JPS5931953A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide color photographic sensitive material contg. a cyan copler, having small absorption in the green spectral region, and yet, the max. absorption peak in 640-660nm long wavelength region, forming a cyan dye sufficiently fast to heat, light, and humidity, developing good color, and causing no loss of the dye even when a bleaching or bleach-fixing bath is fatigued by long running. CONSTITUTION:The present silver halide color photographic sensitive material is characterized in that it contains as a cyan dye forming coupler a compd. represented by general formula I in which R1 is 1-8C straight or branched alkylene; and Ar is aryl having at least one alkyl. Further, a cyan dye forming couler represented by general formula II is preferably used. In this formula, R<1> is same as R1 and R<2> is alkyl, n is an integer of 1-3, and when n is 2 or 3, each of R<2> may be same or different.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Background Technical Field of the Invention The present invention relates to a silver halide color photographic phase material which is particularly suitable as a photosensitive material for printing.

Prior art and its problems To form a color photographic image using a silver halide color photographic light-sensitive material (hereinafter simply referred to as "sensitive material"), an aromatic primary amine-based color developing agent is usually used to develop the exposed light-sensitive material. When the silver halide grains contained therein are reduced, they are themselves oxidized, and this oxidized product reacts with the coupler previously contained in the sensitive material to form a dye image. Since couplers usually reproduce colors using the subtractive color method,
All three pigments of yellow, magenta, and cyan are formed 3
A neck coupler is used.

Phenols are widely used as couplers for forming cyan dyes contained in photosensitive materials for printing.

One of the phenolic cyanogens is 2,5-diacylaminophenol (for example.

U.S. Patent Nos. 2,772,162 and 2,895,82
No. 6, No. 2,369,929, etc.).

This 2,5-diacylaminophenol cyan coupler, even if the bleach bath or bleach fixer characterized by EDTA ferric salt suffers from thinning, there is little loss of the dye obtained by reaction with the color developing agent. It has extremely excellent characteristics in that respect. Moreover, the dye obtained from it has excellent heat resistance.

However, the color forming properties of couplers are still unsatisfactory, and the dyes obtained have poor light resistance.

A 2,5-diacylaminophenol cyan coupler that overcomes these drawbacks is U.S. Patent No. 3,758.
, No. 308, No. 3,880,661, etc.

Although such a 2,5-cyacylaminophenol 2-equivalent cyan coupler does have improved color development to some extent and also improves the light resistance of the resulting dye, the light resistance of the unreacted coupler remains. It has drawbacks such as yellow staining and problems with color reproduction in the green area due to poor sharpness on the short wavelength side of the coloring dye.

That is, conventional 2,5-diacylaminophenol 2
The equivalent cyan coupler has 1) maximum absorption wavelength of 640-6
60 nm, but there is a lot of absorption in the green region of the absorption spectrum (particularly from 500 to 550 nm), and ii) the cyan dye formed does not have sufficient fastness to heat, light and moisture. Furthermore, iii) characteristics required for cyan couplers, such as poor color development, could not be satisfied.

II. Purpose of the Invention The present invention has been made in view of the above-mentioned circumstances, and includes: i) absorption in the green region of the absorption spectrum is small, and the maximum absorption wavelength is at a long wavelength of 640 to 660 nm, and ii) The cyan dye that is formed has sufficient fastness against heat, light, and moisture, and iii) has good color development, is cheap in bleaching baths, and retains its color even when the bleach-fix bath is fatigued by running. An object of the present invention is to provide a silver halide color photographic material containing a cyan coupler without loss.

These objects are achieved by the present invention as follows. In other words, the present invention is realized by a silver halide color photographic light-sensitive material characterized by containing a compound represented by the general formula [I] as a cyan dye-forming coupler.

(In the general formula (I), R1 represents a linear or branched alkylene group having 1 to 8 carbon atoms, R2 represents an alkyl group, and n is an integer of 1 to 3.

When n is 2 or 3, R2 may be the same or different. ) III. Specific constitution of the invention In the cyan coupler of the present invention represented by the above general formula [I], the number of carbon atoms in R1 is 1 to 8, and even if R1 is a straight chain, it does not have a branch. Although it may exist, it is particularly preferable that R1 has 1 to 7 carbon atoms. and R1 is represented by CH2, and R has 3 to 6 carbon atoms.
Particularly preferred are the following.

On the other hand, the alkyl group represented by R2 may have 1 to 20 carbon atoms, such as methyl group, ethyl group, 1-propyl group, butyl group, -butyl group, pentyl group, sec-bengel group, etc. group, t-pentyl group, t-octyl group, nonyl group, dodecyl group, sec-dodecyl group, octadecyl group, etc.

And, R2 has 1 to 3 bonds to the benzene ring, but 2
Or when three are combined, each may be the same or different.

However, the total number of carbon atoms in R7 or a plurality of R2 is preferably 8 to 18.

And R1 and R2 are the above 1. It becomes the base of the outside,
Furthermore, when the script-off group is other than Cl,
The desired effects of the present invention are not realized.

Next, typical examples of cyan couplers used in the present invention will be described, but the couplers used in the present invention are not limited thereto.

Compound Examples Such compounds represented by the above general formula [I] can generally be synthesized according to the following reaction formula.

Next, examples of synthesis of specific compounds will be shown.

Synthesis Example 1 Coupler No. 1: 2-(2,3,4,5,6-pentafluorobenzamide)-4-chloro-5-(α-(4-
Dimedylaminosulponylaminophenoxy)tetradecanamide)phenol (A) 18.9g (0.10m
ole) 2-amino-4-chloro-5-ditrophenol was dispersed in 100 ml of acetonitrile and 23.1
A solution of 2.3.45.6-pentafluorobenzoic acid chloride (0.10 mole) in 50 ml acetone was added dropwise. After 3 hours of heating, the reaction solution was cooled on ice, the precipitated solid was collected, washed with cooled acetonitrile, and dried to give 2-(2,3,4,5,6-bentafluorobenzamide)-4. -Chloro-5-ditrophenol 32.
5 g (yield: 85%) was obtained.

(B) 16 g (0.042 mole) of the above crude crystals
It was dissolved in 0 ml of alcohol, a palladium-carbon catalyst was added, and catalytic reduction with hydrogen was carried out at room temperature under normal use.

Next, the palladium-carbon catalyst was separated, and the oral fluid was concentrated.

The residue was dissolved in 200 ml of acetonitrile and recrystallized to obtain 11 g of 2-(2,3,4,5,6-pentafluorobenzamide)-4-chloro-5-aminophenol. (Yield 74%) (c) 10 g (0.028 mole) of the above phenol derivative and 13.8 g (0,030 mole) of α-(4
-dimedylaminosulfonylaminophenoxy)tetradecanoic acid chloride was dissolved in 150 ml of latrahydrofuran, and 4 g (0.050 mole) of hyridine was slowly added dropwise under water cooling. After stirring at room temperature for 2 hours, the solvent was distilled off under reduced pressure. The residue was recrystallized from 200 ml of a 1:1 mixed solvent of n-hexane and ethyl acetate, yielding 12.4 g (
The desired coupler 1 was obtained with a yield of 53%.

The analytical values were as follows.

Melting point 102-104℃ Yield 364.7 Elemental analysis C (%) H (%) N (%) S (%)
F (%) theoretical value 55.02 6.41 5.35
4.0B 16.92 Actual value 55.11 6.3
9 5.31 4.12 16.84 Such couplers are generally lipophilic, and in order to incorporate them into a sensitive material, at least one compound represented by the general formula (1) is added with a high boiling point as a so-called oil protector. It is dissolved in an organic solvent or the like and incorporated into a silver halide emulsion layer (generally a red-sensitive emulsion layer or a layer adjacent thereto) of a sensitive material.

The coupler of the present invention can be incorporated into the emulsion layer of a color sensitive material using conventionally known methods, such as a high-boiling organic solvent with a boiling point of 175°C or higher such as tricresyl phosphate or dibutyl phthalate, or butyl acetate, butyl propionate, etc. After dissolving the coupler of the present invention in a low boiling point solvent alone or optionally in a mixture thereof, the coupler is mixed with a gelatin water bath solution containing a surfactant,
Next, after emulsifying with a high-speed rotary mixer or a colloid mill, it can be added to silver halide to prepare the silver halide emulsion used in the present invention.

In this way, when the above-mentioned coupler is contained in the photosensitive layer of a photosensitive material, it has the advantage of improving color staining etc. because it shows no bad interaction with color development and has particularly good reactivity. . Furthermore, the dye obtained using the coupler of the present invention satisfies the above-mentioned excellent color absorption properties.

The photosensitive layer (silver halide emulsion layer) of the photosensitive material containing the cyan coupler according to the present invention is generally red-sensitive, and the silver halides used include silver bromide, silver chloride, iodobromide, etc. Any of those used in conventional silver halide emulsions, such as silver, silver chlorobromide, and silver chloroiodobromide, are included.

The silver halide emulsion constituting the silver halide emulsion can be produced by various methods including the usual method, for example, the method described in Japanese Patent Publication No. 7772/1983, or the method described in U.S. Pat. No. 592,250, i.e., forming an emulsion of silver salt grains consisting of at least a portion of a silver salt whose solubility is greater than that of silver bromide, and then at least a portion of the grains being mixed with silver bromide. It can be produced by any production method such as a so-called conversion emulsion production method, such as conversion into salt or silver iodobromide, or a Lippmann emulsion production method consisting of fine-grained silver halide having an average grain size of 0.1 μm or less.

In addition, the silver halide emulsions may contain sulfur sensitizers, such as allylthiocarbamide, thiourea, cystine, etc., active or inactive selenium sensitizers, and reduction sensitizers, such as stannous salts, polyamines, etc., noble metals. Sensitizers, such as gold sensitizers, in particular potassium aurithiocyanate, potassium chloroaurate, 2-olosulpobenzthiazole methyl chloride, etc., or sensitizers of water-soluble salts such as ruthenium, rhodium, iridium, etc. Specifically, it can be chemically sensitized by using ammonium chlorobaratate, potassium chlorobratinate, sodium chlorovaradite, etc. alone or in combination as appropriate.

The silver halide emulsion can also contain various known photographic additives.

The silver halide containing the coupler of the present invention is spectral sensitized by selecting an appropriate sensitizing dye in order to impart sensitivity to the wavelength range required for red-sensitive emulsions. Various spectral sensitizing dyes are used, and these may be used alone or in combination of two or more. Spectral sensitizing dyes advantageously used in the present invention include, for example, U.S. Pat. 629
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in the specifications of No. 2,776,280 and others.

Such red-sensitive emulsion layers are generally provided on a reflective support.

Then, it is usually laminated with other known green-sensitive and evening-sensitive emulsion layers according to a known method to form a light-sensitive material.

(2) Specific Uses of the Invention The photosensitive material of the present invention is usually developed with a color developer after being exposed to light through a photographic photosensitive material.

A suitable color-forming crude drug is one containing an aromatic primary amine color-forming developing agent as a main component. Typical examples of this color developing agent include those based on p-phenylenediamine, such as diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, -Amino-5
-diethylaminotoluene hydrochloride, 2-amino-5-(
N-ethyl-N-dodecylamino)-toluene, 2-amino-5-(N-ethyl-N-β-methanesulfonamidoethyl)aminotoluene sulfate, 4-(N-ethyl-
N-β-notanesulfonamidoethylamino)aniline, 4-(N-ethyl-N-β-hydrokineethylamino)aniline, 2-amino-5-(N-edyl-N-β-
methoxyethyl)amine toluene and the like.

These color developing agents may be used alone or in combination of two or more, and if necessary, in combination with a black and white developing agent such as hydroquinone. Furthermore, color developing solutions generally contain alkaline agents such as sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium sulfate, sodium sulfite, etc., and various additives such as alkali metal halides such as potassium bromide, or developing agents. It may also contain agents such as cidradic acid.

Next, various known processing is performed to obtain a color photographic image.

■Specific Effects of the Invention According to the present invention, a cyan color line image having a maximum absorption wavelength of 640 to 660 nm can be obtained, and moreover, a cyan color line image having a maximum absorption wavelength of 640 to 660 nm can be obtained.
The absorption scale at 0 nm is extremely small, and an extremely good cyan dye image can be obtained.

The dyes formed are also extremely robust to heat, light, and moisture.

Furthermore, the coloring property is also very good. In addition, even if you get tired from bleaching, bleach-fixing, or running, there is very little loss of pigment.

The present inventors conducted various experiments to confirm the effects of the present invention.

An example is shown below.

Experimental Example 1 Using couplers of the present invention and comparative couplers as shown in Table 1 below, 10 g of each coupler was added to a mixed solution of 5 ml of dibutyl slate and 30 ml of ethyl acetate, and heated to 60°C. It was completely dissolved.

This solution was mixed with 5 ml of a 10% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) and 200 ml of a 5% aqueous gelatin solution, and emulsified using a coroite mill to prepare a dispersion of each coupler.

This clouder dispersion was then added to 500 g of gelatin-silver chlorobromide (containing 20 mol% silver bromide) emulsion, applied to polyethylene coated paper, and dried to form six types of silver halide color photographic sensitizers. Created the material. These samples were subjected to extraction processing using wedge exposure according to a conventional method.

Color stock processing Preliminary stage Color development processing Process contents The processed composition is as follows.

Color developer composition Bleach-fix solution Photographic properties of each sample obtained after tissue processing were measured.

The results are shown in Table 1.

Note that the sensitivity values in the table are expressed as relative sensitivities with the sensitivity of sample No. 1 set as 100.

This measurement was performed using a PDA-60 type densitometer (Konishi Rokusha Tei Kogyo ■).
(manufactured by) was used.

In addition, "D (λ550)" in the table evaluates the short wavelength side cutoff of the reflection spectrum after coloring of the cyan coupler, and is the wavelength when the peak reflection spectrum after cyan coloring is 16. is the reflected concentration absorption at 550 nm. This indicates the influence of the cyan coupler on the color reproducibility of the green area after color development, and since human visibility is particularly high in this area, this
Even if the value of ``D(λ550)'' changes slightly, the color tone will appear to change greatly to the human eye. The smaller the size, the better.

Comparative coupler (A) (Compound described in U.S. Pat. No. 2,758,308) Comparative coupler (B) Comparative coupler (C) As is clear from Table 1, the cyan coupler according to the present invention has a preferable spectral characteristic in terms of photographic performance. It has reflection characteristics (reflection maximum wavelength and D (λ550)), and has significantly improved human visibility in the green sensitive area, and has photographic and sexual performance unmatched by conventional technology.

Furthermore, when compared with any of the comparative couplers, it shows a higher color density, indicating that it is a cyan coupler with extremely good photographic properties.

Experimental Example 2 Samples 7 to 12 in which 16 types of cyan dye images were formed were obtained in the same manner as in Experimental Example 1 using the couplers of the present invention and comparative couplers as shown in Table 2.

Then, light resistance, heat resistance, and moisture resistance were examined.

The results obtained are shown in Table 2.

In addition, light resistance is determined after 200 hours of exposure to each image using a xenon fade meter, heat resistance is determined after 2 weeks at 77°C, and humidity resistance is determined after 2 weeks at 60°C and 70% relative humidity. The respective residual concentrations at a concentration of 1.0 are shown. (Residual density %) In addition, stain is expressed as a percentage increase in blue density in the unexposed area of the sample subjected to the light resistance test.

Comparative coupler (D) As is clear from Table 2, comparative coupler (D) has extremely poor heat resistance and moisture resistance, and comparative coupler (C) has extremely poor light resistance. In addition, the comparative coupler (B), which showed relatively good results among the comparative couplers in Experimental Example 1, also showed significant stain deterioration and was inferior in light resistance, heat resistance, and moisture resistance compared to the cyan coupler according to the present invention. I understand that.

It can be seen that the cyan coupler according to the present invention has extremely excellent performance in these respects as well. .

Agent Yoshimi Kuwabara Procedural Amendment Written August 31, 1980 Kazuo Wakasugi, Commissioner of Patents 1 Indication of the case 2 Name of the invention Silver halide color photographic tourism material 3 Person making the amendment Relationship to the case Patent applicant address Tokyo Shinjuku-ku Nishi-Shinjuku 1-26-2 Name (1
27) Representative Director of Konishiroku Photo Industry Co., Ltd. Nobuhiko Kawamoto, 4th generation employee Address: 191 Sakura-cho, Hino-shi, Tokyo Inside Konishiroku Photo Industry Co., Ltd. Name: Yoshikumi Kuwabara Date of 5th amendment order Subject of voluntary 6th amendment Application form and Contents of Amendment to Specification 7: Inscription of application and specification (no change in content) Procedural amendment dated September 6, 1980, Commissioner of the Japan Patent Office Mr. Kazuo Wakasugi, Case 1 Patent application submitted on August 17, 1980 (3) )2 Name of the invention Silver halide color photographic light-sensitive material 3. Relationship with the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (1
27) Nobuhiko Kawamoto Representative Director, Konishiroku Photo Industry Co., Ltd. Agent Address: 1 Sakura-cho, Hino-shi, Tokyo 191 Konishiroku Photo Factory Co., Ltd. Name: Yoshimi Kuwabara 5. Date of amendment order: Self-initiation 6. Column 7 of "Detailed Description of the Invention" Contents of the Amendment The detailed description of the invention is amended as follows.

1. Delete lines 4 to 7 on page 10 and add the following sentences.

"Coupler No. 2: 2-(2,3,4,5,6-pentafluorobenzamide)-4-chloro-5-(5-α-
(2,4-di-tert-amylphenoxy)-n-butanamido)phenol” 2, page 11, lines 7 to 12
Delete the fourth line of the page and add the following sentence.

"(C) 3.2 g (0.009 mole) of the above phenol derivative was added to a solution of 30 ml of acetic acid and 0.9 g of sodium acetate, and while stirring at room temperature, α-(2,4-di-tert
-butylphenoxy)-n-butanoic acid chloride 3.7
A solution of g of acetic acid (10 ml) was added dropwise. After reacting for 30 minutes at room temperature, the mixture was poured into 300 ml of water to coagulate the precipitated solid. The product was recrystallized from solid acetonitrile to obtain 3.5 g (yield 60%) of the desired coupler No. 2. The structure of the target product was confirmed by mass spectrum, elemental analysis, and NMR spectrum.

Synthesis Example 2 Coupler No. 4: 2-(2,3,4,5,6-pentafluorobenzamide)-4-chloro-5-(α-(2.
4-di-tert-methylphenoxy)-n-hexaneamido)phenol Intermediate of Synthesis Example I above 2-(2,3,4,5,6-pentafluorobenzamide)-4-chloro5-aminophenol 4 .5g was added to 80ml of acetic acid and 25l of sodium acetate solution, and while stirring at room temperature, α-(2.4-dite
A solution of 5.7 g of rt-amylphenoxy)-n-hexanoyl chloride in 20 ml of acetic acid was added dropwise. After reacting at room temperature for 30 minutes, the mixture was poured into 300 ml of water and the precipitated solid was collected by filtration. Recrystallize with acetonitrile to obtain a melting point of 200~
Target coupler No. 4 was obtained at 201°C. ” Procedural amendment October 18, 1980 Kazuo Wakasugi, Commissioner of the Japan Patent Office 1 Display of the case 1982 Patent Application No. 142839 2 Name of the invention Silver halide color photographic light-sensitive material 3 Person making the amendment Relationship to the case Patent Applicant Address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (1)
27) Representative Director of Konishiroku Photo Industry Co., Ltd. Nobuhiko Kawamoto 4 Agent 191 Address 1 Sakura-cho, Hino-shi, Tokyo Konishiroku Photo Industry Co., Ltd. Name Yoshimi Kuwabara Date of 5th amendment order Voluntary statement subject to 6th amendment "Detailed Description of the Invention" Column 7, Contents of the Amendment The detailed description of the invention is amended as follows.

Procedural amendment January 14, 1980 Kazuo Wakasugi, Commissioner of the Japan Patent Office 1 Display of the case 1982 Patent Application No. 142839 2 Name of the invention Silver halide color photographic light-sensitive material 3 Person making the amendment Relationship to the case Patent application Address: Tokyo and Nishi-Shinjuku 1-26-2 Name (127) Representative Director of Konishiroku Photo Industry Co., Ltd.
Nobuhiko Kawamoto 4 Agent residence Address: Konishiroku Photo Industry Co., Ltd., 1 Sakura-cho, Hino-shi, Tokyo 191, Japan Name Yoshimi Kuwahara 5 Date of amendment order Voluntary 6 Column of ``Claims'' of the specification subject to amendment 6 and ``Invention'' Contents of amendment in column 7 of ``Detailed explanation of the invention'' (1) The scope of claims is amended as shown in the attached sheet.

(2) The detailed description of the invention is amended as follows.

2. Claims: A silver halide color photographic material containing a compound represented by the following general formula as a cyan dye-forming coupler.

(In the general formula, R1 represents a linear or branched alkylene group having 1 to 8 carbon atoms, and Ar represents an aryl group having at least one alkyl group.)

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material characterized by containing a compound represented by the following general formula [1] as a cyan dye-forming coupler. (In the general formula [11, R1 represents a linear or branched alkylene group having 1 to 8 carbon atoms, R2 represents an alkyl group, and n is an integer of 1 to 3. n is 2 or 3. When R2 may be the same or different.)