US3615605A

US3615605A - Light-sensitive silver halide color-photographic material containing naphthal color couplers

Info

Publication number: US3615605A
Application number: US714336A
Authority: US
Inventors: Isabro Inoue; Shui Sato; Yutaka Takei
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 1967-03-22
Filing date: 1968-03-19
Publication date: 1971-10-26
Anticipated expiration: 1988-10-26
Also published as: FR1558147A; DE1768001B1; BE712616A; GB1210463A

Abstract

WHEREIN X is hydrogen, halogen, sulfonic or sulfonate groups, Y is -(CH2)3-or -CH2-CH(CH3)-and R is an aliphatic hydrocarbon radical of eight to twenty carbon atoms.
Light-sensitive silver halide color-photographic emulsions comprising cyan couplers of the formula:

Description

United States Patent [72] lsabro Inoue;

Shui Sato; Yutaka Takei, all of Tokyo, Japan Mar. 19, 1968 Oct. 26, 1971 Konishiroku Photo Industry Co., Ltd. Tokyo, Japan Mar. 22, 1967 Japan Inventors App]. No. Filed Patented Assignee Priority U.S.(l V M 96/100 Int. Cl G03c 1/40 Field of Search 96/100, 55

[5 6] References Cited UNITED STATES PATENTS 3,135,609 6/1964 Klinger 96/100 Primary Examiner-J. Travis Brown AnorneyWaters, Roditi, Schwartz & Nissen ABSTRACT: Light-sensitive silver halide color-photographic emulsions comprising cyan couplers of the formula:

I p X wherein X is hydrogen, halogen, sulfonic or sulfonate groups, Y is -(CH,) -or Cl-l CH(Cl-l;,)-and R is an aliphatic hydrocarbon radical of eight to twenty carbon atoms.

LIGHT-SENSITIVE SILVER HALIDE COLOR- PHOTOGRAPHIC MATERIAL CONTAINING NAPHTHAL COLOR COUPLERS This invention relates to a light-sensitive silver halide colorphotographic emulsion capable of forming a cyan-colored image, which comprises a novel cyan coupler of the formula wherein X is hydrogen atom,thalogen atom or a sulfonic or sulfonate group, Y is (CH -orCH CH(Cl-l and R is an aliphatic hydrocarbon radical of eight to 20 carbon atoms.

As a conventional cyan coupler usable for a light-sensitive color-photographic material positive material including a color-photographic printing paper and a transparent photographic positive there are known l-hydroxy-Z-naphthoalkyl amide derivatives which, for example, have any one of the following structures:

CONHCnHgr I S03N8 (PB Report F 546) A color-photographic material in which the above-mentioned coupler '[l] or [ll] is incorporated has many advantages, e.g. high photographic speed and maximum color density obtained by the usual color development, and good spectral absorption characteristics of cyan-colored images. Further, it is relatively free from staining of unexposed areas. However, the said material is still not entirely satisfactory because the resulting cyan-colored image varies in its density depending on the pH of a developing bath and the time of water-washing during color development. Further, the color image is sensible to light, heat and humidity so that it may be changed or faded out in color during storage. This is a disadvantage when the said material is intended for use as photographic positive.

The present invention provides a light'sensitive silver halide color-photographic material which does not suffer from the above-mentioned disadvantages.

The coupler of the above-indicated structural formula which is usable for the present invention is a new compound whose structural characteristic is that a cyan coupler component is connected through a C -alkylene chain by an amide linkage with a diffusion-inhibiting component which includes a water-solubilizing group. Such compounds may be prepared by using phenyl-l-hydroxy-Z-naphthoate propylenediamine, long chain alkyl succinic anhydride, etc.

Typical couplers which are suitably used in the present invention include the following:

AOaNB CONE-CHr-CH -CHy-NHC O-GH -CH-C H15 4 O OH As is apparent from these structural formula, the coupler compounds of the present invention contain three carbon atoms in the alkylene chain linking the cyan coupler component and the diffusion-inhibiting component. ln contrast to this, the conventionally known cyan couplers which are known have at most two carbon atoms in the corresponding alkylene chain, as shown, for example, by the following structuralfonnula Such a conventionally known coupler as [lll] is not free from the aforementioned defects. For additional information, a corresponding cyan coupler having a C -alkylene chain is synthesized only by using expensive starting materials. Another corresponding coupler having a C -aIkylene chain is difficult to be synthesized. These should be construed as support, for patentability of new cyan couplers used in this invention.

The following examples will serve to show the preparation of some new cyan couplers used in this invention.

SYNTHESIS OF COMPOUND (1) 53 g. of phenyll -hydroxy-2-naphthoate are added to a solu- 5 tion of 45 g. of 1,3-propane diamine in 200 ml. of acetonitrile at a temperature below C. After stirring the resulting mixture for 2 hours, the formed precipitate is collected by filtration and recrystallized from n-butyl alcohol. N-(3- aminopropyl)-l-hydroxy-2-naphthoamide (intermediate product) melting at l83-l 84 C. is obtained as white crystalline needles. This intermediate product (12 g.) is heated together with 18 g. of n-octadecyl succinic anhydride and 60 ml. of glacial acetic acid at 70-80 C. for 15 minutes. The resulting reaction mixture is cooled to room temperature and the formed precipitate is collected by filtration and washed with glacial acetic acid and then with acetone and dried. Recrystallization from Apercent alcohol yields a white powder melting at l l5l 16 C. This corresponds to compound l SYNTHESIS OF COMPOUND (3) In a similar manner to thatfor obtaining the intermediate product in the synthesis of compound (1), phenyl-l-hydroxy- 4-chloro-2-napthoate is reacted with l,3-propane diamine. N- (3-aminopropyl)-l-hydroxy-4-chloro-2-naphthoamide (intermediate product) melting at 190 C. is obtained. The intermediate product is reacted with n-dodecyl succinic anhydride under the same condition as mentioned in the synthesis of compound (1), thereby to yield compound (3) melting at lO4-l06 C.

SYNTHESIS OF COMPOUND (4) In the process for obtaining the intennediate product of the compound (1), l,2-propane diamine is used in place of 1,3- propane diamine to give N-(2-methyl-2-aminoethyl)-l-2- naphthoamide melting at 231 C. (intermediate product). The intermediate product is reacted with n-octyl succinic anhydride under the same condition as mentioned in the synthesis of compound (1), thereby to yield compound (4) melting at I 80-1 8 1 C.

SYNTHESIS OF COMPOUND (5) In a similar manner to that for obtaining the intermediate product of compound (1), phenyl-l-hydroxy-4-chloro-2- naphthoate is reacted with l,2-propane diamine. N-(Z-methyl- 2-aminoethyl)- l -hydroxy-4-chloro-2-naphthoamide (intermediate product) melting at 227-228 C. is obtained. This intermediate product is reacted with n-hexadecyl succinic anhydride under the same condition as mentioned in the synthesis of compound (1), thereby to yield compound (5) melting at 140-142 C.

SYNTHESIS OF COMPOUND (2) For 3 hours, 59 g. of compound (1) and 240 ml. of acetic acid are boiled. The mixture is then allowed to cool at room temperature and the precipitate formed is collected by filtration and washed with methyl alcohol and dried. Recrystallization from 500 ml. of ethyl alcohol yields N-[3- (n-octadecyl succinimido)propyl]-l-hydroxy-2-naphthoamide melting at 87-88 C. (intermediate product). 7

This intermediate product (58 g.) is suspended in 500 ml. of acetonitrile and, to this suspension, 35 ml. of chlorosulfonic acid are added in one batch at 20 C. while stirring. The temperature of the suspension rises to 4550 C. and crystals are dissolved therein. After allowing to stand at room temperature, the precipitate formed is filtered off. The filtered precipitate is washed two times with 100 ml. of acetonitrile and dried. The product is then dissolved in a mixture of 300 ml. of N-caustic soda aqueous solution and 300 ml. of methyl alcohol, and the resulting solution is made acidic with acetic acid. The precipitate formed is filtered off and washed with 50 percent methanol and dried. The compound (2) melting at l69-l74 C. is obtained as a white powder.

SYNTHESIS OF COMPOUND (6) Calculated Found Compound 0 H N C II N The data relating to the compounds (2) and (6) are those obtained from the corresponding monohydrates, respectively.

The coupler compound thus prepared is dissolved in an aqueous alkali hydroxide or alkali carbonate solution or in an aqueous alcohol solution and then the resulting solution is dispersed in a light-sensitive silver halide color-photographic emulsion, which in turn is coated on an appropriate support, e.g. photographic film base or baryta paper, and then dried, to thereby produce a light-sensitive color-photographic material. The coupler content of the silver halide emulsion may vary depending on the type of the emulsion and molecular weight of the coupler, but it should preferably be within the range of from 0.017 moles to 0.l47 moles per mole of the silver halide present.

Any color developer which is commonly used for development of conventional color-photographic materials is usable for the color-photographic material of this invention. For example, N,N-diethyl-p-phenylenediamine, N-ethyl-N-hydroxyethyl-p-phenylenediamine, N-ethyl-N-hydroxyethyl-Z- methyl-p-phenylenediaminc, N,N-diethyl-2-methyl-p-phenylenediamine, N-ethyl-N-B-methanesulfonamidoethyl-3- methyl-4-aminoaniline, etc., and their sulfates, sulfites or hydrochlorides are suitable color developers.

A light-sensitive color-photographic material which contains a cyan coupler of the present invention has high photographic sensitivity even by usual color development. Further, it has good spectral absorption characteristics for photographic positives because the absorption maximum of the resulting cyan-colored image exists at around 690 mu. Still another advantage is the stability of color image density irrespective of variation in the pH of the treating bath and the time of water-washing during color development. The resulting color image is quite stable against heat, light and humidity and so it can be preserved for a long period of time.

The present invention is further illustrated by the following examples which are not intended to limit the scope of the present invention:

EXAMPLE 1 In 30 ml. of N-potassium hydroxide solution, 8.0 g. of the coupler compound (3) are dissolved and the solution is diluted with water to ml. The resulting solution is added to 1 kg. of a red-sensitive silver chloride emulsion and the mixture is adjusted to pH 6.7 with an aqueous citric acid solution.

The resulting emulsion is coated on a baryta paper and dried. The light-sensitive material thus prepared is exposed to light and then treated at 20 C. for minutes in a developing bath having the following formulation:

N-Ethyl-N-hydroxyethyl-p-phenylenediamine sulfate 2.5 g. Anhydrous sodium sulfite 2.0 g. Hydroxylamine hydrochloride 1.0 g. Sodium carbonate (monohydrate) 82.0 g.

Potassium bromide 2.

Water to make up 1,000 ml.

Immediately after dipping in a stopping bath which comprises 10 ml. of glacial acetic acid, 3.0 g. of caustic soda and 1,000 ml. of water, the light-sensitive material is dipped in an acidic hardening fixing bath for 4 minutes. The developed light-sensitive material is washed with water for 10 minutes and subsequently treated at C. for 8 minutes in a bleaching bath having the following formulation:

Sodium ethylenediamine tetraacetate 40 g. Ferric chloride g. Sodium carbonate (monohydrate) 20 g. Potassium bromide 30 g. Sodium thiosulfate 200 5.

Water to make up L000 ml.

The bleached product is washed with water for 20 minutes and then dipped in a stabilizing bath for 2 minutes and dried. Cyan colored image having an absorption maximum of 690 mp. is obtained.

Fading properties of the cyan-colored image obtained from the coupler compound (3) of this invention and the cyan-' colored images obtained from the known couplers [I], [II] and [III] were tested. Thecyan-c olored images obtained from the known cyan couplers [I], [II] and [III] by the similar treatment as above were used as controls. The fading ratio of the colored images after standing at 50 C. for 7 days under 80 percent of relative humidity and the fading ratio after standing at C. for 4 days in Fade O-meter are shown in the table 1 below.

Table l Fading Ratio (Residual color density percent to l00% oforiginal color image density) Under 80% of relative humidity at 50 C. for By Fade-o-meter Cyan Coupler 7 days (k) Compound (3) of 98 94 this invention Known compound [l] 52 80 Known compound [II] 60 8| Known compound [ill] 65 80 As is apparent from table 1, the color images of the photographic materials containing the cyan couplers of the present invention are excellent in fastness against light, heat and humidity. Further, the image density of the cyan-colored image obtained by using compound (3) is stable, irrespective of the pH of the treating bath and the time of water-washing.

EXAMPLE 2 10 minutes with a developing solution of the following formulation:

Methol 3 g. Anhydrous sodium sulfite 60 g. Hydroquinone 6 g. Anhydrous sodium carbonate 50 g.

Potassium bromide Water to make up 1.000 ml.

After the usual procedures for stopping, hardening and waterwashing, the film is reexposed to white light and then treated at 20 C. for 12 minutes with a developing solution of the following formulation:

N,N-diethyl-pphenylenediamine sulfate 5 g. Anhydrous sodium sulfite 2 gv Sodium carbonate (monohydrate) 82 g.

Potassium bromide Water to make up 1,000 ml.

Thereafter, stopping, fixing, rinsing and bleaching are effected in the usual manner. Then the photographic film is washed with running water for 20 minutes and dried to obtain a cyancolored positive image which has an absorption maximum at 690 mp. and which is stable against light, heat and humidity.

EXAMPLE 3 N,N-diethyl-p-phenylenediamine sulfate 2.5 g. Anhydrous sodium sulfate 2.0 g. Sodium carbonate (monohydrate) 82.0 g. Potassium bromide 2.0 g.

Water to make up 1.000 ml.

Stopping and fixing are carried out in the usual manner. After water-washing for l0-l5 minutes, this photographic film is treated for 5 minutes in a bath of the following formulation:

Potassium ferricyanide Potassium bromide Water to make up L000 ml.

The film is washed with water for further 10 minutes and then dipped for 5 minutes in a bath of the following formulation:

Sodium thiosult'ate Water to make up 1.000 ml.

After water-washing and drying, a cyan-colored image with an absorption maximum of 700 m is obtained which is stable against light, heat and humidity.

What is claimed is:

l. A light-sensitive silver halide color-photographic material, containing a cyan coupler having the general formula:

wherein X is hydrogen atom, halogen atom, or sulfonic or sulfonate group, Y is(Cl-l -,or CH -CH(CH and R is on an aliphatic hydrocarbon radical of eight to 20 carbon atoms. I

2. A light-sensitive silver halide color-photographic material CONHCH,-CH,CH NHC OCH,C H-C1gHz5 as claimed in claim 1, wherein said cyan coupler is: C 0H OH v C0NHCHzCHg-CH2NHCOCH2-CHC13H37 I 00H 5. A light-sensitive silver halide color-photographic material as claimed in claim 1, wherein said cyan coupler is:

OH 3. A light-sensitive silver halide color-photographic material I as claimed in claim 1, wherein said cyan coupler is: c0 CH NHc0 cH,-CH-G,H

5 CH; O O H O CHPNH C Hr CHE 6. light-sensitive silver halide color-photographic material as claimed in claim 1, wherein said cyan coupler is: C O OH I S OaNa V CONHCHg-?HNHCO CH CHC1QH33 CH; C O OH 4. A light-sensitive silver halide color-photographic material I as claimed in claim 1, wherein said cyan coupler is: c

Claims

2. A light-sensitive silver halide color-photographic material as claimed in claim 1, wherein said cyan coupler is:
3. A light-sensitive silver halide color-photographic material as claimed in claim 1, wherein said cyan coupler is:
4. A light-sensitive silver halide color-photographic material as claimed in claim 1, wherein said cyan coupler is:
5. A light-sensitive silver halide color-photographic material as claimed in claim 1, wherein said cyan coupler is:
6. A light-sensitive silver halide color-photographic material as claimed in claim 1, wherein said cyan coupler is: