyes having good light transmission characteristics and excellent dye stability. The good transmission characteristics are unexpected since previous experience with other phenols and u-naphthols having hetero- Patented Mar. 21, 1961 cyclic groups in the 2-position would lead one to expect dyes with absorption maxima in the near infrared region of the spectrum. The couplers of Frohlich et al. U.S. Patent 2,373,821, for example, produce dyes that have a specially high light absorption in the infrared region of the spectrum with maximum light absorption in the 700 to 730 m range. .Our couplers produce dyes that have maximum light absorptions in the region of wavelengths from 596 to 680 mu.

In accordance with the invention, we use as cyanforming couplers, compounds of the formula:

lit-C N i e wherein Z is a combination of non-metallic atoms necessary to form either unsubstituted or substituted heterocyclic triaza rings; Ar--OH is a phenol or an a-naphthol group substituted at the carbon in the 2-position with the triaza ring and at the carbon in the 4-position with R which may be a hydrogen atom, a halogen atom such as a chlorine atom, or a sulfo radical. When R is a sulfo group on an a-naphthol nucleus, the sulfo group is usually attached on the carbon in the 6 position as Well as the carbon in the 4 position.

More specifically, the preferred compounds of our invention have the formula:

aromatic amino. developing agents, sodium 'sulfite and the other chemicals commonly used in color developer solutions.

Color developers containing our couplers develop ,ex-

posed photographic emulsions to produce cyan dyeimages having good spectrophotometric characteristics-with maximum light absorption in theregion of wavelengths from 680 to 596 11111.. These good spectrophotometric characteristics are retained by the dye images over long periods of time. The dye images from our couplers are more's'table upon exposure to heat and light than are the dyes from some commercially used couplers. These very desirable characteristics make our couplers particu-' larly valuable for use in color photography.

The compounds employed according to our invention can be prepared by the reaction of equal molar quantities of heterocyclic hydrazine with phenyl-l-hydroxy 2-naphthoate or phenyl-l-hydroxy-2-benzoate. p

The invention is illustrated by the following typical compounds embodying the invention although it willbe understood that the invention is not limited to the particular embodiments described nor to thcirf u se asillustrated unless otherwise specifically indicated. t

3 EXAMPLE A The following compound embodies the invention:

I II c CouplerI 3- (1-l1ydroxy-2-nnphthyl -8-thia-1,2,Ba-triazacyclopent [ed-indent:

A mixture of 16.5 g. of 2-hydrazinobenzothiazole, 26.4 g. of phenyl-l-hydroxy-Z-naphthoate in 100 ml. of amethyl naphthalene was refluxed for 3 hours, distilling off the water and phenol as formed. The reaction mixture was then cooled, and filtered. The crude product thus obtained was crystallized from butanol to give 21 g. of product, M.P. 258-9" C.

Analysis calculated for C I- N 51 C, 68.0; H, 3.5. Found: C, 68.3; H, 3.4.

EXAMPLE B Another compound embodying the invention is:

Coupler II 3-(1-hydroxy-4,6-disu1fo-2-na hthyl)-8-thia-1,2,3a-trlazaeyclopent Pahndene which was prepared by heating five parts of Coupler I and fifteen parts of concentrated sulfuric acid on a steam bath for four hours. The solution was cooled and poured into water, causing precipitation of Coupler II, which was then filtered, washed with distilled water, and dried. Analysis calculated for C H O N S C, 45.3; H, 2.3. Found: C, 45.8; H, 2.5.

EXAMPLE C Another compound embodying the invention is:

s I f OH Coupler III 3- (1-hydroxy-2-pheny1) -8-thia-1,2,3a-triazacyc1opent[a1indene which was prepared by the same procedure as was used for Coupler I by substituting phenyl-1-hydroxy-2-benzoate for phenyl-l-hydroxy-2-naphthoate. Coupler HI melted at 284 C.

Analysis calculated for C I-I ON S: C, 62.8; H, 3.4. Found: C, 62.6; H, 3.6.

EXAMPLE D Another compound embodying the invention is:

50:11 Coupler IV 3-(2-hydroxy-5-sulfophenyl)-8-thla-1,2,3a-trlazacyclopent [alindene which was prepared by sulfonating Coupler III by the same procedure that was used to prepare Coupler II from Coupler 1.

Analysis calculated for C H O S N C, 48.4; H, 2.6. Found: C, 47.8; H. 3.3.

4 EXAMPLE E Another compound embodying the invention is:

Coupler V l-(l-hydroxy-Z-naphthyl) -2,3,9h-triazabenz[g1 indene which may be prepared by the following process which we used.

A mixture of Z-hydrazinoquinoline and 27.0 g. of phenyl-l-hydroxy-Z-naphthoate in ml. of trichlorobenzene was refluxed for 3 hours; The phenol and water were removed as formed. The reaction mixture was cooled and the precipitated product was collected by filtration and crystallized from 1,2,4-trichlorobenzene to give 24 g. of product (77% M.P. 289 C.

Analysis calculated for C H ON C, 77.1; H, 4.2. Found: C, 77.3; H, 4.0.

EXAMPLE F Another compound embodying the invention is:

Analysis calculated for C H ON CI: C, 69.9; H, 3.2. Found: C, 69.9; H, 3.4.

EXAMPLE G Another compound embodying the invention is:

.mljjr Coupler VII 1- (1-hydroxy-,G-disulfo-Zmaphthyl) -2,3,9b-trlazabenz [g] lndene which was prepared by sulfonating Coupler V in the same manner that Coupler II was prepared from Coupler I.

Analysis calculated for C H O N S C, 50.0; H, 2.5. Found: C, 51.0; H, 2.5.

ridine for Z-hydrazinoquinoline.

. EXAMPLE H Another compound embodying the invention is:

Coupler VIII 1-(1-hydroxy-2-pheny1)-2,3,9b-trlazabenz[glindene which was prepared in the same manner as Coupler V with the substitution of phenyl-l-hydroxy-2-benzoate in place of phenyl-1-hydroxy-2-naphthoate. The coupler had a melting point 290 C.

Analysis calculated for C H ON C, 73.5; H, 4.2. Found: C, 73.5; H, 4.5.

EXAMPLE I Another compound embodying the invention is:

Analysis calculated for C H O N S: C, 56.2; H, 3.24. Found: C, 56.4; H, 3.10.

EXAMPLE J Another compound embodying the invention is:

Cou let X 3- (1-hydroxy-2-napht liyl) -l,2,3a-triazaindene which was prepared by the same procedure used to prepare Coupler V with the substitution of Z-hydrazinopy- The Coupler X had a melting point of 238-9" C.

The analysis calculated for C H ON was: C, 73.5; H, 4.4. Found: C, 73.7; H, 4.5.

The objects of this invention can be accomplished with other cyan-forming couplers as defined herein having a nucleus consisting of a phenol or an a-naphthol group connected through the carbon in its 2-position to a triaza ring substituted with the combination of nonmetallic atoms necessary to form either substituted or unsubstituted rings consisting of pyridine, quinoline or benzothiazole. Our couplers are characterized by producing, upon color development, indoaniline dyes having unexpectedly good spectrophotometric properties which are valuable for color photography, and are also characterized by forming upon color development dyes having unusually good stability to both heat and light.

All of our couplers are further characterized by having good solubility in primary aromatic amino color developers containing the sulfite of an alkali metal such as sodium sulfite, and the-other constituents, and addenda commonly found in color developers.

Our couplers are designed for use in processes in which the coupler is incorporated in the developing solution such as those described in Mannes and Godowsky U.S.

'Patent 2,113,329, granted April 5, 1938, or Mannes,

Godowsky and Wilder U.S. Patent 2,252,718, granted August 19, 1941.

The following composition illustrates a typical developer solution in which our couplers are used.

EXAMPLE K Solution A: Gms. p-Amino diethylaniline hydrochloride 2 Sodium sulfite 5 Water to 950 cc.

Solution B:

Coupler V gms 2.0 Sodium hydroxide do 0.7 BA Alcohol cc 50 ments that the color developer must satisfy. For example, any of the Well-known antifoggants, silver halide solvents, competing couplers, competing developers and other constituents such as potassium bromide, sodiunr carbonate used in developer solutions may be incorporated in developer compositions containing our couplers. Any color-forming developer containing a primary aromatic amino group may be used. These inelude developers having two primary amino groups as well as those having one of the amino groups-substituted or having substituents in the ring such as alkylphenylenediamines and alkyl toluylene diamines. These compounds are usually used in the salt form such as the hydrochloride or the sulfate which are more stable than the amines themselves. Suitable developing agents are diethyl-p-phenylene-diamine hydrochloride, mono-- methyl-p-phenylenediamine hydrochloride, dimethyl-pphenylenediamine hydrochloride and 2-amino-5-diethylamino-toluene hydrochloride. The p-arninophenols and their substitution products may also be used Where the amino group is unsubstituted. All of these developers have an unsubstituted amino group which enables the oxidation products of the developer to couple with the color-forming compounds to form a dye image.

Our development process can be employed for th production of cyan-colored images in light sensitive silver halide emulsion layers containing gelatin or other carrier such as collodion, organic esters of cellulose or synthetic resins. The carrier may be supported by a transparent material such as glass, a cellulose ester or a non-transparent reflecting medium such as paper or an opaque cellulose ester. The photographic light sensitive emulsion may be coated as a single layer on the support or as superposed layers on one or both sides of the support. The superposed layers may be differently sensitized. Usually the cyan-forming layer is used in conjunction with yellow and magenta image forming layers for the purpose of natural color photography by the subtractive process. The superposed cyan, yellow and magenta image forming layers may be arranged in any order on the support. 1

The following example illustrates a typical way. in which our couplers are used in color developers for de veloping cyan dye images in exposed silver halide emulsion layers.

EXAMPLE L A film coated with an ordinary photographicsilver bromoiodide emulsion for color photography was exposed G. 2,4-diarnino phenyl hydrochloride Sodium sulfite 50 Potassium bromide 5 Water to 1 l.

The film was exposed through the base for about 20 seconds to 100 foot candles of light through a red filter transmitting light of longer wavelength than 6400 A.U. to expose the emulsion layer. Following this exposure, the film was developed for 12 minutes in the color forming developer given in Example K, washed and then the silver image and the residual silver halide was removed by treating the film for 5 minutes in a potassium ferricyanide potassium bromide bleach, washing for 5 minutes and fixing in a hypo fixing bath for 5 minutes. After a minute final wash, the film was dried. The result was a positive dye image having a A value of 676 m EXAMPLE M A negative cyan dye image having a A value of 676 m was produced in another sample of the film used in Example L. After being exposed to an image as in Example L, it was developed for 12 minutes in the color developer, Example K, followed by the subsequent treat ment used in Example L to remove the silver and silver halide images from the emulsion.

The cyan dye images produced in Examples L and M were found not only to have a very desirable x max. value but to have excellent stability upon exposure to heat and light. For example, the most dense areas of the dye image formed in Examples L and M changed only 0.02 density unit to red light as a result of one weeks storage at 140 F. and 75% relative humidity. A 50 hour exposure of this cyan dye image in a xenon fadeometer produced only a 0.12 density unit change.

All of our couplers can be incorporated in developer solutions such as we have described in Example K and used to develop cyan dye images in photographic silver halide emulsions. Cyan dye images produced by developers containing our couplers not only have desirable spectrophotometric properties for use in color photography but are also stable upon exposure to heat and light. The following table illustrates these properties as shown by typical examples:

Our couplers have demonstrated good solubility when incorporated in developer solutions. They couple actively with the oxidized developing agent to form cyan dye images in the exposed silver halide emulsion layer upon development.

The novel class of cyan-forming couplers of our invention described hereinabove has very desirable properties which make them unusually valuable for color photography. All of our couplers react with the oxidized primary aromatic amino developing agents during color development to produce good cyan colored dyes having very desirable spectral properties characterized by )t max. values in the range of 680 to 596 m These characteristics are unexpected since previous experience with other phenols and a-naphthols having heterocyclic groups in the 2-position would lead one to expect the dyes produced from them would have absorption maxima in the near infrared region of the spectrum, and thus be greenishcyan in color. Furthermore, the excellent stability to heat and light shown by cyan dyes produced from our couplers makes them especially valuable for use in color photography. Our couplers are readily soluble in color developers and have good reactivity with the developing agents used.

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.

We claim:

l. A cyan color-forming photographic developer comprising a primary aromatic amino developing agent and a coupler compound having the formula:

and

wherein Z is a combination of non-metallic atoms necessary to form a ring selected from the group consisting of the pyridine ring, the quinoline ring, and the benzothiazole ring and R is a member selected from the group consisting of hydrogen atoms, chlorine atoms and sulfo radicals.

2. A cyan color-forming photographic developer comprising a primary aromatic amino developing agent and the coupler 3-(l-hydroxy-Z-naphthyl)-8-thia-l,2,3a-triazacyclopenta [a]indene.

3. A cyan color-forming photographic developer comprising a primary aromatic amino developing agent and the coupler l-(l-hydroxy-Z-naphthyl)-2,3,9b-triazabenz [g]indene.

4. A cyan color-forming photogaphic developer comprising a primary aromatic amino developing agent and the coupler 1-(1-hydroxy-4-chloro-2-naphthyl)-2,3-9b-triazabenz[g]indene.

5. A cyan color-forming photographic developer comprising a primary aromatic amino developing agent and the coupler 1-(1-hydroxy-4,6-disulfo-2-naphthyl)-2,3,9btriazabenz[g]indene.

6. A cyan color-forming photographic developer comprising a primary aromatic amino developing agent and the coupler 3-( l-hydroxy-Z-naphthyl) -l,2,3 a-triazaindene.

7. The method of producing a colored photographic image in a silver halide emulsion layer which comprises exposing said emulsion and developing it with a primary aromatic amino developing agent in the presence of a coupler compound of the formula:

I 2,976,146 9 19 a d sary to form a ring selected from the group consisting OH of the pyridine ring, the quinoline ring, and the heme- C N consisting of hydrogen atoms, chlorine atoms and sulfo I l 5 radicals.

\ References Cited in the file of this patent UNITED STATES PATENTS thiazole n'ng and R is a member selected from the group wherein Z is a combination of non-metallic atoms neces- 10 2,353,754 Peterson July 18, 1944.

Claims

1. A CYAN COLOR-FORMING PHOTOGRAPHIC DEVELOPER COMPRISING A PRIMARY AROMATIC AMINO DEVELOPING AGENT AND A COUPLER COMPOUND HAVING THE FORMULA: