JPS5969755A - Cyan coupler for photography - Google Patents

Abstract

PURPOSE:To obtain a cyan coupler for photography of which the image is highly resistant to water, heat, moisture, etc. by incorporating a benzamide group of which the ortho position is substd. with a fluorinated alkyl group into the 2nd position of phenol and an acyl amino group into the 5th position. CONSTITUTION:The compd. expressed by the formula I (Rf is alkyl substd. with a fluorine atom; R<1> is alkyl, aryl; R<2> is H, halogen, univalent org. group; Z is H, a group that can be eliminated by coupling to the oxidant of a coloring developing agent; n is 1-3) is used as a cyan coupler for photography. The compd. of the formula I is exemplified by the formula II, the formula III, etc. for example, the exemplified compd. of the formula III is obtd. by bringing 2- amino-4-chloro-5-nitrophenol and 2-trifluoromethyl benzoic chloride into reaction, reducing the resulting product of reaction and bringing the same into reaction with alpha-(4-dimethyl aminosulfonamide phenoxy)tetradecanicchloride.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel cyan dye image-forming couplers;
The present invention further relates to a silver halide color photographic light-sensitive material containing the above-mentioned cyan coupler and having improved photographic properties.

In general, in silver halide color photographic light-sensitive materials, silver halide grains exposed to light are reduced with an aromatic primary amine color developing agent, and the oxidation products of the color developing agent and yellow, magenta, and A color dye image can be obtained by oxidative coupling with a coupler forming each cyan dye in a silver halo saponide emulsion layer.

The couplers commonly used to form the cyan dyes are phenols or 7-tols.

The above-mentioned phenolic cyan couplers are particularly useful in the green region (500
The absorption at ~55QnmJ is small, and the maximum absorption wavelength is on the longer wavelength side (645-660nmJ, and the spectral absorption characteristics are good and color reproducibility is excellent, but the light resistance, heat resistance, and moisture resistance of the dye However, it cannot be said that the fastness or storage stability against corrosion, etc., or the occurrence of staining under such conditions are necessarily sufficient. There is still room for improvement regarding fading or loss of dye during running treatment, and furthermore, it is desirable to have better color development and color density.

Therefore, research has been carried out to satisfy the above-mentioned requirements, but a cyan coupler that can satisfy all of the above-mentioned required properties has not yet been found.

For example, the phenol cores described in U.S. Pat. No. 2,772,162 and U.S. Pat. A 2,5-diacylaminophenol cyan coupler having an acylamino group at the 5-position and the 5-position is excellent in terms of dye heat resistance and spectral absorption characteristics, but is significantly inferior in terms of light resistance and color development of the coupler itself. Inferior.

One of the couplers that has improved these drawbacks is Fehl's nuclear four, which performs a coupling reaction with the oxidized form of a color developing agent.
U.S. Pat. No. 3,758,308 describes the use of a so-called 2-equivalent type coupler in which a fluorine atom is introduced in place of hydrogen at the 2-equivalent position, and has shown excellent performance. It also has the undesirable property of easily causing yellow staining.

Mata, 7 A 2,5-diacylaminophenol cyan coupler in which a pentafluoro-tetrabenzamide group is introduced into the 2-position of the enol nucleus is described in U.S. Pat. Nos. 3,758°308 and 3,880,661. Furthermore, a phenolic cyan coupler in which an 0-sulfonamide hensamito group was introduced into the 2-position of the phenol nucleus was disclosed in Japanese Patent Application Laid-open No. 56-8.
No. 0045.

Although this type of coupler is excellent in terms of spectral absorption characteristics, it is not necessarily satisfactory in terms of dye fastness, which is another important characteristic.

On the other hand, as an example of a cyan coupler that improves the fastness of the above-mentioned dye, 2,5-diacylaminophenol cyan coupler in which a sulfonamide group is introduced as the Fj8 group at the 5-position of the phenol nucleus is used. 1096
No. 30, No. 56-29235, No. 55-163537
No. 56-99341, No. 56-116030,
It is known from No. 56-55945. However, these couplers do not necessarily have satisfactory performance.

Furthermore, a 2,5-diacylaminophenol cyan coupler having a benzamide group substituted with at least one fluorine atom at the 2-position of the phenol nucleus has also been developed and is described, for example, in JP-A-56-161542. Although these couplers have excellent dye fastness, they have problems with spectral absorption characteristics and coupler color development. SUMMARY OF THE INVENTION Therefore, the object of the present invention is to improve the above-mentioned conventional drawbacks, and to provide not only excellent maximum dye density and color reproducibility, but also excellent light resistance, heat resistance, moisture resistance, and stain resistance. Another object of the present invention is to provide a phenolic cyan coupler for photographic use in which the occurrence of the above-mentioned phenolic photographic couplers is prevented. It is about providing.

As a result of various studies conducted by the present inventors, the above objective was to have a phenol acylamino mole substituted at the ortho position with a fluorinated alkyl group at the 2-position of the phenol nucleus, and an acylamino stalk at the 5-position. It has been found that this can be achieved using a phenolic photographic cyan coupler.

According to the present invention, the cyan coupler of the present invention can preferably be represented by the following general formula (I).

General formula (I) In the formula, Rf represents an alkyl substituted with at least one fluorine atom, preferably an alkyl having 1 to 6 carbon atoms (e.g., fluoromethyl, trifluoromethyl, heptafluoroisopropylph), and Ro represents It represents an alkyl group or an aryl group, and nt represents a hydrogen atom, a halogen atom, or a monovalent organic group. Also, 2 represents a hydrogen atom or a group that can be eliminated by coupling with an oxidized product of a color developing agent. n represents It represents an integer of 1 to 3, and when n is 2 or more, Ro may be the same or different groups.

The alkyl group represented by R1 above may be linear or branched. Examples of straight chain or branched alkyl groups include:
There are various groups such as t-butyl, n-octyl, n-dodecyl, and n-hexadecyl, and examples of alkyl groups having a substituent include aralkyl groups (specifically, phenethyl, etc.), alkoxyalkyl groups (specifically, n-hexyloxyethyl, etc.), aryloxyalkyl groups [specifically, 1-(2,4-di-t-acylphenoquidinoprobyl, 3-(2,4,6-)lychlorf Examples include enoxynododecyl, 1-(3-butanesulfonylaminophenoxynononyl, etc.).

Furthermore, the aryl group represented by R′ above is, for example, f x =
Ate, m-hentadecylphenyl group, p7 uroylaminophenyl group, naphthyl group, etc. are included.

Next, the halogen atom represented by R2 is preferably a fluorine atom or a chlorine atom, and the monovalent organic group represented by R1 is an alkyl group (also in this case, it may be substituted, may be the same as the substituents for the alkyl group mentioned above), argylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, alkoxy group, aryloxy group, cyano group, carboxyl group. group, an alkylsulfonamide group, an arylsulfonamide group, and the like.

In addition, as a group that can be eliminated by coupling with a heavy color developing agent represented by 2, for example, a halogen atom (
For example, fluorine atom, chlorine atom λ, alkoxy group, aryloxy group, heteroyloxy group, alkylthio group, arylthio group, heteroylthio group, alkylsulfonamide group, arylsulfonamide group, ryosyl group, heteroyl group, arylazo group, phosphor group. Examples include a nyloxy group.

Typical specific examples of the cyan coupler of the present invention represented by the general formula (I) are listed below, but the present invention is not limited thereto.

(Exemplary compound) ○Art Hu(t) 00+@Hgy(nJ N = N (13) ! (14) 011H2l(”) (20) (2υ (22) (24) (25) H (Otori 'Jlft111 (27 no. (28) 0H.

(4H17(n) (3(υ 1) Next, typical synthesis steps and synthesis examples of the cyan coupler of the present invention will be described.

Synthesis Example 1 (Synthesis of Exemplified Compound 6 (1) Synthesis of 2-(2-)lifluoromethylbenzamidono-4-chloro-5-ditrophenol; 2-amino-4-chloro-5 in 200 ml of acetonitrile
-9.43 g of ditrophenol and 10.43 g of 2-trifluoromethylbenzoic acid chloride were added, and the mixture was stirred and refluxed for 6 hours. After removing the insoluble matter, the mixture is cooled, and the resulting precipitate is collected, washed, and dried to obtain 12.66 g of the desired product in the form of yellowish brown needle crystals.

(2) 2- (2-) IJ Synthesis of fluoromethylbenzamide-4-chloro-5-aminephenol hydrochloride; Catalytic reduction was carried out under normal pressure by adding 9.02 g of trophenol, 15 rnll of hydrochloric acid, and 1 g of 5% palladium on carbon.

After the theoretical amount of hydrogen has been absorbed, the catalyst is separated from P and concentrated under reduced pressure to obtain 8.64 g of the target product as a grayish white powder.

(3) Synthesis of Exemplified Compound 6; 3.6 ml of amine hydrochloride obtained by the above synthesis method in 5 oml of acetic acid
After adding 1.97 g of anhydrous sodium acetate and stirring at room temperature, α-(4-dimethylaminosulfonamide phenoxynotetradecanoic acid chloride 5
．． A solution containing 0.01 g was added dropwise to the reactor for 1 hour at room temperature. The reaction solution was added to ice water (5 oom/ml), and 3 ml of ethyl acetate was added.
Extract with ooml. After washing with water and dehydrating with anhydrous magnesium sulfate, concentrate under reduced pressure. The obtained residue was separated and purified by column chromatography using a toluene-ethyl acetate mixture as an eluent. Recrystallization from acetonitrile yields the desired product 2.879 as a pale yellow-white powder. It was confirmed by nuclear magnetic resonance spectroscopy and mass spectrometry that the obtained product had the structure of the target product.

Synthesis Example 2 (Synthesis a of Exemplified Compound 15) In 15 oml of tetrahydrofuran, (2
) and 2 ml of pyridine were added, and while stirring under ice-water cooling, α-(2,4,6-)lichlorophenoxif was added to 3 oml of tetrahydro7ran. Dodecanoyl chloride 4.14. A solution of ji+ is added dropwise, and the mixture is further reacted at room temperature for 30 minutes. The reaction solution was added to 1 liter of ice water containing 5 d of hydrochloric acid, and 300 ml of ethyl acetate was added.
Extract with +J. After washing with water and dehydrating anhydrous magnesium sulfate,
Decompression densification. By recrystallizing the obtained crude product twice from acetonitrile, the desired product as white crystals was obtained as 2.
Obtain 31g.

Synthesis Example 3 (Synthesis of Exemplified Compound 20) (1) Synthesis of 2-[2,6-bis(trifluoromethylnobenzamide]-4-chloro-5-ditrophenol; 2-amino- 9.43 g of 4-chloro-5-nitrophenol and 2,6-bis(
Trifluoromethylbenzoic acid chloride 14.53g
was added, and the mixture was stirred and refluxed for 15 hours.

Cool, collect the resulting precipitate, wash with acetonitrile,
After further washing with dioxane and drying, 8.15 g of the desired product as a yellowish brown powder was obtained.

(2) Synthesis of Exemplary Compound 2 Dissolve 4.279 2-[2,6-bis(trifluoromethylnobenzamido]-4-chloro-5-ditrophenol) in 10011/liter of tetrahydrofuran, and remove the insoluble matter by 1 Separate. Ethanol yornl and 0.5 g of 5% palladium on carbon were added to the r liquid, and catalytic reduction was performed under normal pressure. After the theoretical amount of hydrogen absorption had occurred, the catalyst was separated and concentrated under reduced pressure. Add 1 fl of tetrahydrofuran to the residue.
o #Ij and 1 ml of pyridine were added, and α-(2,4-
G-tert-pentylphenoquidinobutyric acid chloride 3
．． 73. A solution containing li+ was added dropwise, and the mixture was further reacted at room temperature for 1 hour. The reaction solution was added to 1 ml of ice water containing 2 ml of hydrochloric acid, and extracted with 300 g of ethyl acetate. After washing with water and dehydrating with anhydrous magnesium sulfate, concentrate under reduced pressure. The obtained crude product is recrystallized from a mixture of acetonitrile and ethyl acetate to obtain 3.22 g of the desired product as white crystals.

It was confirmed by nuclear magnetic resonance spectroscopy and mass spectrometry that the product had the structure of the target object.

The thus obtained silver halide color photographic material containing the cyan coupler of the present invention not only has excellent sensitivity, color density, and color reproducibility, but also has higher dye light resistance than conventional couplers. It has excellent properties such as hardness, heat resistance, and moisture resistance, prevents staining, and has good image characteristics.

Further, the present invention will be described in detail.

In order to incorporate the cyan coupler according to the present invention into an emulsion, a conventionally known method may be followed. For example, high boiling point organic solvents with a boiling point of 175°C or higher such as tricresyl phosphate and dibutyl phthalate, or low boiling point solvents such as butyl acetate and butyl propionate. After dissolving the coupler of the present invention alone or in a mixture thereof as necessary, the coupler is mixed with an aqueous gelatin solution containing a surfactant, and then heated using a high-speed rotary mixer and ultrasonic waves. After emulsifying with a disperser or colloid mill, it can be added to silver halide to prepare the silver halide emulsion used in the present invention. When the coupler according to the present invention is added to a silver halide emulsion, it is usually an average of 0.07 to 0.7 mol, preferably 0.1 mol to 0.4 mol, per 1 mol of silver halide. The coupler according to the present invention is added within the range of .

The halogenated color photographic material containing the cyan coupler of the present invention may be a monochrome element or a multicolor element.

When used in multicolor elements, the cyan dye-forming couplers of this invention are normally included in red-sensitive emulsions, but may be incorporated into unsensitized emulsions or emulsion layers sensitive to the three primary regions of the spectrum other than red-sensitivity. It may be contained inside. Each unit of the multicolor element may consist of either a single emulsion layer or multiple emulsion layers sensitive to a certain region of the spectrum. The layers of the element, including the layers of imaging units, can be arranged in various orders as is known in the art. A typical multicolor photographic element comprises a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer having at least one cyan dye-forming coupler (at least one of the cyan dye-forming couplers being a coupler of the invention). ) a magenta dye image-forming unit consisting of at least one green-sensitive silver halide emulsion layer having at least one magenta dye-forming coupler; at least one blue-sensitive silver halide emulsion layer having at least one yellow dye-forming coupler; It consists of a yellow dye image-forming structural unit supported on a support.

The silver halide used in the silver halide emulsion of the photosensitive layer in the present invention includes conventional silver halides such as silver bromide, silver chloride, silver iodobromide, tin chlorobromide, and silver chloroiodobromide. Any used in emulsions is included.

The silver halide emulsion constituting the silver halide emulsion layer used in the present invention can be produced by various manufacturing methods including the usual manufacturing method, such as the method described in Japanese Patent Publication No. 46-7'772. , or U.S. Patent No. 2,592,25
The method described in No. 0 is to form an emulsion of silver salt grains consisting of at least a portion of silver salt whose solubility is greater than that of silver bromide, and then at least a portion of the grains to be treated with silver bromide or iodobromide. It can be prepared by any manufacturing method such as a so-called conversion emulsion manufacturing method, such as converting it into silver, or a Lippmann emulsion manufacturing method consisting of fine-grained silver halide having an average grain size of 0.1 μm or less.

Furthermore, the above silver halide emulsion may contain sulfur sensitizers such as allylthiocarbamide, thiourea, cystine, etc., active or inactive selenium sensitizers, and reduction sensitizers.
For example, stannous salts, polyamines, etc., noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurosulfobenzthiazole methyl chloride, etc., or, for example, rutinium, rhodium, iridium. Chemical sensitization can be carried out using water-soluble salt sensitizers such as ammonium chloroparadate, potassium chlorooleate, and sodium chloroparadite alone or in combination as appropriate.

Further, the above-mentioned silver halide emulsion can contain various known photographic additives. For example, Reeearc
h Disorosure I 97 B December Item 17643 as a photographic additive.

The silver halide used in the present invention is spectral sensitized by selecting an appropriate sensitizing dye in order to impart photosensitivity 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.
, No. 378, No. 2,442,710, No. 2゜45
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in the specifications of No. 4.629 and No. 2.776,280.

The color developing solution that can be used in the present invention is preferably
The main component is an aromatic primary amine thread color developing agent. Typical examples of color developing agents include those based on p-phenylenediamine, such as diethyl-p-7enylenediamine in acid m, monomethyl-
p-7 enylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2-reminor 5-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N
-dodecylamino-toluene, 2-reminnow 5-(N
-Ethyl-N-β-methanesulfone and midoethyl 2-aminotoluene #! salt, 4 (N-ethyl-N-β-methanesulfonamidoethyl-minonoacholine, 4-(N
The first examples include -ethyl-N-β-hydroxyethylminonoaniline, 2-amino-5-(N-ethyl-N-β-methoxyethyl)aminotoluene, and the like.

These color developing agents may be used alone or in combination of two or more, and if necessary, in combination with black and white developing agents such as hydridetetraquinone, phenidone, etc.

Furthermore, color developers 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 development regulators such as citrazine. It may also contain an acid or the like.

The present invention will be specifically described below with reference to Examples. It is not limited to these.

Example 1 Using exemplary couplers of the present invention and comparative couplers as shown in Table 1 below, 10 g of each coupler was
-Butyl phthalate was added to a mixture of 51 rtl and 30 m of ethyl acetate and heated to 60°C to completely dissolve. This solution was mixed with 5 ml of Alkanol B (alkylnaphthalene sulfonate, DuPont horn 10% aqueous solution) and
% gelatin aqueous solution and emulsified using a colloid mill to prepare a 1 L (7) cuff color dispersion. Next, this coupler dispersion was added to 500 g of gelatin-silver chlorobromide emulsion, coated on polyethylene-coated paper, and dried to produce six types of silver halide color 'q true light-sensitive materials listed in Table 1. did. These samples were subjected to wedge exposure according to a conventional method, and then subjected to the following processing.

Processing process (30℃) Processing time Color development 3 minutes 30 seconds Bleach fixing 1 minute 30 seconds Wash with water 2 minutes The composition of each treatment is shown below.

[Color developing solution composition] [Bleach-fixing solution composition] The photographic properties of each of the samples obtained by the above processing were measured. For the measurements, a PDA-60 type densitometer (manufactured by Konishiroku Photo Industry Co., Ltd.) was used. The obtained results are shown in Table 1 below.

The 11+Y degree value in the table indicates the value of the sample with maximum sensitivity by 1
The relative sensitivity was expressed as 00.

(Comparative Caprano (U.S. Patent No. 2,801,171a)
-109630) H (Described in JP-A-56-80045) As is clear from the above table, all samples 1 to 3 containing the coupler of the present invention had excellent color development and good sensitivity. It was found that it had the highest concentration and the spectral absorption characteristics were also good.

Example 2 Using exemplary couplers of the present invention and comparative couplers as shown in Table 2 below, a cyan dye image was obtained by carrying out the dew YC1 development process in the same manner as in Example 1. ii for each sample on which this dye image was formed! JI(k) was tested for yC resistance, heat resistance, moisture resistance, etc. The obtained results are shown in Table 2 below.

In the table above, the light resistance is measured after exposing each image to a xenon fade meter for 200 hours, and the heat resistance is measured after 77
After storage for 2 weeks at ℃, further humidity resistance is 60℃, relative humidity 8
The residual rate at the initial concentration of 1.0 after storage for 2 weeks at 0% is expressed as a percentage.

Table 2 (Comparative coupler) 04H0 (described in U.S. Pat. No. 2,895,826) As is clear from the above Table 2, the comparative couplers (A) that had good color development properties in the above Table 1 were: In particular, they are inferior in heat resistance and moisture resistance, and comparative couplers (0) and (D) have significant problems in light resistance, making it difficult to put them to practical use.

In contrast to this, the coupler of the present invention can be used for any of the above. It can be seen that the film also showed very excellent performance in terms of the above, and had stable image storage properties. In addition, staining was not observed during storage. There wasn't.

Agent Yoshimi Kuwahara procedural amendment? ! 1. I detective 11 Rikuchi Kazuo Wakasugi 2 Name of the invention Photographic cyan coupler Ii hli 11 minutes 8 if ('L to 0) Relationship special fr11i Ii
Person 1 Location 14゛II 26' Nishi-Shinjuku, Shinjuku-ku, Tokyo
#2.

Name (+271 Konishi Roku Photo-1, Industry Co., Ltd. 1st generation l
<jry, for closing Nobuhiko Moto 4 agent 〒191 notification 1su I East 1; Town II! IIf Nakaguri 1 town 1
if; Jiko Nishi Roku', 'j', l'Ll Industry Co., Ltd. t1
5Jllilligi<t [1a.16, Column 7 of "Detailed Description of the Invention" of the specification to be amended, contents of the amendment The detailed description of the invention is amended as follows.

Claims (1)

[Claims] A phenol-based photographic cyan coupler, characterized in that the phenol has a penduamide group substituted at the ortho position with a fluorinated alkyl group at the 2-position of the phenol, and an acylamino group at the 5-position. coupler.