JPH08278612A - Silver halide photosensitive color photographic element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve stability of dispersion vs. crystallization after a long time cold storage by specifying the respective mixing ratios of a phenol type cyanic coupler and an organic solvent having a high boiling point in a colloidal layer containing both of the coupler and the solvent. SOLUTION: This color photographic element comprises a supporting body having a hydrophilic colloidal layer containing a phenol type cyanic coupler having a formula I and organic solvents with high boiling points and having formulas II, III. The weight ratios of the high boiling point organic solvents having the formulas II, III to the weight of the coupler having the formula I in the hydrophilic colloidal layer is within 0.1-0.5. In the formula I, R1 , R2 stand for aliphatic groups and aromatic groups, R3 for hydrogen atom and halogen atoms, X for hydrogen atom and a group which can be released at the time of coupling reaction with an oxidation product of a developer, n for 0 or 1. In the formula II, R4 , R5 respectively stand for alkoxycarbonyl group with 8 or less carbons and m for 1-10 integer. In the formula III, R6 stands for alkyl groups and alkenyl groups, R7 and R8 independently stand for hydrogen and a part of the groups selected from R6 .

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to dispersions of phenolic cyan dye-forming photographic couplers prepared without the use of any permanent organic coupler solvent. The present invention further relates to silver halide photographic materials and methods of making the same, and more particularly to photographic materials comprising a particular phenolic cyan dye-forming photographic coupler and a limited amount of a particular high boiling organic solvent.

[0002]

2. Description of the Prior Art In designing a silver halide light-sensitive multilayer photographic material, it is desirable to minimize the dry thickness of the coating layer. Thinning is advantageous for reasons such as improved image sharpness due to reduced light scattering during exposure and improved developability due to shorter diffusion paths through the multilayer structure. By improving the developability, the coating amount of silver and / or the coupler can be reduced, so that the material cost can be reduced.

Photographic dye-forming couplers, as well as other photographically useful compounds, are generally formed into a layer by first forming an aqueous dispersion of the coupler and mixing the dispersion with a layer coating solution. Be incorporated. Organic solvents are commonly used to dissolve the coupler and the resulting organic solution is dispersed in an aqueous medium to form an aqueous dispersion.

The organic phase of these dispersions often contains high boiling or permanent organic solvents. Permanent high boiling point solvent is
A sufficiently high boiling point (typically 150) at atmospheric pressure so that it does not evaporate during normal dispersion manufacturing and photographic layer coating operations.
C.). Permanent high boiling coupler solvents are used by conventional "oil protect" dispersion methods, which inherently leave the organic solvent in the dispersion, thereby incorporating the organic solvent into the emulsion layer coating solution and finally into the photographic element. Be done.

It is of utmost importance to minimize the amount of permanent coupler solvent coated in the element in order to reduce the coating thickness of the photographic layer. In fact, reducing the amount of coupler solvent also results in a reduction in the amount of gelatin that further reduces the applied dry thickness. U.S. Pat. No. 5,173,398 and the like describe photographic elements having a coupler-containing layer that is substantially free of high boiling solvent, where the coupler is incorporated in the form of a precipitation dispersion. There is. But,
Lower coupler solvents can also result in excessive crystals of dispersible organic compounds in aqueous dispersions and coating solutions containing photographic compounds that tend to crystallize.

These crystallization problems can lead to filter plugging during the manufacture of photographic materials or physical defects in the coated product. Another problem with reducing coupler solvent is that the dispersed photographically useful agent, e.g., dye-forming coupler, is added in an amount below that which produces the desired dye density upon processing of the photographic material. It is possible to reduce the amount.

Dispersions of photographic couplers made without the use of permanent coupler solvents are well known in the art. Such dispersions are generally made with a cosolvent which is removed from the dispersion prior to coating.
The co-solvent can be a water immiscible, a volatile solvent, or a solvent with limited water solubility that is not completely water miscible. In fact, U.S. Pat. No. 2,801,1
As described in 70, there are many photographic compounds which can be dispersions with or without permanent solvent without crystallization problems. However, if the dispersed photographic compound is prone to crystallization, then US Pat.
As described in US Pat. Nos. 19,441 and 5,112,729, the tendency to crystallize generally increases as the amount of coupler solvent decreases relative to the coupler.

Phenolic cyan dye-forming couplers are well known in the art and are known to have a high tendency to crystallize. US Pat. No. 4,885,
Due to its crystallinity, these couplers are often dispersed as a mixture of several types of couplers to avoid crystallization problems, as described in EP 234 and EP 434,028. . However, the use of these methods requires the synthesis of additional photographic couplers that increase manufacturing costs. U.S. Pat. No. 4,333,99
No. 9, No. 4,609,619, European Patent No. 097,0.
42, 102, 839, 389, 817, German Patents 3,624,777, 3,700, 57.
No. 0, and 3,936,300, phenolic cyan dye-forming couplers are usually dispersed with a high boiling solvent to achieve sufficient coupler reactivity. It is also well known that reducing coupler solvent can reduce coupler reactivity, as described in US Pat. No. 2,801,170. This document also describes the blending of solventless couplers with dispersions of high boiling coupler solvents.

US Pat. No. 5,112,729 describes a photographic material containing a cyannaphthol coupler and a high boiling solvent present in the layer in a weight ratio to said coupler of not more than 0.3. Has been done. Although various possible solvents have been described, the use of phosphoric acid esters and phthalic acid esters is described as preferred for use in these couplers. Methods for enhancing dye formation in oil-free cyan coupler dispersions are described in Research Disclosure 14532 (May 1976). The specific cyan couplers described in these references are outside the scope of this invention. Crystallization of phenolic cyan couplers is also described in EP 361,924.

It is to provide a coupler dispersion which is free of permanent solvent, exhibits good stability to crystallization and which, when applied to silver halide light-sensitive photographic materials, provides sufficient coupler reactivity. desirable. In addition, it exhibits improved stability to crystallization while at the same time providing high coupler reactivity in photographic materials to obtain higher dye densities during processing when the dispersion is used in coupler-rich multilayer structures. It would be desirable to provide a silver halide photographic element made from a solvent-free dispersion of a particular phenolic cyan coupler that achieves. Further, it is also desirable to achieve a reduction in coupler laydown in such elements to reduce the dry thickness applied. The aim of the present invention is in the above direction.

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a dispersion of phenolic cyan couplers having improved stability to dispersion crystallization after long term cold storage. Furthermore, it is an object of the present invention to provide a coating solution for a silver halide light-sensitive photographic material containing a phenolic cyan coupler dispersion that exhibits improved stability against crystallization at long melt hold times. Is.

Another object of the present invention is to provide a silver halide photosensitive photographic material having a reduced coating dry thickness. Another object of the present invention is to provide a silver halide photographic material having a high cyan coupler reactivity so as to obtain a sufficient cyan dye density during processing of the photographic material. It is a further object of the present invention to provide photographic materials having such properties made from cyan coupler dispersions that have improved stability against crystallization after long term cold storage.

[0013]

The above-mentioned object of the present invention is
A silver halide photographic comprising a support having thereon a coated coupler dispersion containing layer containing a specific type of phenolic cyan dye-forming coupler and a limited amount of a specific high boiling organic solvent. This is accomplished by providing the material.

[0014]

DETAILED DESCRIPTION OF THE INVENTION In one aspect of the invention there is disclosed a dispersion comprising particles of a phenolic cyan photographic coupler of Formula I dispersed in an aqueous gelatin solution substantially free of permanent organic solvent.

[0015]

[Chemical 6]

(Wherein R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group, and R ₃ represents a hydrogen atom, a halogen atom, an aliphatic group, or an acylamino group. , X represents a hydrogen atom or a group which can be released during a coupling reaction with an oxidation product of a developing agent, and n represents 0 or 1.

Dissolving the dispersions of the invention, preferably in a cosolvent, the coupler of formula I, dispersing the cosolvent and the dissolved coupler in an aqueous gelatin solution, and removing the cosolvent from the dispersion. Generated by. A) a silver halide light-sensitive photographic material, a) dispersing the coupler of formula I in an aqueous gelatin solution substantially free of permanent organic solvent, and b) preparing an aqueous coating solution containing the dispersion from a). , And c) the solution derived from b) is coated on a photographic support.

In another aspect of the invention, (a) preparing a first dispersion of a phenolic cyan coupler of Formula I dispersed in an aqueous medium; (b) Formula II dispersed in an aqueous medium. Preparing a second dispersion of a high boiling organic solvent having the following formulas: III, III, IV, V or a combination thereof:

[0019]

[Chemical 7]

(In the formula, R ₄ and R ₅ each represent an alkoxycarbonyl group having 8 or less carbon atoms, and m is
Is an integer of 1 to 10);

[0021]

Embedded image

[0022] (wherein, R ₆ represents an alkyl or alkenyl group, and R ₇ and R ₈ are independently a group of the moiety selected from hydrogen and R _6, R _6, R
₇ and the total number of carbon atoms contained in R ₈ is at least 10);

[0023]

[Chemical 9]

(In the formula, R₉ And R_TenIs hydrogen or straight chain
Or a branched chain alkyl group, R ₉ Or R_Tenof
At least one is a linear or branched alkyl group
Yes, R₉ And R_TenThe total number of carbon atoms is 9 to 20
And R_TenIs a phenolic hydroxyl group
In the para or meta position);

[0025]

[Chemical 10]

(Wherein R ₁₁ represents an aliphatic group, an aromatic group, or a heterocyclic group, and R ₁₂ represents a hydrogen atom, a hydroxy group, an alkoxy group, or an aliphatic group); c) mixing the first dispersion and the second dispersion in an aqueous coating solution, provided that the weight ratio of the high boiling organic solvent of the formulas II, III, IV and V to the coupler of the formula I in the coating solution. Is 0.1 to 0.5; and (d) applying the coating solution onto a photographic support, and a method for producing a silver halide color photographic light-sensitive material is disclosed.

Further, in an embodiment of the present invention, a layer comprising a coupler of formula I and a high boiling organic solvent of formula II, III, IV or V, wherein formula II, III, IV for the coupler of formula I is present.
The weight ratio of the high-boiling organic solvents V and V in the layer is 0.
Silver halide color photographic light-sensitive material comprising a support having a thickness of 1 to 0.5). In the cyan coupler represented by the formula I, R ₁ and R ₂ are each an aliphatic group (preferably an aliphatic group having 1 to 32 carbon atoms, for example, methyl, butyl, dodecyl, cyclohexylallyl) or an aryl group. (Eg, phenyl, naphthyl) or a heterocyclic group (eg, 2-pyridyl, 2-imidazolyl, 2-furyl, 6-quinolyl). Throughout the present specification, when a substituent is referred to by making the group containing a substitutable hydrogen the same, unless otherwise specified, not only the unsubstituted form of the substituent but also other photographically useful substituents are used. It is understood that the form substituted with a group is also included.

For example, such substitutable groups can be substituted with one or more photographically acceptable substituents. Such photographically useful substituents are, for example, alkyl groups, aryl groups, heterocyclic groups, alkoxy groups (eg methoxy, 2-methoxyethoxy), aryloxy groups (eg 2,4-di-t). -Amylphenoxy, 2
-Chlorophenoxy, 4-cyanophenoxy), alkenyloxy group (for example, 2-propenyloxy), acyl group (for example, acetyl, benzoyl), ester group (for example, butoxycarbonyl, phenoxycarbonyl, acetoxy, benzoyloxy, butoxysulfonyl). , Toluenesulfonyloxy), an amide group (for example,
Acetylamino, methanesulfonylamino, dipropylsulfamoylamino), carbamoyl group (eg, dimethylcarbamoyl, ethylcarbamoyl), sulfamoyl group (eg, butylsulfamoyl), imide group (eg, succinimide, hydantoynyl), ureido group (eg For example, phenylureido, dimethylureido), an aliphatic or aromatic sulfonyl group (for example, methanesulfonyl, phenylsulfonyl), an aliphatic or aromatic thio group (for example, ethylthio, phenylthio), a hydroxy group, a cyano group, a carboxy group, It is selected from the group consisting of a nitro group, a sulfo group, and a halogen atom. Usually, the substituent has less than 30 carbon atoms,
Typically less than 20 carbons.

R ₃ represents a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group or an acylamino group. When R _{3 in} formula I represents a group which itself can be substituted, it can be further substituted with one or more substituents selected from those mentioned for R ₁ and R ₂ . In formula I, X represents a hydrogen atom or a coupling-off group released upon coupling. Examples of groups released upon coupling include halogen atoms (eg, fluorine,
Chlorine, bromine), an alkoxy group (for example, ethoxy, dodecyloxy, methoxycarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy), an aryloxy group (for example, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy), Acyloxy group (for example, acetoxy, tetradecanoyloxy, benzoyloxy), sulfonyloxy group (for example, methanesulfonyloxy, toluenesulfonyloxy), amide group (for example, dichloroacetylamino, heptafluorobutyrylamino, methanesulfonylamino, Toluenesulfonylamino), alkoxycarbonyloxy group (eg ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy group (eg , Phenoxycarbonyloxy), aliphatic or aromatic thio groups (eg ethylthio, phenylthio, tetrazolylthio, mercaptopropionic acid), imide groups (eg succinimide, hydantoinyl), sulfonamide groups and aromatic azo groups (eg phenylazo) Is included.

These coupling-off groups are known in the art, for example, US Pat. Nos. 2,455,169, 3,227,551, 3,432,521 and 3,476,563. No. 3,617,291, No. 3,880,661, No. 4,052,212 and No. 4,134,766; and British Patent and Publication, No. 1,466,728, Same as 1,531,927
Issue No. 1,533,039 Issue No. 2,006,755A
And No. 2,017,704A. These groups can have a photographically useful group.

In formula I, R ₁ is preferably an aryl or heterocyclic group. More preferred is one selected from a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group and a cyano group. It is an aryl group substituted with the above substituents. Most preferred are aryl groups substituted with one or more halogen or cyano substituents.

In formula I, R ₂ is preferably an alkyl or aryl group, more preferably an alkyl group substituted with an aryloxy group, and R ₃
Is preferably a hydrogen atom. X is preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group or a sulfonamide group.
Further, it is preferable that n is 1. In a specific preferred embodiment of the invention, n is 1 and X in formula I is a hydrogen atom, a halogen atom or an aryloxy group.

Preferred examples of cyan couplers represented by formula I of the present invention are set forth below but should not be construed as limiting the invention thereto.

[0034]

[Chemical 11]

[0035]

[Chemical 12]

[0036]

[Chemical 13]

[0037]

Embedded image

Dispersions of cyan couplers of formula I for use in the present invention can be prepared by dissolving the coupler in a low boiling or partially water-soluble auxiliary organic solvent. In one embodiment of the invention, such dispersions are used with high boiling permanent organic solvents, including solvents of formula II-V in which the ratio of solvent to coupler in the dispersion is 0.50 or less, or It can be created without using it. The resulting organic solution can then be mixed with an aqueous gelatin solution, the mixture being a mechanical stirrer suitable for high shear or turbulent mixing, which is generally suitable for preparing photographic emulsion dispersions, for example , Colloid mill, homogenizer,
Micro fluidizer, high speed mixer, ultrasonic disperser,
It is passed through a blade mixer, a device for pumping a liquid stream at high pressure through an orifice or an interaction chamber, a Gorin mill, a compounding machine, etc. to form small particles of the organic phase suspended in the aqueous phase.

The dispersion may be prepared using one or more devices. Then, the auxiliary organic solvent is removed by evaporation, noodle washing, or membrane dialysis. The dispersion particles are
Preferably, the average particle size is less than 2 μm, generally about 0.0.
2 to 2 μm, more preferably about 0.02 to 0.5 μm. These methods are described in US Pat. No. 2,322,02.
No. 7, No. 2,787,544, No. 2,801,170
Nos. 2,801,171, 2,949,360 and 3,396,027.

Examples of suitable cosolvents which can be used in the present invention are ethyl acetate, isopropyl acetate, butyl acetate, ethyl propionate, 2-ethoxyethyl acetate.
2- (2-butoxyethoxy) ethyl acetate, dimethylformamide, 2-methyltetrahydrofuran, triethylphosphate, cyclohexanone, butoxyethyl acetate, methyl isobutyl ketone, methyl acetate, 4-methyl-2-pentanol, diethylcarbitol, 1, 1,
2-trichloroethane, 1,2-dichloropropane, etc. are included. Preferred cosolvents included ethyl acetate and 2- (2-butoxyethoxy) ethyl acetate.

In a preferred embodiment of the invention, the couplers of formula I are dispersed without the use of high boiling organic solvents to make coupler dispersions substantially free of permanent organic solvents. For purposes of the present invention, terms such as "substantially free of permanent organic solvent", "solvent-free", etc. are intended to indicate the absence of permanent solvent in trace or above impurity levels. It has been found that such solvent-free dispersions unexpectedly give improved performance against crystallization problems compared to low solvent content dispersions.

The aqueous phase of the coupler dispersion of this invention preferably comprises gelatin as a hydrophobic colloid.
It can be gelatin or modified gelatin such as acetylated gelatin, phthalated gelatin, oxidized gelatin and the like. Gelatin may be subjected to base treatment such as lime-treated gelatin or acid treatment such as acid-treated ossein gelatin. Also, other hydrophilic colloids such as water-soluble polymers or copolymers may be used. They include, but are not limited to, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate-co-vinyl alcohol, hydroxyethyl cellulose, polyacrylic acid, poly (1-vinylpyrrolidone), sodium polystyrene sulfonate, poly (2 -Acrylamide-2-
Methane sulfonic acid) and polyacrylamide are included.
Copolymers of these polymers with hydrophobic monomers may be used.

Surfactants may be present in the aqueous or organic phase and the dispersions can be prepared without surfactant. Surfactants include cationic, anionic,
It can be zwitterionic or nonionic. The ratio of surfactant to liquid organic solution is generally in the range of 0.5 to 25% by weight when forming small particle photographic dispersions. In a preferred embodiment of the present invention, an anionic surfactant is contained in the gelatin aqueous solution.

Particularly preferred surfactants for use in the present invention include alkali metal salts of alkali-lene sulfonic acids,
For example, sodium salt of dodecylbenzene sulfonic acid or sodium salt of isopropyl naphthalene sulfonic acid, a mixture of sodium di-isopropyl- and triisopropyl-naphthalene sulfonate; alkali metal salt of alkyl sulfonic acid, such as sodium dodecyl sulfate; Included are alkali metal salts of succinate, such as sodium bis (2-ethylhexyl) succinate sulfonate.

Dispersions of couplers according to embodiments of the present invention include:
Although one or more cyan couplers of Formula I can be included, it is not necessary to use one or more coupler to obtain the benefits of the present invention. In a preferred embodiment of the invention, a single class of Formula I substantially free of other cyan dye-forming couplers is used.
The cyan coupler dispersion of is used. By "substantially free" is meant free of other cyan dye-forming couplers in trace or above impurity levels.

The high boiling organic solvents represented by Formulas II-V are described below. In formula II, R ₄ and R ₅ may be the same or different and are each methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl,
An alkoxycarbonyl group having 8 or less carbon atoms such as butoxycarbonyl and benzyloxycarbonyl, and m is 1
It is an integer of 10 to 10, preferably 4 to 8.

Representative examples of high boiling organic solvents according to Formula II are:

[0048]

[Chemical 15]

[0049]

Embedded image

In formula III, the alkyl or alkenyl group represented by R ₆ can be substituted or unsubstituted, and R ₇ and R ₈ are independently hydrogen and R ₆
The total number of carbon atoms contained in R ₆ , R ₇ , and R ₈ is at least 10, although the total number of carbon atoms is at least 10. In a preferred embodiment, at least one of R ₇ and R ₈ is hydrogen, more preferably both R ₇ and R ₈ are hydrogen.

Representative examples of compounds of formula III are:

[0052]

[Chemical 17]

[0053]

Embedded image

In formula IV, R₉ And R_TenRepresented by
The group is hydrogen or a linear or branched alkyl group.
R₉ Or R_TenAt least one of
R ₉ And R_TenThe total number of carbon atoms is 9 to 20, and
R_TenIs in the para position relative to the phenolic hydroxyl group
Or in the meta position. Of the compound represented by formula IV
Representative examples are shown below:

[0055]

[Chemical 19]

[0056]

Embedded image

In formula V, the group R ₁₁ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₁₂ represents a hydrogen atom, a hydroxy group, an alkoxy group or an aliphatic group.
Such groups R ₁₁ and R ₁₂ may be further substituted or unsubstituted. Representative examples of compounds of formula V are shown below:

[0058]

[Chemical 21]

[0059]

[Chemical formula 22]

In a preferred embodiment, the cyan coupler of formula I is dispersed without the use of high boiling organic solvents as described above, followed by the formula II-V in an aqueous coating solution.
Mix with another dispersion of the high boiling solvent. Aqueous dispersions of high boiling solvents of Formulas II-V are prepared in the same manner as coupler dispersions (eg, solvent is added to the aqueous medium and the mixture is subjected to high shear or turbulent mixing as described above). This aqueous medium is preferably a gelatin solution, but also surfactants and cosolvents can be used, as described above. In a preferred embodiment, US Pat. No. 5,468,60
Hydrophobic additives are dissolved in a solvent to prevent particle growth as described in US Pat.

The mixture is then passed through a mechanical stirrer such as a colloid mill, homogenizer, microfluidizer, high speed mixer, ultrasonic disperser, etc. to form small particles of organic solvent suspended in the aqueous phase. . If a cosolvent is used, it is later removed by evaporation, noodle washing, or membrane dialysis. These methods are described in detail in the references cited above relating to dispersion production. The solvent dispersion can be a "blank" dispersion that does not contain any additional photographically useful compound, or the solvent can be part of the photographically useful compound dispersion.

Then a cyan coupler dispersion and formulas II-V
Can be combined with another dispersion of the high boiling organic solvent of to prepare an aqueous coating solution according to the present invention. The solution can also contain silver halide emulsions, dispersions or solutions of other photographically useful compounds, additional gelatin, or other components such as acids and bases for pH adjustment. Then, before coating, at a high temperature (eg, 30 to 50 ° C.) for a short time (eg, 5 minutes to 4).
These components can be mixed with a mechanical device over time.

In one embodiment of the present invention, the coupler dispersion and the solvent dispersion have a weight ratio of high boiling organic solvent of formulas II-V to coupler of formula I in the coating solution of 0.
1 to 0.5, more preferably 0.1 to 0.35, most preferably 0.2 to 0.3, in the solution. It is an unexpected advantage of the present invention that certain high boiling solvents render couplers of formula I relatively more reactive at lower levels of coupler solvent compared to other conventional high boiling solvents. When used at a lower ratio than the above,
Coupler reactivity generally does not increase to the desired high levels. Higher proportions are undesirable because they diminish the benefits associated with reducing the amount of coupler solvent.

Using the present invention, a particular phenolic cyan coupler is used with a minimum amount of high boiling organic solvent,
Halogen, which maintains high coupler reactivity to obtain the desired dye density when processing photographic materials, and which has a reduced dry thickness applied while avoiding the crystallization problems found in low solvent dispersions of these couplers. A silver halide photographic light-sensitive material can be produced.

Photographic elements comprising the coupler dispersion of this invention can be single color elements or multicolor elements. Multicolor elements contain image dye-forming units sensitive to each of the three primary regions of the spectrum. Each unit can comprise a single emulsion layer or multiple emulsion layers sensitive to a given region of the spectrum. The layers of the element, including the layers of the image-forming units, can be arranged in various orders as known in the art. In another format, emulsions sensitive to each of the three primary regions of the spectrum can be arranged as a single segmented layer.

A typical multicolor photographic element is a cyan dye image-forming unit containing at least one red-sensitive silver halide emulsion layer having at least one cyan dye-forming coupler associated therewith, and at least one magenta dye associated therewith. A magenta dye image-forming unit containing at least one green-sensitive silver halide emulsion layer having a forming coupler, and a yellow dye image containing at least one blue-sensitive silver halide emulsion layer having at least one yellow dye-forming coupler associated therewith. It comprises a support carrying the production units. The element can include additional layers such as filter layers, interlayers, antihalation layers, overcoat layers, subbing layers and the like.

If necessary, this photographic element can be used for research
Closure , Item 34390, November 1992, (Ken
neth Mason Publication Ltd., Dudley House, 12a Nor
thStreet, Emsworth, Hampshire PO10 7DQ, England, ed.). Further, the dispersion of the present invention, Lisa
Over Ji Disclosure, Item 36230, 1994 6
It is also conceivable to use it in combination with techniques useful for small format films such as those described in Moon.

The following discussion of emulsions that can be used in combination with this photographic element and materials suitable for use in the element is discussed in Research Disclosure , 1994.
See September 36544, item 36544. This document will be referred to as " Research Disclosure " hereinafter. The following citations are Research Disclosures , Items
36544 chapter.

The silver halide emulsions used in the photographic elements of the present invention can be either negative or positive working. Compatible emulsions and their preparation and 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 image formers and modifiers are described in Section X. Various additives such as UV dyes, optical brighteners, luminescent dyes, antifoggants, stabilizers, light absorbing and scattering substances, coating aids, plasticizers, lubricants, antistatic agents, and matting agents, For example, it is described in Chapters VI to IX. Layers and layer arrangements, color negative and color positive features, scan facilitating features, supports, exposure and processing are described in XI-XX.

Other photographic couplers may be included in the photographic elements of this invention in addition to the cyan couplers of formula I contained in the dispersions of this invention. Couplers that react with oxidized color developing agents to produce cyan dyes are described in US Pat.
No. 7,531, No. 2,423,730, No. 2,47
4,293, 2,772,162, 2,89
5,826, 3,002,836, 3,03
4,892, 3,041,236, 4,33
3,999, 4,883,746, and "Farbkuppler-Eine Literatur Ubersicht", Agfa Mit.
Teilungen, Band III, pages 156-175 (1961), and other representative patent specifications and sensitizers.

Preferably, such couplers are phenols and naphthols that react with oxidized color developing agents to form cyan dyes. Also preferred are, for example, European Patent Applications Nos. 544,322 and 55.
6,700, 556,777, 565,096
No. 570,006 and 574,948. A particularly preferred embodiment of the present invention involves the use of cyan couplers of formula I as the principle cyan dye-forming image coupler.

Can be incorporated into the elements of the invention,
Couplers that react with oxidized color developing agents to form magenta dyes are: U.S. Pat. Nos. 2,600,788, 2,369,489, 2,343,703, 2,311,082. Nos. 2,908,573, 3,062,653, 3,152,896, 3,159,429, and "Farbkuppler-Ei".
ne Literatur Ubersicht ", published by Agfa Mitteilungen,
Band III, pages 126-156 (1961), in representative patent specifications and publications. Preferably, such couplers are pyrazolones, pyrazolotriazoles, or pyrazolobenzimidazoles that react with oxidized color developing agents to form magenta dyes.

Particularly preferred couplers are 1H-pyrazolo [5,1-c] -1,2,4-triazole, and 1H.
-Pyrazolo [1,5-b] -1,2,4-triazole. 1H-pyrazolo [5,1-c] -1,2,4-
Examples of triazole couplers are described in British Patent No. 1,247,
No. 493, No. 1,252,418, No. 1,398,9
79, U.S. Pat. Nos. 4,443,536 and 4,51
4,490, 4,540,654, 4,59
0,153, 4,665,015, 4,82
2,730, 4,945,034, 5,017,
No. 465, and 5,023,170. 1H-pyrazolo [1,5-b] -1,2,4
-Examples of triazoles are described in European Patent Application No. 176,804.
No. 177,765, U.S. Pat. No. 4,659,
Nos. 652, 5,066,575, and 5,25
No. 0,400 can be found in each specification. Especially preferred are the pyrazolone couplers as described in US Pat. No. 4,853,319.

Couplers useful in the elements of this invention which react with oxidized color developing agents to produce yellow dyes are: US Pat. Nos. 2,875,057 and 2,407,210.
No. 3,265,506, 2,298,443,
Nos. 3,048,194, 3,447,928, 4,022,620, 4,443,536 and "Farbkuppler-Eine Literatur Ubersicht", Agfa.
Representative patent specifications and publications, such as Mitteilungen, Band III, pages 112-126 (1961). Such couplers are typically open chain ketomethylene compounds. Particularly preferred are, for example, European Patent Applications Nos. 482,552, 510,535 and 52.
No. 4,540, 543, 367, and U.S. Pat. No. 5,238,803.

It is desirable to include high molecular weight hydrophobic or "ballast" groups in the component molecules to control the migration of the various components coated in the photographic layer. Representative ballast groups include substituted or unsubstituted alkyl or aryl groups having 8 to 40 carbon atoms.
Typical substituents on those groups typically have 1 carbon
~ 40 alkyl, aryl, alkoxy, aryloxy, alkylthio, hydroxy, halogen, alkoxycarbonyl, aryloxycarbonyl, carboxy, acyl, acyloxy, amino, anilino, carbonamide (also known as acylamino),
Includes carbamoyl, alkylsulfonyl, arylsulfonyl, sulfonamide, and sulfamoyl groups. Moreover, such a substituent may be further substituted. Alternatively, the molecule can be immobilized by attachment to the polymer backbone.

US Pat. Nos. 4,301,235, 4,
It would be useful to use a combination of couplers that can have known ballast or coupling-off groups, such as those described in 853,319 and 4,351,897. Research Disclo
Ja, February 1995, in Volume 370, "Typical and Pref
erred Color Paper, Color Negative, and Cololor Rev
It is also contemplated that the materials and processes described in "ersal Photographic Elements and Processing" may be used to advantage with the dispersions of this invention.

The materials of this invention can be used in combination with further image-improving compounds such as "development inhibitor releasing" compounds (DIR's). DIR's useful in combination with the compositions of the present invention are known in the art, examples of which are described in the following patent specifications. That is, U.S. Pat. Nos. 3,137,578, 3,148,022, 3,148,062, 3,227,554, 3,384,657, and 3,379,529. , 3,615,506, 3,617,291, 3,620,746, 3,701,783, 3,733,201, 4,049,455. 4,095,984, 4,126,459, 4,149,886, 4,150,228, 4,211,562, 4,248,962, 4, 259,437, 4,362,878, 4,409,323, 4,477,563, 4,782,012, 4,962,018, 4,500. 634, 4,579,816, 4,607,004, and , 618,571, 4,678,739, 4,746,600, 4,746,601, 4,791,049, 4,857,447, 4,865. , 959, 4,880,342, 4,886,736, 4,937,179, 4,946,767, 4,948,716, 4,952,485. Nos. 4,956,269, 4,959,299, 4,966,835, 4,985,336; and British Patent Publication Nos. 1,560,240 and 2,000.
7,662, 2,032,914, 2,09
9,167; German Patent No. 2,842,063,
Nos. 2,937,127, 3,636,824, 3,644,416; and European Patent No. 272,57.
No. 3, No. 335, 319, No. 336, 411, No. 3
46,899, 362,870, 365,25
No. 2, No. 365, 346, No. 373, 382, No. 3
76,212, 377,463, 378,23
No. 6, No. 384, 670, No. 396, 486, No. 4
No. 01,612 and No. 401,613.

Also, such compounds are represented by Photographic S
cience and Engineering , 13: 174, 1969, CR Barr, JR Thirtle and PW Vittum.
"Developer-Inhibitor-Releasing (DIR) Couplers for
Also disclosed in "color Photography". Particularly useful for use with the present invention are tabular grain silver halide emulsions. Suitable tabular grain emulsions are described in various conventional papers such as those described in the following references. You can choose from the teachings of.
That is, Research Disclosure, Item 22534,
January 1983; and U.S. Pat. No. 4,439,520
Issue No. 4,414,310 Issue No. 4,433,048
No. 4,643,966, No. 4,647,528
Issue No. 4,665,012, No. 4,672,027
No. 4,687,745, 4,693,964
Issue No. 4,713,320 Issue No. 4,722,886
Nos. 4,755,456 and 4,775,617
No. 4,797,354, 4,801,522
Issue No. 4,806,461 Issue No. 4,835,095
No. 4,853,322, 4,914,014
No. 4,962,015, 4,985,350
No. 5,061,069, No. 5,061,616 and No. 5,320,938.

These emulsions are surface-sensitive emulsions (ie,
These emulsions can form an internal latent image, mainly on the surface of silver halide grains, or these emulsions can form an internal latent image mainly on the inside of silver halide grains. These emulsions can be negative working emulsions (such as surface sensitive emulsions or unfogged internal latent image forming emulsions) or use unfogged, internal latent image forming type, uniform exposure or nucleating agents. When developed in the presence of, a positive-working direct positive emulsion can be obtained.

Se and Ir-doped tabular emulsions as described in US Pat. No. 5,164,292 are contemplated and preferred. It is particularly contemplated and preferred to use the present invention in combination with the lamina described in US Pat. No. 5,322,766. Emulsions of the present invention may include, for example, polymethine dye classes (including cyanines, merocyanines, cyanines and complexes of merocyanines, oxonols, hemioxonols, styryls, merostyryls and streptocyanines). Spectral sensitization can be carried out using any dye known in the photographic art. In particular, US Pat. No. 5,316,90
4, No. 5,292,634, No. 5,354,651
It may be advantageous to use the low-staining sensitizing dyes described in U.S. Pat.

The photographic elements can be exposed to actinic radiation (typically the visible region of the spectrum) to form a latent image which can then be processed to form a visible dye image. Processing to form a visible dye image includes the step of contacting the photographic element with a color developing agent to reduce developable silver halide and oxidize the color developing agent. The oxidized color developing agent is
It then reacts with the coupler to form a dye.

[0082]

EXAMPLE 1 Cyan coupler C-1 (30 g) was mixed with di-n-butyl phthalate (DBP) (30 g) and ethyl acetate (60 g).
g) at 75 ° C. Then, this oil phase solution was used as a 10% solution of gelatin (40 g) and Alkanol-XC (Dupont) (3
2 g) and an aqueous phase solution containing distilled water (308 g). Then, this mixture was passed through a Gaolin colloid mill five times, and then ethyl acetate was removed by a rotary evaporator. Then, distilled water was added, and the dispersion A containing 6% of coupler and 8% of gelatin was returned. Dispersions BG were similarly prepared using various amounts of DBP as described in Table I. These dispersions were stored in the refrigerator for 26 weeks, then kept at 45 ° C. for 6 hours and examined for crystallization by light microscopy. The results are summarized in Table I. According to microscopy, only the dispersion without coupler solvent was
It showed good resistance to crystal formation after long-term refrigeration and melt holding at high temperature.

Holding these dispersions at 45 ° C. for long periods of time resulted in very severe coupler crystallization and solid dispersions throughout the dispersion. The time required for this solidification to occur is
It is another indicator of dispersion stability and is shown in Table I. These results clearly show that the solvent-free dispersions have significantly improved melt retention stability compared to solvent-containing dispersions.

[0084]

[Table 1]

Example 2 Dispersions H and I were prepared in the same manner as Dispersions A and C, respectively (with and without DBP). And these dispersions were made 1: 8 with 8% gelatin.
Diluted with 1 to produce a coating solution consisting of 3% coupler and 8% gelatin. Each coating solution (5
00g) at 45 ° C for 24 hours and under pressure [3
4.5 kPa (5 psi)] and passed through a Grade 24 glass fiber depth filter (Hollingworth and Vose). The time required for the coating solution to pass through this filter is an indicator of the stability of the dispersion in which it is prepared. More stable dispersions are filtered faster than less stable dispersions. The filterability of the coating solution
The weight of the coating solution passing through the filter as a function of time was measured and evaluated. The results of the two replicate trials (illustrated in FIG. 1) show that the coating solution containing the solventless cyan coupler dispersion passes through the filter more rapidly than the solution with the solvent containing dispersion.

Example 3 Cyan coupler C-12 (30 g) was treated with ethyl acetate (9
0 g) at 70 ° C. Then, this oil phase solution was used as a 10% solution of gelatin (30 g) and Alkanol-XC (30
g) and an aqueous phase solution containing distilled water (320 g). And 5 to this mixture Gorlin colloid mill
In turn, the ethyl acetate was removed on a rotary evaporator. Then, distilled water was added, and the dispersion J containing 6% of coupler and 6% of gelatin was returned. Dispersions K and L were similarly prepared, with DBP in the oil phase in the amounts listed in Table I. These dispersions were stored in the refrigerator for 1 week, then kept at 45 ° C. for 4 hours and subsequently examined for crystallization by light microscopy. Further, these dispersions were kept at 45 ° C. for a long time, and the time required for solidification to occur was measured. The results are summarized in Table II.

[0087]

[Table 2]

This result also shows that the solvent-free dispersion was
It is shown to have improved melt retention stability as compared to solvent containing dispersions. Example 4 Dispersions J and L were diluted 1: 2 with 6% gelatin to produce a coating solution consisting of 2% coupler and 6% gelatin. Each coating solution (500
g) was kept at 45 ° C. for 6 hours and tested for filterability as described in Example 2. The results of the two replicate trials (shown in Figure 2) again demonstrated that the coating solution containing the solvent-free cyan coupler dispersion was more filterable than the solution with the solvent-containing dispersion.

Example 5 Dispersions M, N and O were prepared in the same manner as Dispersions J, K and L of Example 3, except that cyan coupler C-9 was replaced with cyan coupler C-12. These dispersions were stored in the refrigerator for 2 weeks, then kept at 45 ° C. for 40 hours and subsequently examined by light microscopy for crystallization. The results are summarized in Table III.

[0090]

[Table 3]

The solventless dispersions were significantly more stable than prior art low solvent dispersions. Example 6 Dispersions AA-OO were prepared as described in Example 3 using the photographic comparative compound, coupler solvent and incubation conditions described in Table IV. The results of microscopic evaluation are shown below.

[0092]

[Table 4]

These results indicate that dispersions without coupler solvent are substantially less prone to crystallization than their solvent-containing controls in a wide variety of photographically useful compounds that have a tendency to crystallize in the dispersion. Demonstrate greatness.

[0094]

[Chemical formula 23]

Example 7 Photographic Sample 101 (Comparison Control) A color photographic recording material for color negative development was prepared by coating the following layers in the order listed on a cellulose triacetate support. The side of the support to be coated is prepared with a gelatin subbing layer, the opposite side of the support is soluble in basic aqueous solution and useful for providing a removable black antihalation backing with antistatic properties. , Containing a carbon pigment (REMJET coating) dispersed in a non-gelatin binder. The amount of silver halide is expressed in g of silver per m ² . The quantities of other materials are expressed in g / m ² .
The cyan dye-forming coupler C-1 used in the low and high speed red sensitive layers was prepared as in Comparative Dispersion A of Dispersion Example 1 with a ratio of high boiling solvent di-n-butyl phthalate to coupler of 1.0. Generally dispersed. The various compounds used in this photograph example are the same in the following examples.

Layer 1: Low-Sensitivity Red-Sensitive Layer This layer contains the slower-sensitivity red-sensitive silver iodobromide emulsion (3.0 mol% iodide, diameter 0.58 μm) and the higher-sensitivity red-sensitive layer. , Silver iodobromide emulsion (4.0% iodide, diameter 0.86 μm). Low-speed emulsion 1.356 High-speed emulsion 0.581 DIR coupler D-1 0.031 Bleach accelerator coupler BAR-1 0.021 Cyan dye-forming coupler C-1 0.288 HBS-1 0.124 HBS-20 .288 HBS-3 0.021 TAI 0.031 gelatin 2.523

Layer 2: High-sensitivity red-sensitive layer Red-sensitized silver iodobromide emulsion [6.0 mol% iodide, average grain diameter 1.14 μm]. Emulsion 0.969 DIR coupler D-2 0.076 Cyan dye forming magenta colored coupler CM-1 0.028 Cyan dye forming coupler C-1 0.093 HBS-2 0.093 HBS-4 0.150 TAI 0.016 Gelatin 1.388

Layer 3: Interlayer Compensation Print Density Yellow Dye MM-1 0.059 Oxidized Developer Scavenger DOXS-1 0.095 Compensation Print Density Magenta Dye MD-1 0.024 Gelatin 0.947.

Layer 4: Low-Sensitivity Green-Sensitive Layer This layer contains the lower-sensitivity, green-sensitive, silver iodobromide emulsion [3.0 mol% iodide, average grain diameter 0.44 μm] and higher sensitivity. Green-sensitive, silver iodobromide emulsion [6. 0% iodide, average grain diameter 0.77 μm]. Low-speed emulsion 0.162 High-speed emulsion 1.185 DIR coupler D-3 0.022 Magenta dye forming yellow colored coupler MM-2 0.135 Magenta dye forming coupler M-1 0.236 Magenta dye forming coupler M-20 .101 Oxidized developing agent scavenger DOXS-2 0.015 HBS-1 0.481 TAI 0.022 gelatin 1.822

Layer 5: High sensitivity green sensitive layer Green sensitized silver iodobromide emulsion [3.0 mol% iodide, average grain diameter 0.81 μm]. Emulsion 0.861 DIR coupler D-3 0.019 Magenta dye forming yellow colored coupler MM-2 0.027 Magenta dye forming coupler M-3 0.060 Oxidized developing agent scavenger DOXS-2 0.012 HBS-1 0.152 TAI 0.014 Gelatin 1.250

Layer 6: Yellow filter layer compensation print density Yellow dye MM-1 0.091 Yellow filter dye YD-1 0.154 Oxidized developing agent scavenger DOXS-1 0.118 Gelatin 0.947

Layer 7: Low Sensitivity Blue Sensitive Layer This layer comprises the less sensitive, blue sensitive, silver iodobromide emulsion [3.0 mol% iodide, average grain diameter 0.56 μm] and higher sensitivity. Blue-sensitive, silver iodobromide emulsion [3. 0% iodide, average grain diameter 0.76 μm]. Low speed emulsion 0.182 High speed emulsion 0.182 DIR coupler D-10 0.009 Yellow dye forming coupler Y-1 0.725 Oxidized developing agent scavenger DOXS-2 0.010 HBS-2 0.372 TAI 0.006 gelatin 1.557

Layer 8: High-sensitivity blue-sensitive layer Blue-sensitized silver iodobromide emulsion [3.0 mol% iodide, average grain diameter 1.07 μm]. Emulsion 0.450 DIR coupler D-4 0.039 Yellow dye forming coupler Y-1 0.133 Oxidized developing agent scavenger DOXS-2 0.019 HBS-2 0.106 TAI 0.001 Gelatin 0.965

Layer 9: UV filter layer Dye UV-1 0.022 Dye UV-2 0.114 Unsensitized silver bromide Lippmann emulsion 0.215 HBS-5 0.136 Gelatin 0.861

Layer 10: Protective overcoat layer Polymethylmethacrylate matte beads 0.009 Soluble polymethylmethacrylate matte beads 0.161 Silicone lubricant 0.057 Gelatin 0.873

These films were treated with 1.8% of total gelatin.
The film was hardened with a coating film containing 0% by weight of a hardener H-1. Surfactant, coating aid, soluble absorber dye and stabilizer,
The various layers of this sample were added as is commonly practiced in the art. Photographic Sample 102 (Invention) A color photographic recording material for color negative development was prepared exactly as Sample 101 above except as described below. The cyan dye-forming coupler C-1 used in the slow and fast red sensitive layers was generally dispersed as in Invention Example C of Dispersion Example 1 without the presence of a high boiling solvent.

Layer 1: Slow red sensitive layer modified partial bleach accelerator coupler BAR-1 0.019 Cyan dye forming coupler C-1 0.262 HBS-1 0.124 HBS-2 0.000 HBS-3 0. 019 Gelatin 2.477

Layer 2: High-sensitivity red-sensitive layer-modified partial cyan dye-forming magenta colored coupler CM-1 0.031 cyan dye-forming coupler C-1 0.104 HBS-2 0.000 gelatin 1.431

Layer 4: Low-sensitivity green-sensitive layer-modified part Magenta dye-forming coupler M-1 0.198 Magenta dye-forming coupler M-2 0.084 HBS-1 0.453 gelatin 1.781

Duplicate samples of photographic recording material samples 101 and 102 were subjected to white light from a 3200 K color temperature tungsten light source through a graded 0-3.0 density step tablet to determine its speed and gamma. Each was exposed for 1/50 second. And, these samples, "Manual for Process
ing Eastman Motion Picture Film ", Publication H-
24,07, Colorman negative treatment described in Eastman Kodak Company, Rochester, NY, KODAK ECN-2 treatment. Other color negative processing, such as this motion picture film color negative processing and color negative amateur film processing C-41, are available in the British Journal of Photography Annual,
1988, pp. 196-198.

After treatment and drying, samples 101 and 1
02 was subjected to Status M densitometry and the duplicate sample concentration data was averaged. The photographic performance of these recording materials is compared in Table V below.

[0112]

[Table 5]

From these photographic data, after directly substituting the comparative control dispersion using di-n-butyl phthalate in a weight ratio of 1.0 to C-1 of the color negative recording material of Example 1, the high boiling point solvent was replaced. It can be seen that the cyan dye-forming coupler C-1 dispersions of the present invention that are not included can produce substantially the same sensitometric performance. Example 8 Photographic Sample 201 (Comparative Control) A color photographic recording material for color negative development was prepared by coating the following layers in the order listed on a cellulose triacetate support. The support side to be coated was prepared with a gelatin subbing layer. The amount of silver halide is expressed in g of silver per m ² . The quantities of other materials are expressed in g / m ² . Cyan dye-forming coupler C-used in low-sensitivity, intermediate-sensitivity and high-sensitivity red-sensitive layers
1 was generally dispersed as Comparative Control Dispersion A of Dispersion Example 1 at a ratio of high boiling solvent di-n-butyl phthalate to coupler of 1.0.

Layer 1: Antihalation Layer Black colloidal silver sol (0.151 g / m ² ). UV-1 0.075 UV-2 0.075 Oxidized developing agent scavenger DOXS-3 0.162 Compensation print density Cyan dye CD-1 0.020 Compensation print density Magenta dye MD-2 0.042 Compensation print density Yellow dye MM-1 0.088 Compensated print density Yellow dye YD-2 0.008 HBS-1 0.426 HBS-5 0.151 Disodium salt of 3,5-di-sulfocatechol 0.270 Gelatin 2.441

Layer 2: Low Sensitivity Red Sensitive Layer This layer is a slower, red sensitized tabular silver iodobromide emulsion [1.3 mol% iodide, average grain diameter 0.53 μm and thickness 0. 0.09 μm] and a more sensitive formulation of a red-sensitized tabular silver iodobromide emulsion [4.1% iodide, average grain diameter 1.04 μm and thickness 0.09 μm]. Low speed emulsion 0.495 High speed emulsion 0.431 Bleach accelerator coupler BAR-1 0.038 Cyan dye forming coupler C-1 0.517 Cyan dye forming magenta colored coupler CM-1 0.027 Oxidized developing agent scavenging Agent DOXS-2 0.010 HBS-2 0.517 HBS-3 0.038 TAI 0.015 Gelatin 1.775

Layer 3: Medium speed red sensitive layer Red sensitized tabular silver iodobromide emulsion [4.1 mol% iodide, average grain diameter 1.39 μm and thickness 0.12 μm]. Emulsion 0.700 DIR coupler D-5 0.011 Cyan dye forming magenta colored coupler CM-1 0.022 Cyan dye forming coupler C-1 0.215 HBS-2 0.215 HBS-4 0.022 TAI 0.011 Gelatin 1.786

Layer 4: High-sensitivity red-sensitive layer Red-sensitized tabular silver iodobromide emulsion [4.1 mol% iodide, average grain diameter 2.93 μm and thickness 0.13 μm]. Emulsion 1.076 DIR coupler D-5 0.020 DIR coupler D-6 0.048 Cyan dye forming magenta colored coupler CM-1 0.032 Cyan dye forming coupler C-1 0.140 HBS-1 0.194 HBS- 2 0.140 HBS-4 0.041 TAI 0.010 gelatin 1.711

Layer 5: Intermediate gelatin 1.292

Layer 6: Low Sensitivity Green Sensitive Layer This layer is a slower, green sensitized tabular silver iodobromide emulsion [1.3 mol% iodide, average grain diameter 0.53 μm and thickness 0. 0.09 μm] and higher sensitivity green sensitized tabular silver iodobromide emulsions [4.1% iodide, average grain diameter 1.04 μm and thickness 0.09 μm]. Low speed emulsion 0.581 High speed emulsion 0.312 Magenta dye forming yellow colored coupler MM-2 0.065 Magenta dye forming coupler M-4 0.269 Oxidized developing agent scavenger DOXS-2 0.023 HBS-1 0.345 TAI 0.014 Gelatin 1.723

Layer 7: Medium speed green sensitive layer Green sensitized tabular silver iodobromide emulsion [4.1 mol% iodide, average grain diameter 1.23 μm and thickness 0.12 μm]. Emulsion 0.969 DIR coupler D-5 0.024 Magenta dye forming yellow colored coupler MM-2 0.065 Magenta dye forming coupler M-4 0.070 Oxidized developing agent scavenger DOXS-2 0.019 HBS-1 0.186 HBS-4 0.048 TAI 0.014 Gelatin 1.399

Layer 8: High-sensitivity green-sensitive layer Green sensitized tabular silver iodobromide emulsion [4.1 mol% iodide, average grain diameter 2.19 μm and thickness 0.13 μm]. Emulsion 0.969 DIR coupler D-3 0.011 DIR coupler D-7 0.011 Magenta dye forming yellow colored coupler MM-2 0.054 Magenta dye forming coupler M-4 0.058 Oxidized developing agent scavenger DOXS -0.016 HBS-1 0.176 HBS-2 0.011 TAI 0.012 Gelatin 1.291

Layer 9: Yellow filter layer Yellow filter dye YD-1 0.108 gelatin 1.292

Layer 10: Low Sensitivity Blue Sensitive Layer This layer is a slower, blue sensitized tabular silver iodobromide emulsion [1.3 mol% iodide, average grain diameter 0.53 μm and thickness 0. 0.09 μm], medium-sensitivity, tabular blue-sensitized silver iodobromide emulsion [4.1 mol% iodide, average grain diameter 0.80 μm and thickness 0.09 μm], and higher sensitivity, tabular blue A formulation of a sensitized silver iodobromide emulsion [6.0% iodide, mean grain diameter 0.96 μm and thickness 0.26 μm] is included. Low-speed emulsion 0.269 Medium-speed emulsion 0.172 High-speed emulsion 0.549 DIR coupler D-8 0.065 Yellow dye-forming coupler Y-1 0.280 Yellow dye-forming coupler Y-2 0.700 Bleach accelerator coupler BAR-1 0.003 Cyan dye forming coupler C-1 0.027 Oxidized developer scavenger DOXS-2 0.005 HBS-2 0.931 HBS-3 0.003 TAI 0.016 Gelatin 2.519

Layer 11: High-sensitivity blue-sensitive layer This layer comprises a lower-sensitivity, blue-sensitized tabular silver iodobromide emulsion [9.0 mol% iodide, average grain diameter 1.06 μm] and higher. Contains a sensitive, tabular blue sensitized silver iodobromide emulsion [4.1% iodide, mean grain diameter 3.37 μm and thickness 0.14 μm]. Low-speed emulsion 0.226 High-speed emulsion 0.570 Yellow dye-forming coupler Y-1 0.080 Yellow dye-forming coupler Y-2 0.200 DIR coupler D-8 0.048 Bleach accelerator coupler BAR-1 0.005 Cyan dye-forming coupler C-1 0.029 Oxidized developer scavenger DOXS-2 0.001 HBS-2 0.317 HBS-3 0.005 TAI 0.013 Gelatin 1.580

Layer 12: UV filter layer Dye UV-1 0.108 Dye UV-2 0.108 Unsensitized silver bromide Lippmann emulsion 0.215 HBS-5 0.215 Gelatin 0.699

Layer 13: Protective overcoat layer Polymethylmethacrylate matte beads 0.005 Soluble polymethylmethacrylate matte beads 0.054 Silica gel particles 0.108 Silicone lubricant 0.039 Gelatin 0.888

These films were treated with 1.7% of total gelatin.
The film was hardened with a coating film containing 5% by weight of the hardener H-2. Surfactants, coating aids, soluble absorber dyes, antifoggants,
Stabilizers, antistatic agents, biocides, and other agents were added to the various layers of this sample as is commonly practiced in the art. Photographic Sample 202 (Invention) A color photographic recording material for color negative development was prepared exactly as Sample 201 above except as described below. The cyan dye-forming coupler C-1 used in the fast red sensitive layer was generally dispersed as in Invention Example C of Dispersion Example 1 without the presence of a high boiling solvent.

Layer 4: High-sensitivity red-sensitive layer modified portion HBS-2 0.000

Sample 203 (Invention) A color photographic recording material for color negative development was prepared exactly as Sample 201 except as described below. The cyan dye-forming coupler C-1 used in the fast red sensitive layer was generally dispersed as in Invention Example C of Dispersion Example 1 without the presence of a high boiling solvent. Another dispersion of HBS-2 was added to the liquid coating solution to give the same coverage (weight) as cyan dye-forming coupler C-1.

Sample 204 (Invention) A color photographic recording material for color negative development was prepared exactly as Sample 202 above except as described below. The red sensitized tabular silver iodobromide emulsion of Layer 4 contained 3.1 mol% iodide (average grain diameter 2.42 μm and thickness 0.
12 μm). This emulsion contained 1.0 mol% less iodide than the emulsion used in Sample 202. This lower concentration iodide emulsion was prepared as described in US Pat. No. 5,164,292.

Sample 205 (Invention) A color photographic recording material for color negative development was prepared exactly as Sample 202 above except as described below. The red sensitized tabular silver iodobromide emulsion of Layer 4 contained 2.0 mol% iodide (average grain diameter 3.07 μm and thickness 0.
12 μm). This emulsion contained 2.1 mol% less iodide than the emulsion used in Sample 202. This lower concentration iodide emulsion was prepared as described in US Pat. No. 5,164,292.

Sample 206 (Invention) A color photographic recording material for color negative development was prepared exactly as Sample 202 above except as described below. Layer 4 did not contain DIR coupler D-5. Layer 4: High Sensitivity Red Sensitive Layer Modified Part DIR Coupler D-5 0.000 HBS-4 0.000 Sample 207 (Invention) Sample 202 above except a color photographic recording material for color negative development is described below. Was prepared exactly as Layer 4 additionally comprises a bleach accelerator releasing compound BAR-
1 was included.

Layer 4: High Sensitivity Red Sensitive Layer Modified Part Bleach Accelerator Coupler BAR-1 0.011 HBS-2 0.000 HBS-3 0.011

Sample 208 (invention) Layer 4 was prepared at higher concentrations of the bleach accelerator releasing compound BAR-1.
A color photographic recording material for color negative development was prepared exactly as Sample 207 above, except that Layer 4: High-sensitivity red-sensitive layer-modified part bleaching accelerator coupler BAR-1 0.027 HBS-2 0.000 HBS-3 0.027

Sample 209 (Invention) A color photographic recording material for color negative development was prepared exactly as Sample 202 above except as described below. Layer 4 additionally comprises a development accelerator compound CHEM-1.
Was included. Layer 4: High-sensitivity red-sensitive layer-modified partial development accelerator compound CHEM-1 0.007 HBS-2 0.000

Photographic recording material samples 201 and 209
550 through a graded 0-4.0 density step tablet to determine its speed and gamma.
Each was exposed for 1/500 seconds to white light from a 3200K color temperature tungsten light source filtered by a Daylight Va filter for 0K. Then, these samples are used in the British Journal of Photography A
nnual, 1988, pp. 196-198, color negative treatment C-41. "Using Kodak Flexicolor C
hemicals '', Publication Z-131, Eastman Kodak Compa
Another description of the C-41 Flexicolor process can be found in ny ,.

After processing and drying, samples 201-20
9 was subjected to Status M densitometry. The photographic performance of these recording materials is compared in Table VI below.

[0138]

[Table 6]

Photographic data for sample 202 directly replaces the comparative dispersion using di-n-butyl phthalate in a weight ratio of 1.0 to C-1 of the fast red sensitive layer of the color negative recording material of Example 2. After that, it is shown that the dispersion of the cyan dye-forming coupler C-1 of the present invention containing no high boiling solvent can give almost the same sensitometric performance. The photographic data for sample 203 show that a dispersion of cyan dye-forming coupler C-1 of the present invention having no high boiling solvent and improved stability was prepared at a weight ratio of HBS-2 of 1.0 when the liquid coating solution was prepared. We show that the same sensitometric response can be given in combination with the dispersion.

Photographic data of samples 204 to 205 are as follows:
The high boiling solvent-free dispersion of the cyan dye-forming coupler C-1 of the present invention is combined with silver halide grains of lower iodide content to maintain sensitivity, enhance gamma of photographic units, and at the same time increase It is shown that a thinner layer can be made with a smaller amount of boiling solvent. Sample 20
The photographic data in Example 6 show the gamma and density response of photographic units comprising the cyan dye-forming coupler C-1 dispersion of the present invention without the high boiling solvent levels of the development inhibitor releasing coupler used in the layer. Show that it can be raised by lowering.

Photographic data for Samples 207 and 208 show bleaching of a dispersion of the cyan dye-forming coupler C-1 of the present invention containing no high boiling solvent to enhance layer developability and increase gamma and maximum density of red sensitive units. It shows that it can be combined with accelerator-releasing compounds. Sample 209
Photographic data show that dispersions of the cyan dye-forming coupler C-1 of this invention without the high boiling solvent can be used with a development accelerating polymeric agent to improve speed.

Example 9 Photographic Sample 301 (Comparison Control) The same color photographic recording material for color negative development as Photographic Sample 201 was prepared. The film was hardened with a coating containing 1.75% by weight of total gelatin of hardener H-2. Surfactants, coating aids, soluble absorber dyes and stabilizers were added to the various layers of this sample as is commonly practiced in the art.

Photographic Sample 302 (Invention) A color photographic recording material for color negative development was prepared exactly as Sample 301 above except as described below. The cyan dye-forming coupler C-1 used in the high-speed red-sensitive layer (layer 4) and the medium-speed red-sensitive layer (layer 3) was prepared as in Inventive Example C of Dispersion Example 1 without the presence of a high-boiling solvent. Dispersed.

Layer 3: Middle sensitivity red sensitive layer modified portion HBS-2 0.000 Layer 4: High sensitivity red sensitive layer modified portion HBS-2 0.000

Photographic Sample 303 (Invention) A color photographic recording material for color negative development was prepared exactly as Sample 301 above except as described below. The cyan dye-forming coupler C-1 used in the high-speed red-sensitive layer (layer 4) and the medium-speed red-sensitive layer (layer 3) was prepared as in Inventive Example C of Dispersion Example 1 without the presence of a high-boiling solvent. Dispersed. Another dispersion of HBS-2 was added to the two layer liquid coating solution to give the same coverage (by weight) as cyan dye-forming coupler C-1.

Photographic Sample 304 (Invention) A color photographic recording material for color negative development was prepared exactly as Sample 301 above except as described below. The cyan dye-forming coupler C-1 used in the high-sensitivity red-sensitive layer (Layer 4), the medium-sensitivity red-sensitive layer (Layer 3), and the low-sensitivity red-sensitive layer (Layer 2) was prepared in the absence of a high-boiling solvent. It was generally dispersed as Inventive Example C of Dispersion Example 1. HBS
-2 was added to the liquid coating solution for the three layers to give the same coverage (by weight) as cyan dye-forming coupler C-1.

Photographic Sample 305 (Invention) A color photographic recording material for color negative development was prepared exactly as Sample 301 above except as described below. The cyan dye-forming coupler C-1 used in the high-speed red-sensitive layer (layer 4) and the medium-speed red-sensitive layer (layer 3) was prepared as in Inventive Example C of Dispersion Example 1 without the presence of a high-boiling solvent. Dispersed. The coverage of coupler C-1 was significantly increased.

Layer 3: Medium speed red sensitive layer modified partial cyan dye forming coupler C-1 0.312 HBS-2 0.000 Layer 4: High sensitivity red sensitive layer modified partial cyan dye forming coupler C-1 0.183 HBS -2 0.000

Photographic Sample 306 (Invention) A color photographic recording material for color negative development was prepared exactly as Sample 305 above except as described below. Development inhibitor releasing coupler D-5 in layers 3 and 4 was added to
Replaced with an equal amount of D-9. D-5 was dispersed with HBS-4, while D-9 was dispersed with HBS-2. Therefore, although the coating amounts of these solvents also changed,
For 5, the overall amount of solvent was maintained. Parent
The photographically useful group of D-9 containing the switch and inhibitor moieties released by the coupler is compared to the photographically useful group of D-5 from the production layer prior to releasing the inhibitor fragment. It has a higher tendency to migrate, and then develop inhibition.

Layer 3: Medium speed red sensitive layer modified partial cyan dye forming coupler C-1 0.312 DIR coupler D-5 0.000 DIR coupler D-9 0.011 HBS-2 0.022 HBS-40. Layer 000 : High-sensitivity red-sensitive layer-modified partial cyan dye-forming coupler C-1 0.183 DIR coupler D-5 0.000 DIR coupler D-9 0.020 HBS-2 0.041 HBS-4 0.000

Photographic recording material samples 301 to 306
Gradual zero to determine its speed and gamma
~ 4.0 Density step through tablet 5500K
Filtered by Daylight Va filter against 3
Each was exposed to white light from a tungsten light source having a color temperature of 200 K for 1/500 seconds. The samples were then processed using the Kodak C-41 process.

Samples 301-30 after treatment and drying
6 was subjected to Status M densitometry. The photographic performance of these recording materials is compared in Table VII below.

[0153]

[Table 7]

Photographic data for sample 302 is a comparison using di-n-butyl phthalate in a weight ratio of 1.0 to C-1 of the high speed and low speed red sensitive layers of the color negative recording material of Example 3. The cyan dye-forming coupler C- of the present invention free of high boiling solvent after direct replacement of the control dispersion.
1 dispersion gives reduced gamma and density performance. Photographic data for Sample 303 shows that a dispersion of cyan dye-forming coupler C-1 of the present invention having no high boiling solvent and improved stability was used to prepare a two layer liquid coating solution at a weight ratio of 1.0. We show that it can give almost the same sensitometric response in combination with a dispersion of HBS-2.

Photographic data for sample 304 shows that the dispersion of cyan dye-forming coupler C-1 of the present invention with improved stability, free of high boiling solvents, was added to all red sensitive layers containing coupler C-1. Shows that almost the same sensitometric response can be obtained when combined with a 1.0 wt% HBS-2 dispersion in the preparation of the liquid coating solution of. The photographic data for sample 305 show that the high stability solvent-free dispersion of the cyan dye-forming coupler C-1 of the present invention with improved stability was used in the higher coating weights without HBS-2 and the gamma of the photographic unit. We show that the response can be improved while at the same time reducing the amount of high boiling solvent to produce thinner layers.

The photographic data for sample 306 show that the gamma and density response of photographic units comprising the cyan dye-forming coupler C-1 dispersions of this invention without the high boiling solvent are higher than the interlayer suppression than the interlayer suppression. It is shown that this can be enhanced by changing the properties of the development inhibitor releasing coupler used in the layer in order to select the compound having.

Example 10 Solventless coupler dispersions were prepared as follows. Cyan coupler C-1 (3300 g) was mixed with ethyl acetate (6
600 g) at 75 ° C. Then, this oil phase solution was mixed with gelatin (4400 g), a 10% solution of Alkanol-XC (Dupont) surfactant (3520 g), and distilled water (3
7,180 g) and the aqueous phase solution. Then add 10350 kP to this mixture Crepaco homogenizer
Ethyl acetate was removed by single pass at a (1500 psi) pressure and then evaporation. Then, distilled water was added, and the dispersion P was made up of 6% coupler and 8% gelatin.

A high boiling solvent dispersion was prepared as follows. Irganox-1076 (Chiba-Geigy) hydrophobic additive (4
g) was dissolved in dibutyl phthalate (400 g) at 50 ° C., and gelatin (400 g), a 10% solution of Alkanol-XC (300 g), Kathon LX (Rohm and Haas) biocide 0.
7% solution (7.2 g), and distilled water (3488.8 g)
Was mixed with an aqueous phase solution containing And using this mixture Silverson mixer for 5 minutes 5000 rp
3450 m in a Crepaco homogenizer by premixing
Dispersion Q consisting of 8% solvent and 8% gelatin was made through one pass at a pressure of 0 kPa (5000 psi).

Dibutyl phthalate (400 g) was added to Table VIII.
A dispersion of another high-boiling solvent was prepared in the same manner as Dispersion Q, except that the other high-boiling solvent (400 g) listed in 1 above was replaced.

[0160]

[Table 8]

The coating solution was prepared as follows. Dispersion P (36.7 g) was mixed with 35% gelatin (1
Dispersion Q with 2.6 g) and distilled water (40.2 g)
(13.8 g). This mixture was heated to 40 ° C. with stirring for 1 hour to give 2.2% coupler, 1.1% solvent.
% And coating solution Q consisting of 8.4% gelatin
Created Q.

Coating solutions containing dispersions of other high boiling solvents were similarly prepared as described in Table IX below. Coating solution PP (without added solvent) is also included as a control. The coupling rate constant (k) for the reaction of the coupler with the oxidized color developing agent CD-4 was determined for these coating solutions in US Pat. No. 5,089,380, column 22.
It was measured using an aqueous competition test with sulfite ion as described in -23. The results are reported in Table IX in units of m ^-1 sec ^-1 .

[0163]

[Table 9]

From these results, it is clear that when used at low levels according to the invention, the solvents of the invention give higher coupler reactivity than the solvents used in the prior art. Example 11 Sample 401 (Comparative Control) A color photographic recording material for color negative development was prepared by coating the following layers in the order listed on a transparent support of cellulose triacetate. The support side to be coated was prepared with a gelatin subbing layer. The amount of silver halide is g of silver per 1 m ^2.
It is represented by. The quantities of other materials are expressed in g / m ² . The cyan dye-forming coupler C-1 used in the red-sensitive layer was dispersed at a ratio of the high boiling solvent HBS-2 to the coupler of di-n-butyl phthalate of 1.0.

Layer 1: Antihalation Layer UV-1 0.038 UV-2 0.038 Oxidized Developer Scavenger DOXS-4 0.108 Compensated Print Density Cyan Dye CD-2 0.016 Compensated Print Density Magenta Dye. MD-2 0.043 Compensated print density yellow dye MM-1 0.097 HBS-2 0.237 HBS-1 0.172 HBS-5 0.060 3,5-Di-sodium salt of di-sulfocatechol 0.270 Gelatin 2.441 Black colloidal silver sol 0.151

Layer 2: Red Sensitive Layer This layer is the less sensitive red sensitized tabular silver iodobromide emulsion [1.3 mol% iodide, average grain diameter 0.53 μm and thickness 0.09 μm. ] And a more sensitive formulation of a red-sensitized tabular silver iodobromide emulsion [4.1% iodide, mean grain diameter 1.04 μm and thickness 0.09 μm]. Low speed emulsion 0.409 High speed emulsion 0.441 Bleach accelerator coupler BAR-1 0.038 Cyan dye forming coupler C-1 0.538 Cyan dye forming magenta colored coupler CM-1 0.027 Oxidized developing agent scavenging Agent DOXS-2 0.010 HBS-2 0.538 HBS-3 0.038 TAI 0.015 Gelatin 1.722

Layer 3: Ultraviolet Filter Layer Dye UV-1 0.108 Dye UV-2 0.108 Unsensitized silver bromide Lippmann emulsion 0.215 HBS-5 0.172 Gelatin 0.699

Layer 4: Protective overcoat layer Polymethylmethacrylate matte beads 0.005 Soluble polymethylmethacrylate matte beads 0.054 Silicone lubricant 0.039 Gelatin 0.888

These films were treated with 1.7% of total gelatin.
The film was hardened with a coating film containing 5% by weight of the hardener H-2. Surfactant, coating aid, soluble absorber dye and stabilizer,
The various layers of this sample were added as is commonly practiced in the art. Photographic Sample 402 (Comparative Control) A color photographic recording material for color negative development was prepared exactly as Sample 401 above except as described below. The cyan dye-forming coupler C-1 used in the red sensitive layer of Sample 401 was generally dispersed as in Dispersion Example 10, Example P, in the absence of a high boiling solvent.

Layer 2: Red sensitive layer modified portion HBS-2 0.000

Photographic Sample 403 (Comparison Control) A color photographic recording material for color negative development was prepared exactly as Sample 402 above except as described below. A red-sensitivity comprising another dispersion of HBS-2, which is typically dispersed as Dispersion Q of Dispersion Example 10, and a coupler C-1, which is generally dispersed as Dispersion P of Dispersion Example 10. Addition to the liquid coating solution of layer (Layer 2) provided a 25% coverage (by weight) of cyan dye-forming coupler C-1.

Layer 2: Red-sensitive layer-modified portion HBS-2 0.135

Photographic Sample 404 (Comparison Control) A color photographic recording material for color negative development was prepared exactly as Sample 402 above except as described below. A red-sensitivity comprising another dispersion of HBS-2, which is typically dispersed as Dispersion Q of Dispersion Example 10, and a coupler C-1, which is generally dispersed as Dispersion P of Dispersion Example 10. The layer was added to the liquid coating solution to give 50% coverage (by weight) of cyan dye-forming coupler C-1.

Layer 2: Red sensitive layer modified portion HBS-2 0.269

Photographic Sample 405 (Comparison Control) A color photographic recording material for color negative development was prepared exactly as Sample 402 above except as described below. A red-sensitivity comprising another dispersion of HBS-2, which is typically dispersed as Dispersion Q of Dispersion Example 10, and a coupler C-1, which is generally dispersed as Dispersion P of Dispersion Example 10. The layer was added to the liquid coating solution to give the same coverage (by weight) as cyan dye-forming coupler C-1.

Layer 2: Red sensitive layer modified portion HBS-2 0.538

Photographic Sample 406 (Invention) A color photographic recording material for color negative development was prepared exactly as Sample 402 above except as described below. Dispersion HBS-9 (Formula II-1
Of dibutyl sebacate) of Dispersion Example 10
C-1 which is generally dispersed, such as dispersion P of
Was added to the liquid coating solution of the red-sensitive layer, which gave a 25% coverage (by weight) of cyan dye-forming coupler C-1.

Layer 2: Red-sensitive layer-modified portion HBS-9 0.129 HBS-2 0.000

Photographic Sample 407 (Invention) A color photographic recording material for color negative development was prepared exactly as Sample 402 above except as described below. A red-sensitivity comprising another dispersion of HBS-9, typically dispersed as Dispersion S of Dispersion Example 10, and a coupler C-1, generally dispersed as Dispersion P of Dispersion Example 10. The layer was added to the liquid coating solution to give 50% coverage (by weight) of cyan dye-forming coupler C-1.

Layer 2: Red sensitive layer modified portion HBS-9 0.269 HBS-2 0.000

Photographic Sample 408 (Comparative Control) A color photographic recording material for color negative development was prepared exactly as Sample 402 above except as described below. A red-sensitivity comprising another dispersion of HBS-9, typically dispersed as Dispersion S of Dispersion Example 10, and a coupler C-1, generally dispersed as Dispersion P of Dispersion Example 10. The layer was added to the liquid coating solution to give the same coverage (by weight) as cyan dye-forming coupler C-1.

Layer 2: Red sensitive layer modified portion HBS-9 0.538 HBS-2 0.000

Photographic recording material samples 401 to 408
Gradual zero to determine its speed and gamma
~ 4.0 Density step through tablet 5500K
Daylight Va Filter and KODAK WRATTEN for
3200 filtered by GELATIN filter (# 9)
1 / for white light from a K light source with a tungsten light source
Each was exposed for 50 seconds. Then, these samples were taken from the British Journal of Photography Annual, 1988,
Processing was carried out using Color Negative Processing C-41 described on pages 196-198. "Using Kodak Flexicolor Chemicals",
Publication Z-131, Eastman Kodak Company, C-41
Another description of the Flexicolor process can be found.

After processing and drying, samples 401-40
8 was subjected to Status M densitometry. The photographic performance of these recording materials is compared in Table X below.

[0185]

[Table 10]

Photographic data for sample 402 is shown in Example 401.
After directly substituting the comparative control dispersion using HBS-2 (di-n-butyl phthalate) in a weight ratio of 1.0 to C-1 of the red sensitive layer of the color negative recording material of No. It is shown that the dispersion of cyan dye-forming coupler C-1 of the present invention provides very low gamma and upper scale density producing ability. Photographic data for Samples 403 and 404 show comparative high boiling solvents (HBS) in the art.
-2) is 0.25 during the preparation of the liquid coating solution
It shows that when mixed with a solvent-free dispersion of a cyan dye-forming coupler C-1 in a weight ratio of 0.50, it still gives a low density-forming response.

Comparative control sample 405 is sample 40
1, which gives substantially the same results as 1 and combines the solvent-free dispersion of coupler C-1 with the dispersion of the high boiling solvent HBS-2 in the red sensitive layer liquid coating solution,
It is shown that a normal ratio of 1.0 yields almost the same performance as making common dispersions of C-1 and HBS-2.

Solvent HBS-9 dispersed as Dispersion S of Example 10 and coupler dispersed without solvent as Dispersion P under the same conditions of use of Samples 406 and 407 at the lower solvent to coupler ratios. The combination with C-1 gives increased gamma response and density production compared to the control (403 and 404).

However, under normal conditions with a solvent to coupler ratio of 1.0, the combination of HBS-9 and C-1 yields HBS
It can be seen that the function is the same as that of -2. Thus, it can be seen that the advantages of the present invention appear at solvent to coupler weight ratios of about 0.5, and are shown in Table X by the relative gamma performance ratios of HBS-9 film to corresponding HBS-2 film. As shown, this improvement increases as the ratio decreases. The gamma ratio is
A typical solvent-to-coupler ratio of 1.0 did not change much, with a solvent-to-coupler ratio of 0.25 yielding a complete 10% performance advantage with HBS-9, which is twice as high as HBS-2. Match performance.

In this manner, the improved crystallization stability of the C-1 solventless dispersions is enjoyed while at the same time the reduction in solvent amount provided by using the high boiling solvents of the present invention with C-1 is reduced. , Reduced material coverage, thinner layers,
And equivalent photographic performance. Example 12 Photographic Sample 501 (Comparative Control) A color photographic recording material for color negative development was prepared by coating the following layers in the order listed on a transparent support of cellulose triacetate. The support side to be coated was prepared with a gelatin subbing layer. The amount of silver halide is g of silver per 1 m ^2.
It is represented by. The quantities of other materials are expressed in g / m ² . Cyan dye forming coupler C-1 used in low, medium and high speed red sensitive layers
Is a high boiling solvent HBS-2 for the coupler, di-n-
The butyl phthalate was dispersed at a ratio of 1.0.

Layer 1: Antihalation Layer UV-1 0.075 UV-2 0.075 Oxidized developer scavenger DOXS-3 0.162 Compensated print density cyan dye CD-1 0.020 Compensated print density magenta dye. MD-2 0.042 Compensation print density yellow dye MM-1 0.088 Compensation print density yellow dye YD-2 0.008 HBS-1 0.426 HBS-5 0.151 3,5-di-sulfocatechol Sodium salt 0.270 Gelatin 2.441 Black colloidal silver sol 0.151

Layer 2: Low Sensitivity Red Sensitive Layer This layer is a slower, red sensitized tabular silver iodobromide emulsion [1.3 mol% iodide, average grain diameter 0.53 μm and thickness 0. 0.09 μm] and a more sensitive formulation of a red-sensitized tabular silver iodobromide emulsion [4.1% iodide, average grain diameter 1.04 μm and thickness 0.09 μm]. Low speed emulsion 0.495 High speed emulsion 0.431 Bleach accelerator coupler BAR-1 0.038 Cyan dye forming coupler C-1 0.517 Cyan dye forming magenta colored coupler CM-1 0.027 Oxidized developing agent scavenging Agent DOXS-2 0.010 HBS-2 0.517 HBS-3 0.038 TAI 0.015 Gelatin 1.775

Layer 3: Medium speed red sensitive layer Red sensitized tabular silver iodobromide emulsion [4.1 mol% iodide, average grain diameter 1.39 μm and thickness 0.12 μm]. Emulsion 0.700 DIR coupler D-5 0.011 Cyan dye forming magenta colored coupler CM-1 0.022 Cyan dye forming coupler C-1 0.215 HBS-2 0.215 HBS-4 0.022 TAI 0.011 Gelatin 1.786

Layer 4: High-sensitivity red-sensitive layer Red-sensitized tabular silver iodobromide emulsion [4.1 mol% iodide, average grain diameter 2.93 μm and thickness 0.13 μm]. Emulsion 1.076 DIR coupler D-5 0.020 DIR coupler D-6 0.048 Cyan dye forming magenta colored coupler CM-1 0.032 Cyan dye forming coupler C-1 0.139 HBS-1 0.194 HBS- 2 0.139 HBS-4 0.041 TAI 0.010 gelatin 1.711

Layer 5: Intermediate gelatin 1.292

Layer 6: Low Sensitivity Green Sensitive Layer This layer is a slower, green sensitized tabular silver iodobromide emulsion [1.3 mol% iodide, average grain diameter 0.53 μm and thickness 0. 0.09 μm] and higher sensitivity green sensitized tabular silver iodobromide emulsions [4.1% iodide, mean grain diameter 1.04 μm and thickness 0.09 μm]. Low speed emulsion 0.581 High speed emulsion 0.312 Magenta dye forming yellow colored coupler MM-2 0.065 Magenta dye forming coupler M-4 0.269 Oxidized developing agent scavenger DOXS-2 0.023 HBS-1 0.345 TAI 0.014 Gelatin 1.723

Layer 7: Medium sensitivity green sensitive layer Green sensitized tabular silver iodobromide emulsion [4.1 mol% iodide, average grain diameter 1.23 μm and thickness 0.12 μm]. Emulsion 0.969 DIR coupler D-5 0.024 Magenta dye forming yellow colored coupler MM-2 0.065 Magenta dye forming coupler M-4 0.070 Oxidized developing agent scavenger DOXS-2 0.019 HBS-1 0.186 HBS-4 0.048 TAI 0.014 Gelatin 1.399

Layer 8: Highly sensitive green-sensitive layer Green sensitized tabular silver iodobromide emulsion [4.1 mol% iodide, average grain diameter 2.19 μm and thickness 0.13 μm]. Emulsion 0.969 DIR coupler D-3 0.011 DIR coupler D-7 0.011 Magenta dye forming yellow colored coupler MM-2 0.054 Magenta dye forming coupler M-4 0.058 Oxidized developing agent scavenger DOXS -0.016 HBS-1 0.176 HBS-2 0.011 TAI 0.012 Gelatin 1.291

Layer 9: Yellow filter layer Yellow filter dye YD-1 0.108 gelatin 1.292

Layer 10: Low Sensitivity Blue Sensitive Layer This layer is a slower, blue sensitized tabular silver iodobromide emulsion [1.3 mol% iodide, average grain diameter 0.53 μm and thickness 0. 0.09 μm], medium-sensitivity, tabular blue-sensitized silver iodobromide emulsion [4.1 mol% iodide, average grain diameter 0.80 μm and thickness 0.09 μm], and higher sensitivity, tabular blue A formulation of a sensitized silver iodobromide emulsion [6.0% iodide, mean grain diameter 0.96 μm and thickness 0.26 μm] is included. Low-speed emulsion 0.269 Medium-speed emulsion 0.172 High-speed emulsion 0.549 DIR coupler D-8 0.065 Yellow dye-forming coupler Y-1 0.280 Yellow dye-forming coupler Y-2 0.700 Bleach accelerator coupler BAR-1 0.003 Cyan dye forming coupler C-1 0.027 Oxidized developer scavenger DOXS-2 0.005 HBS-2 0.931 HBS-3 0.003 TAI 0.016 Gelatin 2.519

Layer 11: High-sensitivity blue-sensitive layer This layer comprises a lower-sensitivity, blue-sensitized tabular silver iodobromide emulsion [9.0 mol% iodide, average grain diameter 1.06 μm] and higher. Contains a sensitive, tabular blue sensitized silver iodobromide emulsion [4.1% iodide, mean grain diameter 3.37 μm and thickness 0.14 μm]. Low-speed emulsion 0.226 High-speed emulsion 0.570 Yellow dye-forming coupler Y-1 0.080 Yellow dye-forming coupler Y-2 0.200 DIR coupler D-8 0.048 Bleach accelerator coupler BAR-1 0.005 Cyan dye-forming coupler C-1 0.029 Oxidized developer scavenger DOXS-2 0.001 HBS-2 0.317 HBS-3 0.005 TAI 0.013 Gelatin 1.580

Layer 12: UV filter layer Dye UV-1 0.108 Dye UV-2 0.108 Unsensitized silver bromide Lippmann emulsion 0.215 HBS-5 0.215 Gelatin 0.699

Layer 13: Protective overcoat layer Polymethylmethacrylate matte beads 0.005 Soluble polymethylmethacrylate matte beads 0.054 Silica gel particles 0.108 Silicone lubricant 0.039 Gelatin 0.888

These films were treated with 1.7% of total gelatin.
The film was hardened with a coating film containing 5% by weight of the hardener H-2. Surfactant, coating aid, soluble absorber dye and stabilizer,
The various layers of this sample were added as is commonly practiced in the art. Photographic Sample 502 (Comparative Control) A color photographic recording material for color negative development was prepared exactly as Sample 501 above except as described below. The cyan dye-forming coupler C-1 used in Red Sensitive Layers 2, 3 and 4 was prepared according to Dispersion Example 1 without the presence of a high boiling solvent.
Generally dispersed as in Example P of 0.

Layer 2: Low sensitivity red sensitive layer modified portion HBS-2 0.000 Layer 3: Medium sensitivity red sensitive layer modified portion HBS-2 0.000 Layer 4: High sensitivity red sensitive layer modified portion HBS-2 0. 000

Photographic Sample 503 (Comparison Control) A color photographic recording material for color negative development was prepared exactly as Sample 502 above except as described below. Generally dispersed H, such as Dispersion R of Example 10
Another dispersion of BS-1 is added to the liquid coating solution of red-sensitive layers 2, 3 and 4 containing coupler C-1 generally dispersed as Dispersion P of Dispersion Example 10 to produce a cyan dye. It gave the same coverage (weight) as coupler C-1.

Layer 2: Low sensitivity red sensitive layer modified portion HBS-1 0.517 HBS-2 0.000 Layer 3: Medium sensitivity red sensitive layer modified portion HBS-1 0.215 HBS-2 0.000 Layer 4: High-sensitivity red-sensitive layer modified portion HBS-1 0.334 HBS-2 0.000 Photographic sample 504 (comparative control) Exactly the same as sample 502 except that a color photographic recording material for color negative development was described below. Was prepared as follows. Generally dispersed H, such as dispersion Q of Example 10
Layers 2, 3 containing coupler C-1 with another dispersion of BS-2 generally dispersed as Dispersion P of Dispersion Example 10.
And 4 in addition to the liquid coating solution to give a 25% coverage (by weight) of cyan dye-forming coupler C-1.

Layer 2: Low sensitivity red sensitive layer modified portion HBS-2 0.129 Layer 3: Medium sensitivity red sensitive layer modified portion HBS-2 0.054 Layer 4: High sensitivity red sensitive layer modified portion HBS-2 0. 035 Photographic Sample 505 (Comparison Control) A color photographic recording material for color negative development was prepared exactly as Sample 502 above except as described below. Generally dispersed H, such as dispersion Q of Example 10
Layers 2, 3 and 4 containing coupler C-1 with another dispersion of BS-2 generally dispersed as in dispersion P of Example 10.
Of the cyan dye-forming coupler C-1 to give 50% coverage (by weight) of the cyan dye-forming coupler C-1.

Layer 2: Low sensitivity red sensitive layer modified portion HBS-2 0.258 Layer 3: Medium sensitivity red sensitive layer modified portion HBS-2 0.108 Layer 4: High sensitivity red sensitive layer modified portion HBS-2 0. A 070 photographic sample 506 (comparative control) color photographic recording material for color negative development was prepared exactly as Sample 502 above except as described below. Generally dispersed H, such as dispersion Q of Example 10
Layers 2, 3 and 4 containing coupler C-1 with another dispersion of BS-2 generally dispersed as in dispersion P of Example 10.
And the same coating weight (weight) as cyan dye-forming coupler C-1.

Layer 2: Low sensitivity red sensitive layer modified portion HBS-2 0.517 Layer 3: Medium sensitivity red sensitive layer modified portion HBS-2 0.215 Layer 4: High sensitivity red sensitive layer modified portion HBS-2 0. 139 Photographic Sample 507 (Invention) A color photographic recording material for color negative development was prepared exactly as Sample 502 above except as described below. Another dispersion of the high boiling solvent HBS-6 (formula III-5), generally dispersed, such as dispersion T of Example 10, was prepared as in Example 1.
A generally dispersed coupler C-, such as dispersion P of 0
1 was added to the liquid coating solution of Layers 2, 3 and 4 to give a coverage (weight) of 25% of cyan dye-forming coupler C-1.

Layer 2: Low sensitivity red sensitive layer modified portion HBS-6 0.129 HBS-2 0.0 Layer 3: Medium sensitivity red sensitive layer modified portion HBS-6 0.054 HBS-2 0.0 Layer 4: High-sensitivity red-sensitive layer modified portion HBS-6 0.035 HBS-2 0.0

Photographic Sample 508 (Invention) A color photographic recording material for color negative development was prepared exactly as Sample 502 above except as described below. Another dispersion of the high boiling solvent HBS-6, which was generally dispersed such as Dispersion T of Example 10, was mixed with Dispersion P of Example 10.
Was added to the liquid coating solutions of Layers 2, 3 and 4 with coupler C-1 generally dispersed as described above to give a coverage (weight) of 50% of cyan dye-forming coupler C-1.

Layer 2: Low sensitivity red sensitive layer modified portion HBS-6 0.258 HBS-2 0.0 Layer 3: Medium sensitivity red sensitive layer modified portion HBS-6 0.108 HBS-2 0.0 Layer 4: High-sensitivity red-sensitive layer modified part HBS-6 0.070 HBS-2 0.0

Photographic Sample 509 (Invention) A color photographic recording material for color negative development was prepared exactly as Sample 502 above except as described below. Another dispersion of the high boiling solvent HBS-7 (formula V-1), generally dispersed, such as dispersion U of Example 10, was prepared as in Example 10
C-1 which is generally dispersed, such as dispersion P of
To the liquid coating solution of layers 2, 3 and 4 containing
A 25% coverage (by weight) of cyan dye-forming coupler C-1 was provided.

Layer 2: Low sensitivity red sensitive layer modified portion HBS-7 0.129 HBS-2 0.0 Layer 3: Medium sensitivity red sensitive layer modified portion HBS-7 0.054 HBS-2 0.0 Layer 4: High-sensitivity red-sensitive layer modified part HBS-7 0.035 HBS-2 0.0

Photographic Sample 510 (Invention) A color photographic recording material for color negative development was prepared exactly as Sample 502 above except as described below. Another dispersion of the high boiling solvent HBS-7, which was generally dispersed as Dispersion U of Example 10, was mixed with Dispersion P of Example 10.
Was added to the liquid coating solutions of Layers 2, 3 and 4 with coupler C-1 generally dispersed as described above to give a coverage (weight) of 50% of cyan dye-forming coupler C-1.

Layer 2: Low sensitivity red sensitive layer modified portion HBS-7 0.258 HBS-2 0.0 Layer 3: Medium sensitivity red sensitive layer modified portion HBS-7 0.108 HBS-2 0.0 Layer 4: High-sensitivity red-sensitive layer modified portion HBS-7 0.070 HBS-2 0.0

Photographic Sample 511 (Invention) A color photographic recording material for color negative development was prepared exactly as Sample 502 above except as described below. Liquid coating solution of layers 2, 3 and 4 comprising coupler C-1 with another dispersion of the high boiling solvent HBS-8 (formula IV-1) generally dispersed as in dispersion P of Example 10. In addition, it gave a coverage (weight) of 25% of cyan dye-forming coupler C-1.

Layer 2: Low sensitivity red sensitive layer modified portion HBS-8 0.129 HBS-2 0.0 Layer 3: Medium sensitivity red sensitive layer modified portion HBS-8 0.054 HBS-2 0.0 Layer 4: High-sensitivity red-sensitive layer modified portion HBS-8 0.035 HBS-2 0.0

Photographic Sample 512 (Invention) A color photographic recording material for color negative development was prepared exactly as Sample 502 above except as described below. Another dispersion of the high boiling solvent HBS-8 was added to the liquid coating solution of Layers 2, 3 and 4 containing coupler C-1 generally dispersed as in Dispersion P of Example 10 to produce a cyan dye. 50% coverage of coupler C-1 (weight)
Was given.

Layer 2: Low sensitivity red sensitive layer modified portion HBS-8 0.258 HBS-2 0.0 Layer 3: Medium sensitivity red sensitive layer modified portion HBS-8 0.108 HBS-2 0.0 Layer 4: High-sensitivity red-sensitive layer modified portion HBS-8 0.070 HBS-2 0.0

Photographic Sample 513 (Invention) A color photographic recording material for color negative development was prepared exactly as Sample 502 above except as described below. Another dispersion of the high boiling solvent HBS-9 (Formula II-1), generally dispersed, such as Dispersion S of Example 10, was prepared as in Example 10
C-1 which is generally dispersed, such as dispersion P of
To the liquid coating solution of layers 2, 3 and 4 containing
A 25% coverage (by weight) of cyan dye-forming coupler C-1 was provided.

Layer 2: Low-sensitivity red-sensitive layer modified portion HBS-9 0.129 HBS-2 0.0 Layer 3: Medium-sensitivity red-sensitive layer modified portion HBS-9 0.054 HBS-2 0.0 Layer 4: High sensitivity red sensitive layer change part HBS-9 0.035 HBS-2 0.0

Photographic Sample 514 (Invention) A color photographic recording material for color negative development was prepared exactly as Sample 502 above except as described below. Another dispersion of the high boiling solvent HBS-9, which was generally dispersed as Dispersion S of Example 10, was mixed with Dispersion P of Example 10.
Was added to the liquid coating solutions of Layers 2, 3 and 4 with coupler C-1 generally dispersed as described above to give a coverage (weight) of 50% of cyan dye-forming coupler C-1.

Layer 2: Low-sensitivity red-sensitive layer modified portion HBS-9 0.258 HBS-2 0.0 Layer 3: Medium-sensitivity red-sensitive layer modified portion HBS-9 0.108 HBS-2 0.0 Layer 4: High-sensitivity red-sensitive layer modified part HBS-9 0.070 HBS-2 0.0

Photographic recording material samples 501-514 were
Gradual zero to determine its speed and gamma
~ 4.0 Density step through tablet 5500K
Filtered by Daylight Va filter against 3
Each was exposed to white light from a tungsten light source having a color temperature of 200 K for 1/500 seconds. The samples were then processed using Color Negative Kodak C-41.

After processing and drying, samples 501-51
4 was subjected to Status M densitometry. The photographic performance of these recording materials is compared in Table XI below.

[0228]

[Table 11]

Photographic data for sample 502 is shown in Example 501.
After direct replacement of the comparative control dispersion using HBS-2 (di-n-butyl phthalate) in a weight ratio of 1.0 to C-1 of the high, medium and low speed red sensitive layers of the color negative recording material of , A dispersion of the cyan dye-forming coupler C-1 of the present invention, which does not contain a high boiling solvent, provides very low gamma and upper scale density producing ability. Sample 5
The photographic data for Example 03 shows that a comparative high boiling solvent (HBS-1) in the art was a solvent-free dispersion of a cyan dye-forming coupler C-1 at a weight ratio of 1.0 when preparing a liquid coating solution. It is shown to give poor sensitometric response when mixed.

Comparative Control Examples 504 and 505 have significantly lower gamma and upper scale density producing ability, and are the C of the high, medium and slow red sensitive layers of the color negative recording material of Example 501.
-1, as a result of subtracting the amount of HBS-2 from a control dispersion using HBS-2 in a weight ratio of 1.0 to -1. Comparative Control Example 506 gave substantially the same results as Example 501, in solvent-free dispersions of coupler C-1 and high boiling solvent HBS- in liquid coating solutions of low, medium and high speed red sensitive layers. It is shown that when mixed with the two dispersions, a normal ratio of 1.0 yields almost the same performance as producing a general dispersion of C-1 and HBS-2.

0.25 or 0.5 for the coupler
High boiling point solvents HBS-6, HBS-7, HBS- at a ratio of 0
8 or all of the examples of the present invention using HBS-9 (5
07-514) gives an overall superior photographic performance of the gamma position and maximum density of this characteristic curve compared to the prior art solvent HBS-2 under the same conditions of use. In fact, the solvents HBS-6 and HBS- mixed with C-1
8 and HBS-9 are solvent / C-1 weight ratio 0.50.
In Comparative Control Example 506, the H
It provides the same or better gamma and density generation capabilities as BS-2 does.

HBS-1 tricresyl phosphate HBS-2 di-n-butyl phthalate HBS-3 N, N-diethyllauramide HBS-4 Nn-butylacetanilide HBS-5 1,4-cyclohexylene dimethylene bis (2-Ethylhexanoate) HBS-6 oleyl alcohol (Formula III-5) HBS-7 Phenylethylbenzoate (Formula V-1) HBS-8 p-dodecylphenol (Formula IV-1) HBS-9 di-n -Butyl sebacate (Formula II-1)

[0233]

[Chemical formula 24]

[0234]

[Chemical 25]

[0235]

[Chemical formula 26]

[0236]

[Chemical 27]

[0237]

[Chemical 28]

[0238]

[Chemical 29]

[0239]

Embedded image

[0240]

[Chemical 31]

[0241]

Embedded image

[0242]

[Chemical 33]

H-1 Bis (vinylsulfonyl) methyl ether H-2 Bis (vinylsulfonyl) methane CHEM-1 poly (2,2′-thiodiethylene glutarate) TAI 4-hydroxy-6-methyl-1,3 Three
a, 7-Tetraazaindene

[0244]

The present invention reduces dispersion crystallization of a substantially permanent solvent-free dispersion of a particular class of cyan coupler. The improved stability is seen with a single type of coupler, contrary to the requirement to use a mixture of more than one coupler. In the present invention, dispersions can be prepared at very high concentrations without the need for the use of steric stabilizers commonly required for precipitation dispersion techniques. Further, the invention is not limited by the type of emulsion that can be used with it.

In addition, the dry thickness applied using a specific phenolic cyan coupler with a minimum level of high boiling organic solvent is thinned, while at the same time higher when processed when the dispersion is used in coupler overloaded multilayer structures. To obtain dye density, it is possible to produce a silver halide light-sensitive photographic material which maintains high coupler reactivity in the photographic material and avoids the coupler crystallization problems exhibited by low solvent dispersions of these couplers. It is possible with the present invention.

It has been unexpectedly found that the coupler solvents used in the present invention are low levels of coupler solvents and provide relatively high coupler reactivity with certain phenolic cyan couplers. Dispersing the cyan coupler of the present invention in a low level of the coupler solvent of the present invention,
It has also been found that it may lead to terrible crystallization problems. However, these problems are avoided by preparing separate dispersions of these cyan couplers and high boiling organic solvents and then mixing the dispersions in the coating solution.

[Brief description of drawings]

1 is a graph showing the filterability of Dispersions I and H described in Example 2. FIG.

FIG. 2 is a graph showing the filterability of Dispersions J and L described in Example 4.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Ronda Ellen Factor New York, USA 14612, Rochester, Applewood Drive 260

Claims (3)

[Claims] 1. A photographic element comprising a support having a hydrophilic colloid layer comprising a phenolic cyan coupler of formula I and a high boiling organic solvent of formula II, III, IV or V, wherein the coupler of formula I A silver halide light-sensitive color photographic element in which the weight ratio of the high boiling point organic solvent of formulas II, III, IV and V to the weight in the hydrophilic colloid layer is 0.1 to 0.5. ] (In the formula, R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group, R ₃ represents a hydrogen atom, a halogen atom, an aliphatic group, or an acylamino group, and X represents , A hydrogen atom or a group that can be released during the coupling reaction with the oxidation product of the developing agent, and n represents 0 or 1); (In the formula, R ₄ and R ₅ each represent an alkoxycarbonyl group having 8 or less carbon atoms, and m is an integer of 1 to 10); (In the formula, R ₆ represents an alkyl group or an alkenyl group, and R ₇ and R ₈ are independently a moiety group selected from hydrogen and R ₆ , but R ₆ , R ₇ , and R 8 The total number of carbon atoms contained in ₈ is at least 10); (Wherein, R ₉ and R ₁₀ is a hydrogen or a linear or branched alkyl group, at least one of R ₉ or R ₁₀ is an alkyl group of straight or branched chain, R ₉
And the total carbon number of the combined R ₁₀ is 9-20, and R ₁₀ is in para or meta position with respect to the phenolic hydroxyl group); embedded image (In the formula, R ₁₁ represents an aliphatic group, an aromatic group, or a heterocyclic group, and R ₁₂ represents a hydrogen atom, a hydroxy group,
Represents an alkoxy group or an aliphatic group). 2. A photographic element according to claim 1, wherein n is 1. 3. Dissolving the coupler of formula I according to claim 1 in a cosolvent; dispersing the cosolvent and the dissolved coupler in an aqueous gelatin solution substantially free of permanent organic solvent. And a method of making a dispersion comprising particles of a phenolic cyan photographic coupler dispersed in an aqueous medium and resistant to undesired crystal growth, comprising removing the cosolvent from the dispersion.