JPH11143035A - Photosensitive silver halide photographic element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable formation of a dye image reduced in thickness after drying and enhanced in stability against light fading and high in maximum density by forming, on a support a yellow image forming hydrophilic colloidal layer containing a specified yellow dye image forming coupler and substantially no high-boiling solvent liable to remain and no nonionic polymer stabilizer on a support. SOLUTION: One of the hydrophilic colloidal layers formed on the support is the yellow image forming layer containing the yellow image dye forming coupler represented by the formula in which R is a substituent; Y is an aryl or heterocyclic group; and Z is a nonmetallic atomic group necessary to complete an N-containing heterocyclic coupling releasable group together with the N atom. The yellow image forming layer does substantially not contain any high-boiling solvent liable to remain, and any nonionic polymer stabilizer, i.e., contains each in an amount of <=1.0 weight % and, preferably, <0.5 weight % of the total yellow coupler contained in this layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION This invention relates generally to the field of light-sensitive silver halide elements, and more particularly to at least one yellow image-forming layer substantially free of residual high boiling coupler solvents and nonionic polymer stabilizers. Photographic elements.

[0002]

BACKGROUND OF THE INVENTION Various techniques are known for dispersing hydrophobic photographically useful compounds, such as photographic couplers, in photographic element layer coating compositions containing hydrophilic colloids. Photographic dye-forming couplers, as well as other hydrophobic photographically useful compounds, typically form an aqueous dispersion of the coupler first in a hydrophilic colloid layer of a photographic element and then apply the dispersion to a layer coating solution. To be included by mixing. Organic solvents are typically used to dissolve the coupler, and then the resulting organic solution is dispersed in an aqueous medium to form an aqueous dispersion.

[0003] The organic phase of these dispersions often contains a high boiling or residual organic solvent alone or with a low boiling or water miscible solvent which is removed after dispersion formation. Since the residual high boiling solvents have a sufficiently high boiling point, generally above 150 ° C. at atmospheric pressure, they do not evaporate in the usual dispersion forming and photographic layer coating operations. Residual high-boiling coupler solvents are used primarily in conventional "oil-protected" dispersion methods, whereby the organic solvent remains in the dispersion and therefore in the emulsion layer coating solution and ultimately in the photographic element. include.

Conventional "oil-in-water" dispersion methods for including hydrophobic couplers are described, for example, in Jelly and Vi.
ttum in U.S. Pat. No. 2,322,027. In such conventional methods, the coupler is dissolved in a high boiling water miscible solvent, mixed with aqueous gelatin, and then dispersed using a colloid mill or homogenizer. The presence of a high boiling solvent provides a stable environment for the hydrophobic coupler, while at the same time generally increasing the reactivity of the coupler during photographic processing.

No. 2,801, Vittum et al.
No. 170 discloses preparing separate dispersions of the coupler and the high boiling solvent, and then mixing these two dispersions with a silver halide emulsion. U.S. Pat. No. 2,787,544 to Godowsky et al.
et) discloses a photographic system forming method. The dispersion of the high boiling solvent is mixed with the coupler dispersion. Both of these methods help to prevent crystallization of the coupler prior to layer coating by keeping the solvent and coupler separate until just prior to coating, while at the same time using a solvent to enhance the reactivity of the coupler in the photographic element. Include in the coating layer.

The presence of a high boiling solvent in certain coupler dispersions of a photographic element may include, for example, sufficient coupler reactivity during photographic processing, low thermal yellowing, hue modification, While often desirable to obtain improved dye dark stability and reduced crystallization, there are also certain advantages resulting from substantially removing high boiling residual solvents from photographic element imaging layers. . Minimizing the amount of residual coupler solvent applied to the photographic element is useful, for example, in reducing the applied thickness of the photographic layer. Reducing the coupler solvent level also results in a reduction in the gelatin level at the same time, further reducing the dry coating thickness. Thinner layers are advantageous because, for example, image sharpness is improved due to reduced light scattering during exposure, and developability is increased due to shorter diffusion steps through the multilayer structure. Increased developability can reduce silver and / or coupler coating levels and thus reduce material costs.

One method of preparing a solvent-free coupler dispersion that can be used to obtain photographic elements with reduced solvent levels is by precipitation as described in European Patent No. 374 837. In this method, the coupler is dissolved in a mixture of a water-miscible organic solvent and an alkali, and the resulting solution is added to water containing an anionic surfactant and a nonionic polymer to form a dispersion. To form The combination of surfactants and non-ionic polymers has been disclosed as a requirement to obtain a stable precipitation dispersion, which can result in unstable dispersions when using a single surfactant without a non-ionic polymer. It is because it forms a body. A significant disadvantage of this method is that the use of nonionic polymers increases the dry thickness of the coating layer, which is contrary to one of the main advantages of being able to reduce coupler-solvent. Another disadvantage of using this method is that small precipitated dispersion particles can react with gelatin to produce a very viscous coating solution, as described in US Pat. No. 5,358,831. It is becoming. The prior art also discloses that dispersions of hydrophobic couplers formed by the precipitation technique can form dispersions that are extremely unreactive even though they have very small particles. These dispersions may require the addition of high boiling coupler-solvents to achieve sufficient coupler reactivity. The low reactivity of the high boiling coupler-coupler in the absence of solvent is also an issue with conventional coupler dispersions.

[0008]

In a color photographic material, it is also desirable to form a dye image which is stable against light fading. Therefore, by using an image forming layer substantially free of a high boiling point residual solvent and a non-ionic polymer dispersant, a dye having a reduced maximum dry thickness and improved stability to light fading, and a high maximum density dye It would be desirable to have a silver halide color photographic material capable of forming an image.

[0009]

According to one embodiment of the present invention, there is provided:
A support comprising at least one yellow image-forming hydrophilic colloid layer comprising a yellow image dye-forming coupler of the following Formula I, wherein said yellow image-forming layer comprises a high boiling point residual solvent and a nonionic polymer. It is directed to light-sensitive silver halide photographic elements that are substantially free of stabilizers:

[0010]

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Wherein R represents a substituent, Y represents an aryl group or a heterocyclic group, and Z together with the nitrogen atom is required to complete a nitrogen-containing heterocyclic coupling-off group. Represents a non-metallic atomic group). In a preferred embodiment, the light-sensitive silver halide photographic element comprises at least one yellow image-forming hydrophilic colloid layer comprising a blue-sensitive silver halide emulsion and a yellow image dye-forming coupler.
Layer, at least one cyan image-forming hydrophilic colloid layer containing a red-sensitive silver halide emulsion and a cyan image dye-forming coupler, and a magenta image-forming hydrophilic colloid layer containing a green-sensitive silver halide emulsion and a magenta dye-forming coupler At least one layer, in turn, a support carried on one side thereof, wherein the yellow image-forming coupler is of Formula I, and the yellow image-forming layer comprises a high boiling residual solvent and It is directed to light-sensitive, halogenated photographic elements that are substantially free of nonionic polymer stabilizers.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The photographic element of the present invention comprises a yellow image-forming hydrophilic colloid layer comprising a yellow image dye-forming coupler and substantially free of high boiling point residual solvents and nonionic polymer stabilizers. It comprises one layer. As used herein, the term "high boiling residual solvent (hi
"gh boiling permanet solvent" means a coupler solvent conventionally used in the photographic industry, for example, a solvent that is typically water immiscible and has a boiling point above 150 ° C. The term “nonionic polymer stabilizer” "A compound as disclosed in European Patent No. 374 837 used to stabilize a precipitated coupler dispersion.
For example, poly (vinylpyrrolidone). For the purposes of the present invention, "substantially free of high boiling permanent solvent"
solvent) ”“ no-solvent ”,
Terms such as "solvent-free" mean that no residual organic solvent is present above trace or impurity levels. Similarly, the absence of a non-ionic polymer stabilizer means that it is not present above trace or impurity levels. The yellow image forming layer of the present invention substantially free of a high boiling point residual solvent and a nonionic polymer stabilizer contains the above component in an amount of preferably 1.0% by weight or less based on the total amount of the yellow coupler in the layer, More preferably, it contains less than 0.5 wt%, and most preferably less than 0.1 wt% based on the amount of yellow coupler. Such solvent-free yellow image-forming coupler dispersions of Formula I provide improved yellowness in exposed and processed photographic elements as compared to using yellow coupler dispersions having significant levels of residual solvent. It has been found that the performance on image dye fade issues is improved and that the coating layers can be made thinner compared to using a yellow coupler dispersion using a nonionic polymer stabilizer.

Couplers of formula I which form a yellow dye upon reaction with an oxidized color developing agent and which contain a nitrogen-containing heterocyclic coupling-off group are well known in the art,
For example, a representative patent, US Pat. No. 3,973,968
No. 4,057,432, 4,221,860
No. 4,269,936, No. 4,314,023
No. 4,327,175, No. 4,404,274
No. 4,456,681, No. 4,581,324
No. 4,748,107 and 4,770,985. Non-metallic atomic groups represented by Z in Formula I include, for example, carbon, oxygen, nitrogen or sulfur atoms. Preferably, Z represents the atoms necessary to complete a 5- or 6-membered heterocycle. Examples of 5- or 6-membered heterocycles formed by such non-metallic atomic groups with nitrogen include 2,5-dioxoimidazolidin, 2,3,5-trioxoimidazolidin, 2,5 −
Dioxotriazolidine, 3,5-dioxotriazolidine, 2,4-oxozolidinedionetriazolidine,
2,4-Thiazolidinedionetriazolidine, pyridone, pyrimidone, pyrazone, tetrazolone, tetrazole, imidazole, triazole, imidazolone, triazolone, pyrazolone, isothiazolone, quinoxazolone, isoxazolone and fluorone.
Preferably, the coupling-off group comprises a diacylamino group attached to the coupling active position of the yellow coupler by a nitrogen atom therein. Such groups include, for example, succinimide, maleimide, phthalimide,
1-methylimidazolidine-2,4-dione-3-yl group, 1-benzylimidoazolidine-2,4-dione-
3-yl group, 5,5-dityloxazolidine-2,4-
Dion-3-yl group, 5-methyl-5-propyloxazolidine-2,4-dione-3-yl group, 5,5-ditylthiazolidine-2,4-dione-3-yl group, 5,5
A dimethylimidazolidin-2,4-dione-3-yl group, a 3-methylimidazolidinyl-1-yl group,
1,2,4-triazolidine-3,5-dione-4-yl group, 1-methyl-2-phenyl-1,2,4-triazolidine-3,5-dione-4-yl group, 1-benzyl- 2-phenyl-1,2,4-triazolidine-3,5
-Dion-4-yl group, 5-hexyloxy-1-methylimidazolidin-2,4-dione-3-yl group, 5-
Methoxy-1-methylimidazolidin-2,4-dione-3-yl group, 1-benzyl-5-ethoxyimidazolidin-2,4-dione-3-yl group and 1-benzyl-
5-docesyloxyimidazolidin-2,4-dione-
And a 3-yl group.

The preferred yellow coupler used in the present invention is represented by the following formula:

[0015]

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(Wherein R ₁ , R ₂ , Q ₁ and Q ₂
Each represents a substituent; Z represents a group of atoms necessary to complete a nitrogen-containing heterocyclic coupling-off group; Y represents an aryl group or a heterocyclic group; and Q ₃ represents a nitrogen-containing heterocyclic group. Represents an organic residue necessary to form with the above-mentioned nitrogen atom; and Q ₄ represents a 3- to 5-membered hydrocarbon ring or at least one heteroatom selected from N, O, S and P. Represents a non-metal atom necessary to form a 3- to 5-membered heterocyclic ring contained in the ring). Preferred couplers are those in which Q ₁ and Q ₂ each represent an alkyl, aryl or heterocyclic group and R ₂ is an aryl or alkyl group (including cycloalkyl and bridged cycloalkyl groups), more preferably tert. -Y representing an alkyl group
ELLOW-1 and YELLOW-4. Particularly preferred yellow couplers for use in the elements of the present invention are
In the formula, Y ₂ is YELLOW-4, wherein R ₂ represents tert-alkyl and Y represents aryl.

Examples of preferred yellow couplers of the formula I include:

[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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For use in the present invention, a dispersion of a yellow imaging coupler substantially free of a high boiling residual solvent and a non-ionic polymer stabilizer comprises dispersing the coupler in a low boiling or partially aqueous solution. It can be prepared by dissolving in an auxiliary organic solvent or by melting a coupler.
The resulting liquid organic phase is then mixed with an aqueous gelatin solution, and the mixture is then mixed with a mechanical mixing device for high shear or turbulent mixing, generally suitable for preparing photographic emulsion dispersions, such as colloids. Mill, homogenizer, microfluidizer, high-speed mixer, ultrasonic disperser, blade mixer, device for pumping liquid stream under high pressure through orifice or mutual reaction chamber, Gulin mill, blender, etc. Form small particles of the organic phase suspended therein. More than one type of equipment is used to prepare the dispersion. The auxiliary organic solvent, if present, can be removed by evaporation, noodle washing or membrane dialysis. If not removed prior to application to the photographic element layer, the partially water-soluble auxiliary organic solvent can diffuse through the hydrophilic colloid layer of the element and then be removed during photographic processing. The dispersion particles are preferably less than 2 microns, generally about 0.02 to 2 microns, more preferably about 0.02 microns.
It has an average particle size of ~ 0.5 microns. These methods are described in U.S. Patent Nos. 2,322,027; 2,787,54.
No. 4, No. 2,801,170; No. 2,801,171
No. 2,949,360 and 3,396,02
No. 7.

Examples of suitable co-solvents which can be used are ethyl acetate, isopropyl acetate, butyl acetate, ethyl propionate, 2-ethoxyethyl acetate, 2- (2-butoxyethoxy) ethyl acetate, triethyl citrate, dimethylformamide , 2-methyltetrahydrofuran, triethyl phosphate, cyclohexanone, butoxyethyl acetate, methyl isobutyl ketone, methyl acetate, 4-
Methyl-2-pentanol, diethyl carbitol,
Examples thereof include 1,1,2-trichloroethane and 1,2-dichloropropane. Preferred co-solvents include ethyl acetate and 2- (2-butoxyethyloxy) ethyl acetate.

The aqueous phase of the coupler dispersion preferably contains gelatin as a hydrophilic colloid. These may be gelatin or modified gelatin, for example, acetylated gelatin, phthalated gelatin, oxidized gelatin and the like. Gelatin may be base-treated, such as lime-processed gelatin, or acid-treated, such as acid-treated ozein gelatin. Other hydrophilic colloids and ionic thickeners,
For example, water-soluble ionic polymers or copolymers such as poly (acrylic acid), poly (sodium styrenesulfonate), poly (2-acrylamido-2-methylpyrropansulfonic acid) can also be used in combination with gelatin, Not limited. Copolymers of these polymers with hydrophobic monomers can also be used.

The yellow image forming layer of the photographic element free of solvent is an adjacent image forming hydrophilic colloid layer containing a cyan or magenta image dye forming coupler and having a high boiling point having a log P value of less than about 5.5. It is particularly useful in combination with a layer that is substantially free of solvent. The logP parameter is a measure of the solubility of the compound in aqueous liquids, as compared to the solubility of the compound in a non-polar organic solvent (octanol), and is well known. The solvent-free yellow image forming layer can also be advantageously used in combination with a solid substituted bisphenol light stabilizer.

The multicolor photographic element according to a preferred embodiment of the present invention preferably has a blue color in the electromagnetic spectrum (about 380-380).
500 nm), green (about 500-600 nm) and red (about 6
And a support carrying a photosensitive image dye-forming layer sensitized in the region (00 to 760 nm). According to a preferred embodiment of the present invention, the element comprises cyan, magenta and yellow dye-forming silver halide emulsion hydrophilic colloid layer units sensitized to the red, green and blue regions of the spectrum.
Each unit can contain a single emulsion layer or multiple emulsion layers sensitive to a given region of the spectrum. The layers of the element, including the image-forming unit layers, can be arranged in various orders as known in the art. However, photosensitive materials that are alternatively or additionally sensitive to one or more regions of the electromagnetic spectrum other than the visible, for example, the infrared region of the spectrum, are also within the scope of the invention. In most color photographic systems, color forming couplers are included in the photosensitive photographic emulsion layer and utilized in the emulsion layer to react with the color developing agent oxidized by the silver halide image development during development. It becomes possible. Non-diffusible couplers are included in the photographic emulsion layer. If the dye image formed is to be used in situ, a coupler that forms a non-diffusible dye is selected. For example, International Publications (WO) ninth such as Edwards
As described in 3/012465, a color photographic system can also be used to form a black and white image from a non-diffusible coupler.

The present invention is particularly useful for color photographic print elements, especially photographic print elements designed for exposure through negative films and projection displays, such as cinema prints and intermediate films. In color photographic element printing, there are usually three recordings, red, green and blue, for recording in the image area frame area of the print film. The original record to be reproduced is preferably an image consisting of a sub-record having irradiation patterns in different regions of the spectrum. Typically, it will be a multicolor record consisting of sub-records formed from cyan, magenta and yellow dyes. The theory by which such materials form color images is based on James' Theory of the Photographic
Process , Chapter 12, Principles and Chemistry of Co
lor Photography, 335-372, 1977, Macm
Suitable materials described in illan Publishing Co. New York and useful for forming the original record are described in Research Di
sclosure , December 1987, Item 17643, Industrial
Opportunities Ltd., Homewell Havant, Hampshire, P
O9 IEF, UK and Research Disclosure , 1994
September 365, Item 36544, Kenneth Mason Publications, Lt
d., Emswarth, Hampshire PO10 7DQ, UK. The material from which such an image is formed may be exposed to the original scene in a camera, or may be a camera origination material.
Copies formed from, for example, the trademark Eastman Color In
It can be a record formed on a color negative intermediate film, such as those shown by termediate films 2244, 5244 and 7244. Alternatively, the original record may be in the form of electronic image data, which may be used to control a printer device for selective imagewise exposure of the print film of the invention, such as a laser printer.

Generally, the image dyes formed on photographic print elements designed for viewing directly or by projection are:
It has been found that degradation due to exposure is much more likely to occur than dyes formed on camera negative films that are typically stored in the dark. Accordingly, the photographic elements of the present invention according to certain embodiments of the present invention are preferably photographic print elements. In order to optimize print quality and enable rapid processing, high chloride emulsions of relatively small grains (e.g., average particle size equivalent circular diameter less than about 1 micron and halide with chloride greater than 50 mole%) Content emulsion) is typically used in photographic print films and papers. Such emulsions typically result in photographic elements having a relatively low speed (photographic speed) as compared to camera negative films. Low speed is compensated for by using relatively intense print lamps or lasers to expose such print elements. By comparison, print films and photographic papers, such as cinema color print films, are typically less than 10 when ranked using, for example, the same international standards used to rank camera negative films. It has an ISO speed rank, which is the lowest sensitivity currently used (slow
est) The stop sensitivity is lower than that of camera negative film.

The following discussion of suitable materials for use in the emulsions and elements that can be used in the present invention can be found in Resear.
ch Disclosure, September 1994, Item 36544
(Available from above, hereinafter referred to as “ Research Disclosu
re ”). Research Di
The contents of sclosure encompasses herein, including patents and publications cited therein, the following sections Researc
h Disclosure , means section 36544.

Suitable silver halide emulsions and their preparation, as well as methods of chemical and spectral sensitization, are described in Sections I and III-IV. Vehicles and vehicle-related additives are described in Section II. Dye imaging agents and modifiers are described in Section X. Various additives such as UV dyes, optical brighteners, luminescent dyes, antifoggants, stabilizers, light absorbing and light scattering materials, coating aids, plasticizers, lubricants, antistatic agents and matting agents For example, in sections VI-IX. The layers and layer arrangement, color negative and color positive properties, scan facilitating properties, support, exposure and processing conditions are described in Sections XI-XX.

Further, the title “ Typical and Preferred Co
lor Paper, Color Negative, and Color Reversal Phot
ographic Elements and Processing ”(Research Disclo
It is also contemplated that the materials and methods disclosed in Sure , February 1995, Item 37038) can also be used to advantage with the present elements. The photosensitive photographic print element of the present invention comprises a silver halide emulsion imaging layer wherein the chloride, bromide and / or iodide are present alone or in a mixture, or in a combination of at least two halides. Can be used. The combination significantly affects the performance characteristics of the silver halide emulsion. The print element is typically a high chloride (e.g., greater than 50 mol% chloride) silver halide emulsion containing no or low amounts of bromide (typically less than 40 mol%), typically In terms of using those that do not substantially contain iodide,
It is distinguished from camera negative elements. As described in Atwell U.S. Pat. No. 4,269,927,
Silver halides with a high chloride content have many very advantageous properties. For example, high chloride silver halide is more soluble than high bromide silver halide, so that development is accomplished in less time. Furthermore, the release of chloride into the developing solution is less effective in suppressing development than bromide and iodide, and thus the developing solution can be used in such a manner as to reduce the consumption of the developing solution. Since the print film is intended to be exposed by a controlled light source, the increased imaging speed obtained in connection with high bromide emulsion and / or iodide addition has little advantage for such print films. Can not be obtained.

Photographic print elements, also known as camera negative elements, are those print elements that typically have an area equivalent to the equivalent circular diameter (ECD) of less than about 1 micron (the ECD of a grain is equal to the projected area of the grain. (Which is the diameter of a circle having a fine silver halide emulsion). The ECD of a silver halide emulsion is typically less than 0.60 microns in the red and green sensitized layers and less than 0.90 microns in the blue sensitized layer of a color photographic print element. Such fine grain emulsions used in printing elements are generally 1.3
An aspect ratio (aspect ratio is the ratio of the ECD of the grain to the thickness of the grain). Such particles can take any equiaxed shape, such as cubic, octahedral or cubo-octahedral (ie, tetradecahedral) particles, and these particles can be aged, twinned And other shapes resulting from screw displacement or the like. Typically, the print element emulsion grains are predominantly surrounded by {100} crystal faces, since the {100} grain faces are exceptionally stable. Specific examples of high chloride emulsions used to prepare photographic prints are described in US Pat.
Nos. 65,962; 5,252,454 and 5,
252,456, the disclosures of which are incorporated herein by reference.

The cyan and magenta dye-forming couplers used in the elements of the present invention can be defined as four or two equivalents, depending on the number of Ag ⁺ atoms required to form one mole of the dye. Four-equivalent couplers can generally be converted to two-equivalent couplers by replacing the hydrogen at the coupling site with a different coupling-off group.
The yellow coupler of Formula I is a two-equivalent coupler because it contains a coupling-off group of a heterocyclic group. A variety of other coupling-off groups are well known in the art. Such groups can alter the reactivity of the coupler. Such a group, after release from the coupler, exhibits functions such as dye formation, color tone adjustment, development promotion or suppression, bleach promotion or suppression, electron transfer promotion, color correction, etc., so that the layer to which the coupler is coated or It can have an advantageous effect on other layers in the photographic recording material. Representative groups of such coupling-off groups include, for example, chloro, alkoxy, aryloxy, hetero-oxy, sulfonyloxy, acyloxy, acyl, heterocyclic, sulfonamide, mercaptotetrazole, benzothiazole, alkylthio (e.g., mercapto Propionic acid), arylthio, phosphonyloxy and arylazo. These coupling-off groups are described, for example, in U.S. Pat. Nos. 2,455,169; 3,227,551;
No. 3,432,521; No. 3,476,563; No. 3,617,291; No. 3,880,661; Nos. 4,052,212 and 4,134,766;
And British Patent Publication No. 1,466,728;
No. 31,927; No. 1,533,039; No. 2,000
Nos. 6,755A and 2,017,704A, the disclosures of which are incorporated herein by reference.

Image dye-forming couplers, such as couplers which form cyan dyes upon reaction with oxidized color developing agents, may be included in the element of the present invention and are described in US Pat. No. 2,367. No. 531, No. 2, 42
No. 3,730, No. 2,474,293, No. 2,77
No. 2,162, No. 2,895,826, No. 3,000
No. 2,836, No. 3,034,892, No. 3,04
Nos. 1,236, 4,883,746 and "Farbku
ppler-Eine Literature Ubersicht ”, Agfa Mitteilun
Gen., Vol. III, pages 156-175 (1961). Preferably, such couplers are phenols and naphthols that form cyan dyes upon reaction with oxidized color developing agents. For example, European Patent Application No. 54
No. 4,322; No. 556,700; No. 556,777.
No. 565,096; 570,006 and 574,948 are also preferred.

A typical cyan coupler is represented by the following formula:

[0037]

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[0038]

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(In the above formula, R₁And R_FiveAre each hydrogen
Or a substituent; R_TwoRepresents a substituent; R_ThreeAnd R
_FourIs the Hammett substituent constant s_paraIs 0.2 or more and R
_ThreeAnd R _FourS_paraElectron withdrawing group whose total value is 0.65 or more
R;₆Means that the Hammett substituent constant is s_paraIs 0.35
X represents hydrogen or a coupling solution
Z represents a dissociative group;₁Is at least one solution
Forming a nitrogen-containing 6-membered heterocyclic ring having a leaving group
Represents a nonmetallic atom required for
For example, -NH-, -CH (R)-and the like (preferably in water
With a pKa value of 3 to 12). Hammet
The substitution constant can be measured as described in the literature.
You. For example, C.I. Hansch and A. J. Leo.J. Me
d. Chem. 16, 1207 (1973);J. Med. Chem.20, 304
(1977); and J. A. Dean.Lange's Handbook of Chem
istry,See 12th Edition (1979) (McGraw-Hill).

More preferred are cyan couplers of the following formula:

[0041]

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(In the above formula, R ₇ is a substituent (preferably,
R ₈ represents a substituent (preferably individually selected from halogen, alkyl and carbonamido groups);
₉ represents a ballast group; R ₁₀ represents hydrogen or a substituent (preferably a carbonamido or sulfonamido group); X represents hydrogen or a coupling-off group;
Is 1-3). Couplers of structure CYAN-7 are most preferred for use in the elements of the invention.

Couplers which form magenta dyes upon reaction with oxidized color developing agents and which can be included in the elements of the present invention are described in US Pat. Nos. 2,311,082 and 2,343.
No. 703, No. 2,369,489, No. 2,600,7
No. 88, No. 2,908,573, No. 3,062,65
No. 3, No. 3, 152, 896, No. 3, 519, 429
And “Farbkuppler-Eine Literature Ubersicht
", Agfa Mitteilungen, Volume III, pp. 126-156.
(1961). Preferably, such couplers are pyrazolones, pyrazolotriazoles, or pyrazolobenzimidazoles that form a magenta dye upon reaction with an oxidized color developing agent. Particularly preferred couplers are 1
H-pyrazolo [5,1-c] -1,2,4-triazole and 1H-pyrazolo [1,5-b] -1,2,4-
Triazole. 1H-pyrazolo [5,1-c]-
Examples of 1,2,4-triazole couplers are described in British Patent Nos. 1,247,493; 1,252,418; 1,398,979; U.S. Pat. No. 4,443,536.
No. 4,514,490; No. 4,540,654
No. 4,590,153; No. 4,665,015
No. 4,822,730; No. 4,945,034
No. 5,017,465 and 5,023,17
No. 0. 1H-pyrazolo [1,5-b]
Examples of -1,2,4-triazoles are described in European Patent Applications 176,804; 177,765; U.S. Patent Nos. 4,659,652; 5,066,575 and 5,250, No. 400.

Typical pyrazoloazole and pyrazolone couplers are represented by the following formula:

[0045]

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In the above formula, R _a and R _b independently represent H or a substituent; R _c is a substituent (preferably an aryl group); R _d is a substituent (preferably anilino, carbonamide) , Ureido, carbamoyl, alkoxy,
X is hydrogen or a coupling-off group; and Z _a , Z _b and Z _c are independently substituted methine groups, = N-, = C, aryloxycarbonyl, alkoxycarbonyl, or N-heterocyclic groups); -, or a -NH-, Z _a -Z _b bond or one of Z _b -Z _c bond is a double bond, and the other is a single bond and Z _b -Z _c bond is a carbon -If it is a carbon double bond, this Z _b
-Z _c bond may form part of an aromatic ring, and Z
_a, represents a methine group connected with at least 1 Tsugamoto R _b of Z _b and Z _c). The yellow image forming layer of the present invention is particularly useful for improving color reproducibility when used in combination with a magenta image forming layer containing a pyrazoloazole dye forming coupler of the formula MAGENTA-1. Typical examples of photographic substituents included in yellow, cyan, and magenta couplers that can be used in the element of the present invention include alkyl, aryl, anilino, carbonamide,
Sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, further halogen, cycloalkenyl, alkynyl, heterocyclyl, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclyloxy, siloxy, Acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclylthio, spiro compound residue and crosslinked hydrocarbon compound residue Groups. Usually, the substituents will have less than 30 carbons, typically less than 20 carbons. Unless otherwise specified, references to groups having a substitutable hydrogen (eg, alkyl, amine, aryl, alkoxy, heterocycle, etc.) refer not only to the unsubstituted form of those substituents, but also to any other photographically useful group. It is to be understood throughout this specification that it also includes those substituted with substituents.

To control the migration of various components (including couplers) applied to the photographic layer, it is desirable to include high molecular weight hydrophobic or "ballast" groups in the component molecules. Representative ballast groups include substituted or unsubstituted alkyl or aryl groups having 8 to 40 carbon atoms. Representative substituents present on such groups include alkyl, aryl, alkoxy, aryloxy, alkylthio, hydroxy, halogen, alkoxycarbonyl, aryloxycarbonyl, carboxy,
Acyl, acyloxy, amino, anilino, carbonamido (also known as acylamino), carbamoyl, alkylsulfonyl, arylsulfonyl, sulfonamido and sulfamoyl groups, these substituents typically having from 1 to 40 Contains carbon atoms.
Such substituents may also be further substituted.
Alternatively, the molecule can be immobilized by binding to the polymer backbone.

US Pat. No. 4,301,235;
It is also useful to use a coupler which may contain a known ballast group or a coupling-off group as described in Nos. 853,319 and 4,351,897. If desired, the photographic elements can be obtained from Research Disclos
ure, November 1992, Item 34390. Research Disclosure, June 1994, Item
It is also specifically contemplated to use the photographic elements of the present invention in combination with techniques useful for small format films as described in US Pat. Research Disclosure
Kenneth MasonPublications, Ltd., Dudley House, 12
North Street, Emsworth, Hampshire PO10 7DQ, issued from the UK.

The photographic elements of the present invention may contain conventional support materials, which may be reflective or transparent. Preferred supports for the elements of the present invention are transparent polymer films, such as cellulose nitrate and cellulose esters (eg, cellulose triacetate and diacetate), polycarbonate, and polyesters of dibasic aromatic carboxylic acids with dihydric alcohols, For example, it includes poly (ethylene terephthalate).
In addition to the photosensitive image-forming layers described above, elements of the invention are known in the art, including, for example, antistatic layers, antihalation layers, subbing layers, interlayers, backing layers and overcoat layers. It may further include properties and layers. Polyester supports, for example, typically employ an undercoat or primer layer to improve adhesion to other layers. Such undercoat layers are well known in the art and include, for example, vinylidene chloride / methyl acrylate / itaconic acid terpolymer or vinylidene chloride / acrylonitrilo / acrylic acid terpolymer, which are disclosed in US Pat. No. 2,627. , 0
No. 88, No. 2,698, 235; No. 2,698, 24
No. 0; No. 2,943,937; No. 3,143,421
No. 3,201,249; No. 3,271,178
No. 3,501,301.

The photographic elements of the present invention preferably contain an antihalation layer containing a process-removable filter dye or silver. The antihalation layer may be located between the photosensitive layer and the support or on the backside of the support opposite the photosensitive layer. The filter dye and / or silver used in the antihalation layer is preferably designed to be solubilized and removed or bleached during photographic processing. Conventional processing of photographic print elements is described in Kodak Publication No. H-24, Manual For Process.
and Kodak ECP-2B process for motion picture print film as described in ing Eastman Color Films.

The following examples illustrate the preparation of the photographic elements of the present invention.

[0052]

EXAMPLE 1 27.0 g of yellow coupler Y-1 and 13.5 g
Was dissolved at 65 ° C. in 54.0 g of ethyl acetate. This oil phase solution is then used for 18.
0 g gelatin, 18.0 g Alkanol-XC
(Dupont) and an aqueous phase solution consisting of 169.5 g of distilled water. This mixture is then
Five passes through a ulin colloid mill, followed by removal of the ethyl acetate by rotary evaporation. Distilled water was then added to form Dispersion A consisting of 9.0% coupler and 6.0% gelatin. Dispersions B to I were prepared using yellow coupler Y-2 instead of Y-1 as shown in Table I.
-Y-6 and comparative yellow couplers CY-1 to CY-3
Were prepared in the same manner, respectively. Dispersions J to R also contained no di-n-butyl phthalate in the oil phase,
A yellow coupler Y-1 to Y-6 and a comparative yellow coupler CY-1 were used except that 3.0 g of distilled water was used for the aqueous phase.
To CY-3, respectively.

[0053] The following layers are formed by rem-je
t) Dispersion A was included in a two-layer monochrome photographic element (Element 1) by coating on a gelatin subbed polyethylene terephthalate support having a carbon black containing backing layer. Layer 1: Blue-sensitive layer AgCl cubic grain emulsion, 0.58 micron, SD-
1, spectral sensitization with 0.3336 mmole / Ag mole, 64
5.6 mg / m ² , AgCl cubic grain emulsion, 0.76 micron, SD-1, spectrally sensitized with 0.2669 mmole / Ag mole, 215.2 mg / m ² , gelatin, 2797.6
mg / m ² Dispersion A from yellow dye-forming coupler (Y
-1) 1291.2 mg / m ² , sequestering compound (SQ-1), 305.8 mg / m ² , sequestering compound (SQ-2), 100.0 mg / m ² . Layer 2: protective overcoat layer gelatin, 977.0 mg / m ² , poly (dimethylsiloxane) 200-CS, 65.9 mg / m ² , poly (methyl methacrylate) beads, 5.03 mg / m ² , soluble blue absorption Agent dye (AD-3), 16.1 mg / m ² , spread (S
(reading) auxiliaries.

As shown in Table I, Dispersions B-R were included in the above photographic element format in place of Dispersion A, respectively, and Elements 2-9-1'-9 'were similarly incorporated. Formed. . In these elements, the molar coating amount of the yellow image forming coupler was kept constant. These elements are
~ 1 with a 3000K tungsten light source through a neutral density step tablet, an endothermic filter and a filter designed to represent a motion picture color negative film.
/ 500 seconds. After exposure, these elements were processed in Process ECP-2B, except that steps specific to soundtrack development were omitted. For this treatment, the preliminary solution (1
0 "), water rinse (20"), color development (3 '), stop solution (40 "), first wash (40"), first fixation (4
0 "), second washing (40"), bleaching (1 '), third washing (40 "), second fixing (40"), fourth washing (1'),
It consisted of a final rinse (10 ") and hot air drying.

The preliminary solution of ECP-2B consisted of: water 800 mL Borax (decahydrate) 20.0 g sodium sulfate (anhydrous) 100.0 g sodium hydroxide 1.0 g Make up to 1 liter with water.

PH: 9.25 ± 0.10 at 26.7 ° C. Color developer of ECP-2B: water 900 mL Kodak anti-calcium No. 4 (pentasodium nitrilotri-tri (methylene phosphonic acid)) 40% solution of salt) 1.00 mL Sodium sulfite (anhydrous) 4.35 g Sodium bromide (anhydrous) 1.72 g Sodium carbonate (anhydrous) 17.1 g Kodak color developing agent, CD-2 2.95 g sulfuric acid (7.0 N) 0.62 mL Make up to 1 liter with water.

The pH was 10.53 ± 0.05 at 26.7 ° C. The stopping solution of ECP-2B consisted of: 900 mL water 50 mL sulfuric acid (7.0 N) 50 mL Make up to 1 liter with water.

The fixer at 0.90 ECP-2B at pH 26.7 ° C. consisted of: 800 mL of water 100.0 mL of ammonium thiosulfate (58.0% solution) 13.0 g of sodium bisulfate (anhydrous) 13.0 g with water Make up to 1 liter.

The pH was 5.00 ± 0.15 at 26.7 ° C. The ferricyanide bleach of ECP-2B consisted of: 900 mL of water 30.0 g of potassium ferricyanide 17.0 g of sodium bromide (anhydrous) 17.0 g of water To liters.

The pH was 6.50 ± 0.05 at 26.7 ° C. The final rinse solution consisted of: 900 mL of water 3.0 mL of Kodak Photo-Flo 200 ™ solution 3.0 mL Make up to 1 liter with water.

The processing of the exposed elements was performed with a color developing solution adjusted to 36.7 ° C. The temperature of the stop, fix, bleach, wash and final rinse solutions was adjusted to 26.7 ° C. The optical density due to dye formation was then measured by a densitometer using a densitometer filter appropriate for the intended use of the photographic element. The dye densities were then graphed against log exposure to obtain red, green and blue D-logE characteristic curves for the photographic element. Maximum blue density (Dma) for each element
Table I shows the blue density reduction% of the element using the solvent-free yellow image-forming layer for x) and the comparative element containing the coupler-solvent in the yellow image-forming layer. In some cases, the element containing the dispersion of the comparative yellow coupler without solvent showed a decrease in blue density at high exposures above Dmax. This is reported in Table I for each element as the amount of blue density formed at the highest level of exposure (Emax). Table I also shows the% reduction in blue density in Emax for the element using the solvent-free yellow image-forming layer relative to the comparative element containing the coupler-solvent in the yellow image-forming layer.

[0062]

[Table 1]

These data clearly show that the yellow coupler of the present invention has a blue Dma higher than that of the comparative yellow coupler even when the coupler solvent is removed from the yellow image forming layer.
This shows that the reduction of x is substantially low. These data indicate that the yellow coupler of the present invention is Emax,
It shows a higher blue density and the removal of coupler-solvent from the yellow image forming layer shows much lower blue density reduction in Emax.

These treated elements were then irradiated with light from a high intensity 50 klux xenon light source for 6 days. After irradiation, the dye concentration was measured again as described above. For each element, the reduction in blue density due to light fade from an initial blue density of 2.5 is reported in Table II.

[0065]

[Table 2]

These data clearly show that the removal of the coupler solvent from the yellow image forming layer significantly improves the light stability of the yellow dye using the coupler of the present invention. The following structure represents the compounds used in the photographic elements described above but not shown above.

[0067]

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[0068]

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Example 2 The multilayer photographic element of the present invention can be prepared by coating the following layers on a gelatin subbed polyethylene terephthalate support. Layer 1: Blue-sensitive layer AgCl cubic grain emulsion, 0.58 micron, SD-
1, spectral sensitization with 0.3336 mmole / Ag mole, 64
5.6 mg / m ² , AgCl cubic grain emulsion, 0.76 micron, SD-1, spectral sensitization at 0.2669 mmole / Ag mole, 215.2 mg / m ² , yellow dye-forming coupler (Y-1) 1291.2 mg / m ² , stabilizer (ST-
1) 322.8 mg / m ² , sequestering compound (SQ-1), 305.8 mg / m ² , sequestering compound (SQ-2), 100.0 mg / m ² , gelatin,
2797.6 mg / m ² , spreading aid, layer 2: intermediate layer developer oxidized scavenger (SC-1), 75.3
mg / m ^2, gelatin, 645.6mg / m ^2, spreading aids, layer 3: Red-Sensitive Layer AgClBr cubic grain emulsions, 25% Br, 0.15 microns, SD-2,0.1808 mmole / Ag mole, supersensitizer compound (SS-1), 0.6327 mmole / Ag m
ole spectral sensitization, 397.0 mg / m ² , AgClBr cubic grain emulsion, 25% Br, 0.24 micron, SD-
2, 0.1356 mmole / Ag mole, supersensitizer compound (SS-1), spectral sensitization with 0.7444 mmole / Ag mole, 44.1 mg / m ² , cyan dye-forming coupler (C-
1), 914.6 mg / m ² , coupler solvent (S-1),
548.8 mg / m ² , coupler solvent (S-2), 54
8.8 mg / m ² , oxidized developer scavenger (SC
-1), 12.9mg / m ^2, gelatin, 3410.9Mg
/ M ² , spreading aid, layer 4: intermediate layer developer oxidized scavenger (SC-1), 75.3
mg / m ^2, gelatin, 645.6mg / m ^2, spreading aids, layer 5: Green-Sensitive Layer AgClBr cubic grain emulsions, 25% Br, 0.15 microns, SD-3,0.5273 mmole / Ag mole, supersensitizer compound (SS-1), 1.1212 mmole / Ag m
ole spectral sensitization, 419.6 mg / m ² , AgClBr cubic grain emulsion, 25% Br, 0.24 micron, SD-
3, 0.4785 mmole / Ag mole, supersensitizer compound (SS-1), 1.3902 mmole / Ag mole, spectral sensitization, 32.3 mg / m ² , magenta dye-forming coupler (M
-1), 645.6 mg / m ² , coupler solvent (S-
1), 193.7 mg / m ² , oxidized developer scavenger (SC-1), 53.8 mg / m ² , gelatin, 19
15.3 mg / m ² , spreading aid, layer 6: protective overcoat layer poly (dimethylsiloxane) 200-CS, 65.9 mg
/ M ² , poly (methyl methacrylate) beads, 5.0
mg / m ^2, gelatin, 977.0mg / m ^2, soluble green absorber dye (AD-1), 32.3mg / m 2, soluble green absorber dye (AD-2), 32.3mg / m ² , soluble blue absorber dye (AD-3), 16.1 mg / m ² , soluble red absorber dye (AD-4), 110.8 mg / m ² , gelatin hardener, spreading aid.

The following structure represents additional compounds in the photographic element.

[0071]

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[0072]

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[0073]

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[0074]

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[0075]

The photographic element of the present invention using a yellow image forming layer containing a yellow dye-forming coupler of Formula I and containing substantially no solvent has a high boiling point coupler compared to other yellow dye-forming couplers. -A coupler in the absence of a solvent-
It has high reactivity and shows an excellent characteristic curve shape. In addition, the yellow dyes formed from the couplers of Formula I, when these couplers are dispersed without high boiling solvents or nonionic polymer stabilizers, are compared to coupler-solvent-containing dispersions of these couplers. It has also been found that they show significantly improved stability against light fade. Further, the absence of a non-ionic polymer stabilizer results in a photographic element having a relatively thin yellow imaging layer.

Although the invention has been described in detail with particular reference to preferred embodiments thereof, it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Brian Thomas USA, New York 14534, Pittsford, Wolf Trap 20

Claims (2)

[Claims] 1. A support comprising at least one yellow image-forming hydrophilic colloid layer comprising a yellow image dye-forming coupler of formula I, wherein said yellow image-forming layer comprises a high boiling point residual solvent. Silver halide photographic element substantially free of and non-ionic polymer stabilizers: Wherein R represents a substituent, Y represents an aryl group or a heterocyclic group, and Z represents a nonmetallic group necessary for completing a nitrogen-containing heterocyclic coupling-off group together with the nitrogen atom. Atom group). 2. The method of claim 1 wherein the yellow image-forming hydrophilic colloid layer is substantially free of high boiling point residual solvents and nonionic polymer stabilizers and comprises a blue-sensitive silver halide emulsion and a yellow image dye-forming coupler of formula I. One layer, at least one cyan image forming hydrophilic colloid layer comprising a red sensitive silver halide emulsion and a cyan image dye forming coupler, and a magenta image forming hydrophilic comprising a green sensitive silver halide emulsion and a magenta image dye forming coupler. A photographic element according to claim 1, comprising a support having at least one colloid layer, in turn, on one side thereof.