JPS5831334A - Cyan dye forming coupler - Google Patents

Abstract

PURPOSE:To obtain a phenol type cyan dye forming coupler exhibiting superior color development sensitivity and high color development density without requiring addition of benzyl alcohol having a problem in environmental pollution. CONSTITUTION:The cyan dye forming coupler of this invention has general formulaeIand II in which R<1>, R<2> are H, alkyl, alkenyl, aryl, heterocyclic, cycloalkyl, acyl, or the like; R<3> is a ballasting group; and X is a group releasing upon reacting the oxidized product of a color developing agent. The compounds of formulaeI, II are obtained, for example, by reacting the compound of formula III with that of formula IV, catalytically reducing the resultant, and reacting it with an isocyanate compound. The cyan dye forming coupler of formulaeIand II are mixed with a silver halide emulsion and this emulsion is coated on a base, thus permitting a silver halide color photographic material superior in sensitivity and the like to be obtained.

Description

[Detailed description of the invention] The present invention is a novel cyan dye color-forming coupler.

and a silver halide color satin photosensitive material containing the same. Normally, color images are produced by the reduction of exposed silver halide grains by an aromatic class 1 adenyl color developing agent. The dye is formed by oxidative coupling with the coupler forming each dye in a silver/silver emulsion.

Couplers commonly used in KAII to form cyan dyes are phenols and naphthols.

Considering the photographic performance of conventional couplers, the basic properties required for 7-enols are that the spectral absorption characteristics of the dye are excellent, that is, the edge region of the speckle should be sharp and without any gaps. The pigment formed is light, heat, moisture II
It should have sufficient toughness for aK, good color development, that is, sufficient color development sensitivity and color density, and a whitening bath or bleach-fixing mainly composed of KBD'rA No. 2 iron wall. Removal of benzyl alcohol added to color developing solution has been taken up as a major issue in the ``Meimen of Dekin'' book. ing. However, the current situation is that sufficient color development cannot generally be obtained unless benzyl alcohol is added.

The decrease in color development due to removal of benzyl alcohol is remarkable in phenolic cyan couplers, and from this point of view, there is a demand for phenolic cyan couplers with high 411 color properties without benzyl alcohol. There is.

Efforts have been made to satisfy the above-mentioned requirements, but as far as we know, a cyan coupler that satisfies all of the above-mentioned required properties has not yet been found.

For example, 6-[α-(2,4-di-t-,-'7-electrophenoxy)butanead]-2,4-cyte is described in U.S. Pat. No. 9,801,171. Although rho-3-methylphenol has good light resistance, it has shortcomings in heat resistance, and in addition, there is a large loss of dye in a tired bleach-fix solution, and color development is highly dependent on benzyl alcohol.
Removal of benzyl alcohol from color developing solutions is difficult. 2-Hepetafluoroptana described in U.S. Pat. No. 2,895,826? )”-5-(α-(2,4-G-t-
Phenol is superior in terms of heat resistance and dye loss in a fatigued bleach-fixing bath, but is inferior in terms of light resistance and color development. Furthermore, the coupler described in JP-A-53-109630 still has problems in terms of removal of benzyl alcohol and light resistance.
No. 4, Japanese Patent Publication No. 47-37421 $1 Publication% 轡金显48-
No. 36894, Special Gil No. 50-10135, No. 50-1174124, No. 5G-1114411),
IIl 5G-1051841, ftfl 50-1
The phenolic cyan couplers described in Publication No. 203344 and the like are also unsatisfactory in terms of heat resistance and removal of benzyl alcohol. ! A phenol coupler having a ureido group in the British patent 1. No. 011,940 and U.S. Patent Tuna 3,446,622-1. No. 3,998,253,
As described in No. 3,758,308, the cyan dye formed by these couplers has a low spectral absorption, and furthermore, the kll station maximum is in the relatively short wavelength region of the red region. Although the phenol coupler having a ureido group at the 2-position described in 4$-@56-65134, which has considerable absorption in the edge region of the spectrum and is unfavorable for color reproduction, has considerably improved series IIK in the spectroscopic region. , other goodness is not enough.

As a result of extensive research into these conventional techniques, the present inventors have found that the couplers represented by the following general formulas (■) and (If) have the characteristics required for the above-mentioned phenolic cyan couplers. I have found that I can add enough.

General formula (II) Kel group, aryl group, heterocyclic group, shifsia alkyl group,
Representing an acyl group (e.g. alkylcarzenyl group, carboel group), for example, an alkyl group, an aryl group, a substituent (fluorine, chlorine or bromine)
, trifluorotetramethyl group, cyano group, hydroxyl group, alpoxy group, acyloxy group, azila group, sulfonamido group, sulfonyl group, sulfonyl group, sulfo group, carboxylic acid group The alkyl group may have a straight chain or a branched chain.

Also, ν, ν are connected across t, ? 5 or IJjlm may be formed.*The atoms constituting R are base atoms.

Oxygen atoms, meet! R1 represents a ballast group, which can be selected from atom and sulfur atom. Here, the ballast group refers to a bulky organic group given to the coupler molecule to prevent it from diffusing from the layer in which the coupler is installed.
For example, there are alkyl groups and aryl groups having a total number of carbon atoms of 8 to 8. Substituents include alkyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylthio groups, arylthio groups, alkylsulfonyl groups, arylsulfonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyl groups, acyloxy groups, sulfonyl groups, etc. do group,
It may have a sulfamoyl group, a halogen atom, a hydroxyl group, a carboxy group, etc., and the alkyl and aryl moieties of these substituents may be further substituted with the above-mentioned substituents.

X represents a group that can be eliminated during a coupling reaction with hydrogen or a color-forming oxidation product; Aryloxy group, carbamyloxy group, carbamoylmethoxy group, acyloxy group, sulfonamide group, co/1 bonded to the coupling position
A more specific example is a phosphoric acid group.
U.S. Patent No. 3,471,563, JP 47-3742
No. 5, Special Publication No. 48-36894, 49 1973-10
No. 135, No. 50-117422, No. 5G-130
No. 441, 51-1088414! I.

So-120384, So-52-tssts,
The methods described in Publications No. 53-52428 and No. 53-105226 are useful.

Examples of cyan couplers defined in the claims of the present invention are shown below, but the invention is not limited thereto.

Typical synthetic routes and synthetic examples of the couplers of the present invention are shown below.

Synthesis example! (Synthesis of Exemplary Coupler I) 2-(α-(2,4-di-tert-pentylphenoxy)tetradecanamide)-4-ri64-5-(3-(
Synthesis of 3-enoxycarbonyl7ethyl)ureido)phenol.

1&, 2-ami'-ri a a -5-x= )
* Dissolve phenol in 1OO- acetonitrile,
i, op pyridine was added. While stirring at 1 m temperature, a melt of 4811 α-(2,4-di-t@rt-pentylphenoxy)tetradecane acid relide dissolved in too sl of acetonitrile was added dropwise over about 1 hour. After further stirring, the reaction *1 was poured into ice water and extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 55I as an oil.

The oily substance obtained as described above is mixed with alcohol.
catalytic reduction was carried out using a palladium-carbon catalyst. After absorbing 1 stoichiometric amount of hydrogen.

The catalyst was removed by filtration. Concentrate the filtrate under reduced pressure,
Crude crystal 53II was obtained by washing with Hekina y.

The above crude crystal 131i was dissolved in toluene.

3.8JII 8-Ethoxycarbonyl 7 After elution with a mixed solvent of hexane and toluene, recrystallization was performed with a mixed solvent of hexane and ethyl acetate. i
e) @ got a promise. The structure of the target product was confirmed by electrolytic desorption mass spectrometry and Psitonkyo B spectrum.

Synthesis Example 2 (Synthesis of Exemplary Coupler 6) 2-(4-(3-dodecyloxyphenoxy)butanyl)-4-Flerot 5-(N,N-betamethyl)
) Ureidophenol tHp 2-A consideration no 4-ri stomach low 5-! Drophenol was dissolved in 100-acetonitrile #cfII, 1,0
Pyridine of j was added. Add 4-(3-dodecyloxyphenoxy)butane in a stirred vessel at room temperature.
A solution of 100% in acetonitrile was added dropwise. After further stirring, the reaction S* was poured into ice water and extracted with ethyl acetate. After washing the extract with water, drying with 9 um of anhydrous sulfuric acid,
It was concentrated under reduced pressure and recrystallized in acetotrile. A white solid of 45I was obtained. The above white solid was subjected to catalytic reduction using 300117 alcohol KW and palladium-carbon catalyst. After absorbing 1 stoichiometric amount of hydrogen, the catalyst was removed by filtration. The filtrate was concentrated under reduced pressure and washed with hemisan to obtain crude crystals 431.

The above crude crystal 129 was dissolved in 100-Toluene yK@, and 10
The 1-piperidine carbon of 7-layer chloride (capital) d-toluene*W was added. After stirring at room temperature for 1 hour, one precipitate was filtered off, and the filtrate was subjected to S condensation. After eluting the concentrated solution with a mixed solvent of hexane and toluene in a silica gel column Coomad Gras 74, a-k) recrystallization from nitrile, 8. s#f
)! I got a deal. The structure of the target product was confirmed by electrolytic desorption mass spectrometry and Psitonran spectrum.

The cyan dye-forming couplers used in this invention are similar to those used in conventional cyan dye-forming couplers. Typically, the coupler is incorporated into a dyed chain emulsion and the emulsion is coated onto a paste to form the photographic element.

A photographic element can be a single color element or a +1 multicolor element. In multicolor elements, the cyan dye-forming couplers of this invention are normally incorporated into red-sensitive emulsions, but may also be incorporated into non-sensitized emulsions or dye image-forming units sensitive to each of the triad regions of the spectrum. have The layers of the element, including layers of 0 image side-forming units, each of which may consist of a single pore layer or multiple emulsion layers sensitive to a certain region of the spectrum, are known in the art. They can be arranged in various orders as shown. A typical multicolor photographic element consists of a cyan dye image-forming unit consisting of at least one red-sensitive hagenated chain emulsion layer having at least one cyan dye-forming coupler (at least one of the cyan dye-forming couplers is present). Pl) at least one inventive coupler! It consists of at least one blue-sensitive silver halide emulsion layer having a zenta dye-forming coupler supported on a yellow dye image-forming unit base.

The bulk can have additional layers, such as a filter layer, an interlayer protective layer, and a primer layer.

In order to incorporate the coupler of the present invention into an emulsion, a conventionally known method may be followed. For example, the boiling point of tricresyl phoscetate, dibutyl 7 Talley F cape is 17! Has a high boiling point of over $ ℃! I! After WS of the coupler of the present invention alone or in combination with a low boiling point solvent such as butyl acetate, butyl acetate, butyl acetate, or a mixture thereof as necessary, a surfactant is added. Contains gelatin water S
The silver halide emulsion used in the present invention can be prepared by mixing with * and first emulsifying it in a high-speed rotating tdP rotary rotary tdP mill or a sulfur mill, and then adding it to silver halide. When this coupler is added to the silver halide emulsion of the present invention, it is usually about 0.07 mol per mole of silver halide.
~G, 7 sth le, preferably Irt 0.1-0
．． The couplers of the invention are added in the range 4-vlf).

Book@l! f) Hap used in Aa silver generator emulsion
Silver genides include any compounds used in conventional silver halide emulsions, such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and Is chloroiodobromide.

The silver halide emulsion constituting the silver halide emulsion of the present invention can be manufactured by various manufacturing methods including the usual manufacturing method, such as the method described in Japanese Patent Publication No. 46-7772, that is, the solubility is higher than that of silver bromide. A method for producing a so-called composite emulsion, which involves forming an emulsion of silver-based grains that are large in size and consisting of at least a portion of silver groups, and then converting at least a portion of the grains into silver bromide or silver iodobromide salt; Or 0.
It can be prepared by any method such as the method for producing a Lippmann emulsion consisting of finely divided hagenated particles having an average grain size of one tone or less.

Furthermore, the silver halide emulsion of the present invention may contain sulfur sensitizers such as allylthiocarbamide, thiourea, cape cystine, active or inactive selenium sensitizers, and reduction sensitizers such as *1 tin sensitizer, boria Noble metal sensitizers 1 For example, gold sensitizers, specifically potassium aurithiocyanate, potassium fluoroate, 2-ester sulfopene
sensitizers such as dithiazole methylchloride, or water-soluble salts such as ruthenium, tetradium, and iridium, specifically, a/quaternium black tetrachloride 5f-F, potassium tetrachloride, etc.
It can be chemically sensitized by using roptilanate and sodium chloroparadia alone or in combination as appropriate.
Wear.

Furthermore, the silver halide emulsion of the present invention can contain various known photographic additives. For example, Re5a+r
A photographic additive as described in d. Disclos Nail (Research Disclosure), December 1978 @ 17643 K.

The halogenated emulsion of the present invention is spectral sensitized by selecting an appropriate sensitizing dye in order to impart photosensitivity in the wavelength range required for red-sensitive emulsions. Various spectral sensitizing dyes are used, and these can be used alone or in combination.

Spectral sensitizing dyes that are advantageously used in the present invention include 1, for example, US IO Patent No. 2,269,234;
270,378-41! , Lock Iff 2,442,71
No. 0, II No. 2,454,629, 2,776 votes counted
j804! Typical examples include □ cyanine dyes, Meda cyanine dyes, and +t complex v-anine dyes as described in various specifications.

HimiflRK#I is preferably a color developing agent containing an aromatic primary amine color developing agent as a main component. Variants of this color developing agent are representatively -7z elm/shea-based ones; for example, diethyl-p-78 nylene diane salt, monomethyl-p-phenylene diane sulfate, dimethyl-T )
=7
Ethyl-N-dobusylaz))-toluene, 2-72no5-(N-ethyl-N-β-methanesulfonanodoethyl)amine toluene sulfate, 4-(N-ethyl-N-
β-Methanesulfone anodoethyl acetate)) Aniline, 4
-(N-ethyl-N-β-hydoxyethylamino)aniline, 2-arano-5-(N-ethyl-N-β-methoxyethyl)amine toluene, and the like.

After development, bleach to remove silver and bald spots.
The usual steps of fixing or bleaching, washing and drying are carried out.

The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example (1) The couplers of the present invention as shown in the AT table and the following comparative couplers (A), CB), and (C) were each weighed in an amount of 0.037, and the same amount of 7-talic acid as the weight was added. The mixture was added to a mixture of dibutyl and 3 times the amount of ethyl acetate and heated to ω°C to completely dissolve KfI. This solution was added to an aqueous solution of alkanol B (alkylnaphthalene sulfonate, DuPont Co., Ltd. 11) and gelatin, and emulsified using cotetrahydride to prepare each coupler dispersion.Next, this coupler dispersion was used as silver. Silver chloride bromide emulsion (2D mole is silver bromide) containing 0.1 mmol was added, coated on polyethylene laminate paper and dried, resulting in six types of silver halide color photographs with stable coating films. Photosensitive materials (sample numbers [!] to [6])
I got it.

U! Comparative coupler [B] Comparative coupler CC) These samples were subjected to wedge exposure according to a conventional method and then subjected to fire treatment. However, color development 11 was carried out for two types of compositions: one with added alcohol ([color developer composition!]) and one without ([color developer composition z]).

〔process〕 Treatment process 1m (30℃) Processing time The composition of each treatment is shown below.

[Color development 1 [IIi formation! ] [Color developer composition 2] [Bleach-fix solution composition] Photographic sensitivity was measured for each of the obtained samples.

Check out the results! ! ! Shown below. The relative sensitivity values in the table are expressed with the maximum sensitivity value when processed with [Color Development** Composition 1] as 100.

As is clear from Table 1, the samples obtained using the coupler according to the present invention are excellent in that good sensitivity and maximum density can be obtained regardless of the presence of benzyl alcohol.

Furthermore, as a result of measuring the color spectrum, it was found that the dye using the coupler of the present invention has a maximum plateau in a relatively long part of the red region, and exhibits excellent color purity with little absorption on the short wavelength side. .

II Vaginal Example (=) Using a sample obtained in the same manner as in Example (1) above, the light resistance, heat resistance, and moisture resistance of the dye image were examined.

In addition, the light resistance in the table is expressed as the residual concentration after 300 hours of exposure of each obtained image in a xenon 7-ade meter, with the concentration before exposure being 100. Moisture resistance was expressed as a residual temperature of 111 degrees after storage for 3 weeks at a temperature of 70 degrees Celsius and a relative humidity of 70 degrees, with the concentration before the test being 100. In addition, the heat resistance is
After storage for 3 weeks at 77℃, the concentration before the test! Expressed as OO. (Only LIIIJ11 degrees 1.
0) #x! As is clear from the table, comparative coupler 1'A) has excellent light resistance, but has a problem with heat and humidity resistance, and comparative couplers CB) and (C) have excellent heat and humidity resistance, but [color development] **Composition 2] has a problem with light resistance.

On the other hand, it can be seen that the exemplary couplers (1), (6) and [7] according to the present invention are couplers having excellent performance in all respects.

Example (3) Couplers of the present invention as shown in Table 3, the above comparative coupler (A), CB'l and the following comparative coupler (D)
0.01% of each was added to the mixture with the same amount of tricresyl phosphate and three times the amount of ethyl acetate, and the mixture was heated to ω° C. to completely dissolve. Alkanol B and an aqueous gelatin solution 1[K were added to this solution, and the mixture was emulsified using a colloid to prepare each coupler dispersion.

This coupler dispersion was then added to an iodobromide chain emulsion containing 0.1 mol of silver (6 mol of iodide II), dried and stabilized on a KII cloth L on a Shichiruta-suacetate film base. Six kinds of silver tetrageyide color photographic light-sensitive materials (sample number [13) 4.[1]] having a coating strength of 100% were obtained.

Comparative coupler CD] These samples were subjected to wedge exposure according to a conventional method and then subjected to fire treatment.

[Button-I]

Processing time (33℃) Processing time [Composition of color developer] [Fixer composition] □ [Stabilized tILII 1ml! ] Hidden! Phosphorus (37qII water soluble 11) 1.5m
j The photographic characteristics of the obtained cyan colored image were measured. The results are shown in Table 3.

As is clear from Table 3 of Table 813, the samples using the coupler according to the present invention were found to be excellent in sensitivity and color development.

In addition, as a result of measuring the spectroscopic spectrum, the sample according to the present invention has a maximum absorption wavelength in the long wavelength region of the red region, and a sharp break in the short wavelength region, which is preferable in terms of color reproduction in the edge region compared to the comparative couplers. It was found that it gives a pigmented image.

Example (4) After performing wedge exposure on samples [1] to [6] obtained in Example (1), [color developer composition l] of Example (1) was applied.
).

On the other hand, development was carried out using bleach-fix 1 (substituted with the following composition) and the fading properties of the cyan dye due to fatigue bleach-fixing tlK were investigated.

[Bleach-fix solution composition]

The maximum reflection density of the cyan dye of the sample obtained by Genrin treatment was measured. The results are shown in Table 4.The dye residual rate in the maximum density area was determined by K as shown below.

W44 Table 4 It can be seen from Table 4 that the sample using the coupler of the present invention shows less fading of the cyan dye when treated with a fatigue bleach-fix solution.

Shizuo Masato Kuwabara

Claims (1)

[Claims] A cyan dye-forming coupler for photography represented by the following general formulas (1) and (II). represents a heterocyclic group, a Schiff carbon alkyl group, or an acyl group, R1 and ν may be combined with each other to form a 5- or 6-membered ring, Bs represents a palust group, and X represents a hydrogen atom or a color developing agent. )