GB2301444A - Photographic elements comprising cyan coupler dispersions - Google Patents

Description

2301444 Photographic Elements Comprising Cyan Coupler Dispersions With

Improved Stability And Increased Activity

Field of the Invention

This invention relates to dispersions of phenolic cyan dye-forming photographic couplers prepared without any permanent organic coupler solvent. This invention additionally relates to silver halide photographic materials and methods of making such materials,and more specifically to photographic materials comprising dispersions of specific phenolic cyan dye-forming photographic couplers and limited amounts of specific high boiling organic solvents.

Background of the Invention

In the design of silver halide lightsensitive multilayer photographic materials, it is desirable to minimize the dry thickness of the coated layers. Layer thinning is advantageous for reasons such as improved image sharpness due to reduced light scattering during exposure and increased developability due to shorter diffusion paths through the multilayer structure. This increase in developability can lead to lower silver and/or coupler coated levels, hence lower materials cost.

Photographic dye-forming couplers, as well as other hydrophobic photographically useful compounds, are generally incorporated into a layer of a photographic element by first forming an,aqueous dispersion of the couplers and then mixing such dispersion with the layer coating solution. An organic solvent is generally used to dissolve the coupler, and the resulting organic solution is then dispersed in an aqueous medium to form the aqueous dispersion.

The organic phase of these dispersions frequently includes high-boiling or permanent organic f solvents. Permanent high boiling solvents have a boiling point sufficiently high, generally above 150'C at atmospheric pressure, such that they are not evaporated under normal dispersion making and photographic layer coating procedures. Permanent highboiling coupler solvents are primarily used in the conventional "oil-protection" dispersion method whereby the organic solvent remains in the dispersion, and thereby is incorporated into the emulsion layer coating solution and ultimately into the photographic element.

in order to reduce the coated thickness of photographic layers, it is essential to minimize the amount of permanent coupler solvent coated in the element. In fact, reductions in coupler solvent level also afford concomitant reductions in gelatin level which leads to further reductions in coated dry thickness. U.S. Patent 5,173,398, e.g., discloses photographic elements with coupler-containing layers having substantially no high-boiling solvent, wherein the couplers are incorporated in the layer in the form of precipitated dispersions. However, coupler solvent reduction can also result in excessive crystallization of the dispersed organic compounds in an aqueous dispersion or coating solution with photographic compounds that have a tendency to crystallize. These crystallization problems can cause filter-plugging during the manufacture of photographic materials or may result in physical defects in the coated product. Another difficulty with coupler solvent reduction is that the reactivity of the dispersed photographically useful chemical, such as a dye-forming coupler, may be reduced to a level below that which would produce desired dye density upon processing of the photographic material.

Dispersions of photographic couplers made without using permanent coupler solvent are well-known in the art. Such dispersions are generally made with auxiliary solvents which are removed from the dispersion prior to coating. Auxiliary solvents may be water immiscible, volatile solvents, or solvents with limited water solubility which are not completely water miscible. In fact, there are many photographic compounds which can be dispersed with or without permanent solvent with no crystallization problems, as noted in U. S. Patent 2,801,170. However, when the dispersed photographic compound is prone to crystallization, the tendency to crystallize generally becomes greater as the amount of coupler solvent, relative to coupler, is decreased, as noted in U.S.

Patents 4,419,441 and 5,112,729.

Phenolic cyan dye forming couplers are well known in the art, and are known to be very prone to crystallization. Due to their crystalline nature, these couplers are often dispersed as mixtures of two or more couplers to avoid crystallization problems, as described in U.S. Patent 4,885,234 and EP 434,028. However, use of these methods requires the synthesis of an additional photographic coupler which results in an increase in manufacturing cost. In order to achieve adequate coupler reactivity, phenolic cyan dye-forming couplers are commonly dispersed with high-boiling organic solvents as described in U.S. Patent 4,333,999, U.S. Patent 4, 609, 619, EP 097, 042, EP 102, 839, EP 389, 817, DE 3,624,777, DE 3,700,570, and DE 3,936,300. It is also well-known, as mentioned in U.S. Patent 2,801,170, that coupler solvent reduction can result in reduced coupler reactivity. This reference also teaches the concept of combining a solvent-free coupler dispersion with a dispersion of a high boiling coupler solvent.

U.S. Patent 5,112,729 describes a photographic material containing a cyan naptholic coupler and a highboiling solvent present in a weight ratio with respect c r 1.

to the coupler in the layer of not more than 0.3. While a variety of possible solvents is disclosed, the use of a phosphoric acid ester and a phthalic acid ester is said to be preferred for use with these couplers.

Methods of increasing the dye yield of oil-free cyan coupler dispersions are disclosed in Research Disclosure 14532 (May, 1976). The specific cyan couplers described in these references fall outside the scope of the present invention. Crystallization of phenolic cyan couplers is also discussed in EP 361,924.

It would be desirable to provide a coupler dispersion which contains no permanent solvent which exhibits good stability toward crystallization and provides adequate coupler reactivity when coated in a silver halide light-sensitive photographic material. It would be further desirable to provide silver halide photographic elements made from solvent-free dispersions of specific phenolic cyan couplers which exhibit improved stability to crystallization, while achieving high coupler reactivity in the photographic material,.in order to obtain higher dye densities upon processing when such dispersions are used in couplerrich multilayer structures. It is further desirable to achieve a reduction in the coated level of coupler solvent in such elements to decrease.coated dry thickness. It is toward these ends that the present invention is directed.

Summary of the Invention

An object of the present invention is to provide a dispersion of a phenolic cyan coupler with improved stability to dispersion crystallization following extended cold storage. A further object of the present invention is to provide a coating solution for a silver halide photographic light-sensitive material containing a phenolic cyan coupler dispersion which exhibits improved stability to crystallization upon extended melt hold time.

Another object of the present invention is to provide a silver halide photographic light-sensitive material with reduced coated dry thickness. Another object of the present invention is to provide a silver halide photographic material having high cyan coupler reactivity to obtain satisfactory cyan dye density upon processing of the photographic material. A further object of the invention is to provide photographic materials possessing such properties which are made from cyan coupler dispersions with improved stability to crystallization following extended cold storage.

The above objects of the invention are attained by providing a silver halide photographic light-sensitive material comprising a support having coated thereon a coupler dispersion containing layer comprising a specific class of phenolic cyan dye forming couplers and a limited amount of specific high boiling organic solvents.

in accordance with one embodiment of the invention, a dispersion is disclosed comprising particles of a phenolic cyan photographic coupler of Formula I dispersed in an aqueous gelatin solution substantially free of permanent organic solvent:

OH 0 R3 NEC(NH)nRI R2CE14 11 # 0 X Formula I wherein Rl and R2 each represent an aliphatic group, an aromatic group, or a heterocyclic group; R3 represents a hydrogen atom, a halogen atom, an aliphatic group, or an acylamino group; X represents a hydrogen atom or a group capable of being released upon a coupling reaction with oxidation product of a developing agent; and n represents. 0 or 1. The dispersions of the invention are preferably formed by dissolving a coupler of Formula I in an auxiliary solvent, dispersing the auxiliary solvent and dissolved coupler in an aqueous gelatin solution, and removing the auxiliary solvent from the dispersion. Silver halide color photographic light sensitive materials may be prepared by performing the steps of a) dispersing a coupler of Formula I in an aqueous gelatin solution substantially free of permanent organic solvent; b) preparing an aqueous coating solution comprising the dispersion resulting from a); and c) coating the solution resulting from b) on a photographic support.

In accordance with another embodiment of the invention, a method of making a silver halide color photographic light sensitive material is disclosed comprising: (a) preparing a first dispersion of a phenolic cyan coupler of Formula I dispersed in an aqueous medium; (b) preparing a second dispersion of a high-boiling organic solvent having Formula II, III, IV, V or combinations thereof dispersed in an aqueous medium:

R,r- (CH 2)-F- R5 Formula 11 wherein R4 and R5 each represent an alkoxycarbonyl group containing not more than 8 carbon atoms, and m is an integer from 1 to 10; R7 1 Rj-f -OH Formula Ill R8 wherein R6 represents an alkyl group or an alkenyl group, and R7 and R8 are individually selected from hydrogen and the group of moieties from which R6 is selected, provided that the total number of carbon atoms contained in R6, R7, and R8 is at least 10; R9 OH Formula IV Rio wherein R9 and R10 are hydrogen or straight chain or branched chain alkyl groups, at least one of R9 or R10 being a straight chain or branched chain alkyl group, the total number of carbon atoms in R9 plus Rjo being from 9 to 20, and R10 being in the para or meta position with respect to the phenolic hydroxyl group; OR,, 1 R12 Formula V wherein R11 represents an aliphatic group, an aromatic group, or a heterocyclic group, and R12 represents a hydrogen atom, a hydroxy group, an alkoxy group, or an aliphatic group; (c) combining said first and second dispersions in an aqueous coating solution, wherein the weight ratio in said coating solution of high-boiling organic solvent of formula II, III, IV and V relative to coupler of formula I is from 0.1 to 0.5; and (d) coating said coating solution on a photographic support.

In accordance with a further embodiment of the invention, a silver halide color photographic light sensitive material is disclosed comprising a support bearing a layer comprising a coupler of formula I and a highboiling organic solvent of formula II, III, IV or V, wherein the weight ratio in said layer of highboiling organic solvent of formula II, III, IV or V relative to coupler of formula I is from 0.1 to 0.5.

Advantages The present invention provides reduced dispersion crystallization for substantially permanent solvent-free dispersions of a specific class of cyan couplers. The improved stability is observed with single couplers as opposed to requiring the use of mixtures of more than one coupler. In the present invention, dispersions can be prepared at much higher concentrations without the use of a steric stabilizer which are generally required for precipitation dispersion techniques. In addition, the present invention is not restricted by the type of emulsion it can be used with.

Additionally, it is possible with the present invention to produce a silver halide light-sensitive photographic material which employs specific phenolic cyan couplers with a minimal level of high-boiling organic solvent to reduce coated dry thickness while maintaining high coupler reactivity to obtain desired dye density upon processing the photographic material and avoiding coupler crystallization problems exhibited by low solvent dispersions of these couplers.

The coupler solvents employed in the present invention have unexpectedly been found to provide relatively higher coupler reactivity with specific phenolic cyan couplers at low levels of coupler solvent. It has also been found that dispersing the cyan couplers of the present invention in low levels of the coupler solvents of the present invention may lead to severe crystallization problems. However, these problems are avoided by preparing separate dispersions of these cyan couplers and of the high-boiling organic solvents, and then combining such dispersions in a coating solution.

Brief Description of the Drawings

Fig 1 is a graph depicting the filterability results of Dispersions I and H as described in Example 2.

Fig 2 is a graph depicting the filterability results of Dispersions J and L as described in Example 4.

Detailed Description of the Invention

In the cyan coupler represented by Formula I, Rl and R2 each represents an aliphatic group (preferably an aliphatic group having from 1 to 32 carbon atoms, e.g., methyl, butyl, dodecyl, cyclohexylallyl), an aryl group (e.g., phenyl, naphthyl) or a heterocyclic group (e.g., 2-pyridyl, 2-imidazolyl, 2-furyl, 6-quinolyl). It is understood throughout this specification that any reference to a substituent by the identification of a group containing a substitutable hydrogen, unless otherwise specifically stated, shall encompass not only the substituent's unsubstituted form, but also its form substituted with any other photographically useful substituents. For example, each such substitutable group can be substituted with one or more photographically acceptable substituents, such as those selected from an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (e.g., methoxy, 2methoxyethoxy), an aryloxy group (e.g., 2,4-di-tert-amyl phenoxy, 2-chlorophenoxy, 4-cyanophenoxy), an alkenyloxy group (e.g., 2-propenyloxy), an acyl group (e.g., acetyl, benzoyl), an ester group (e.g., butoxycarbonyl, phenoxycarbonyl, acetoxy, benzoyloxy, butoxysulfonyl, toluenesulfonyloxy), an amido group (e.g., acetylamino, methane sul f onyl amino, dipropylsul f amoyl amino), a carbamoyl group (e.g., dimethylcarbamoyl, ethylcarbamoyl), a sulfamoyl group (e.g., butylsulfamoyl), an imido group (e.g., succinimido, hydantoinyl), a ureido group (e.g., phenylureido, dimethylureido), an aliphatic or aromatic sulfonyl group (e.g., methanesulfonyl, phenylsulfonyl), an aliphatic or aromatic thio group (e.g., ethylthio, phenylthio), a hydroxy group, a cyano group, a carboxy group, a nitro group, a sulfo group, and a halogen atom. Usually the substituent will have less than 30 carbon atoms and typically less than 20 carbon atoms.

R3 represents a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, or an acylamino group. When R3 in Formula I represents a substituent which can be substituted per se, it may be further substituted with one or more substituents selected from those as described for Rl and R2 above.

In Formula 1, X represents a hydrogen atom or a coupling off group capable of being released upon coupling. Examples of the groups capable of being released upon coupling include a halogen atom (e.g., fluorine, chlorine, bromine), an alkoxy group (e.g., ethoxy, dodecyloxy, methoxycarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy) an aryloxy group (e.g., 4-chlorophenoxy, 4-methox-yphenoxy, 4carboxyphenoxy), an acyloxy group (e.g., acetoxy, tetradecanoyloxy, benzoyloxy), a sulfonyloxy group (e.g., methanesulfonyloxy, toluenesulfonyloxy), an amido group (e.g., dichloroacetylamino, heptafluorobutyrylamino, methanesulfonylamino, toluenesulfonylamino), an alkoxy carbonyloxy group (e.g., ethoxycarbonyloxy, benzyloxycarbonyloxy), an aryloxycarbonyloxy group (e.g., phenoxycarbonyloxy), an aliphatic or aromatic thio group (e. g., ethylthio, phenylthio, tetrazolythio, mercaptopropionic acid), an imido group (e.g., succinimido, hydantoinyl), a sulfonamido, group and an aromatic azo group (e.g., phenylazo). These coupling-off groups are described in the art, for example, in U.S. Patent Nos. 2,455,169, 3,227,551, 3,432,521, 3,476,563, 3,617,291, 3,880,661, 4,052,212 and 4,134,766; and in U.K. Patents and published application Nos. 1,466,728, 1,531,927, 5 1,533,039, 2,006,755A and 2,017,704A. These groups may contain a photographically useful group. In Formula I, Rl is preferably an aryl group or a heterocyclic group. More preferred is an aryl group substituted with one or more substituents selected from a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamido group, a sulfamoyl group, a sulfonyl group, a sulfamido group, an oxycarbonyl group and a cyano, group. Most preferred is an aryl group substituted with one or more halogen or cyano substituents.

In Formula I, R2 is preferably an alkyl group or an aryl group, more preferably an alkyl group substituted with an aryloxy group, and R3 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 sulfonamido group. Also preferred is where n is 1. In a specific preferred embodiment of the invention, n is 1 and X is hydrogen atom, a halogen atom, or an aryloxy group in Formula I.

Preferred examples of the cyan couplers represented by Formula I according to the present invention will now be set forth below, but the present invention should not be construed as being limited thereto.

C-1 OH 0 11 C!Snll-t 5p, NWNH-O-W 0 t-H1IC5-j OC=Ht C4Hg-n c-4 c-5 c-6 C-7 on 0 C5Ell-t 0 COCECNE t-H-1.9 Cc_---J 11.1 C5Ell-t 0 11 t-HIlcs OCEME C4R9 -n cl 1 C'ARg-n cl OR 0 11 C5Ell-t 5p, -CN CN t-Rllc!s- OCEME C4R9 -n OR 0 11 NHCNE-' -CN -, e.,, ' l W OR 0 11 C5H11-t NECM-C- -CN 0 -COCEME t -a, 1 cc- f CN 1 C12E25 cl 0 11 OR C5Ell t NBCM-C- -M 0 t-Ellcs---. OCKMat C09-n cl 0 11 OR NEWE cl C5Rll-t 0 OCIRMH C4Hg-n CN C-9 C-10 C-11 C-12 C-13 on 0 11 NHCNE-C -cl CSE2.1L-t 0 11 t-Ell.CS OCEME 0 -c 1 11 C,&Hg -n 2COCII3 OR 0 11 NECC3r7 C5Ell-t.

0 t-H1lcs OCEME W on 0 11 NW-0 t-Ellcs -0-OCHCNH"" 1 -;12J125 OR 0 11 0 1 NWNH-0-M 11 t-Hilcs O-CHCHN C5H11-t 0 1 C 3 OR 0 11 0 NECNE-0-M H3C CHCRCEN"'C E3C 1 S02C16B33 OR 0 11 NECNE-0-M H3C, 101 CECECHN E3C 1 S02C14H29 C-14 C-15 C-16 on 0 11 E3C 0 NECNE-O-CN CECECEN E3C 1 21;UJM29 0 H3C C2ES H HCNH -Q- M Rkk 1 1 cl t-HI1C OfHCNH -,y C12H25 H J_0 H9C4S02WtOfHCNH C12 H 25 The dispersion of the cyan couplers of Formula I for use in the invention can be prepared by dissolving the couplers in a low-boiling or partially water-soluble auxiliary organic solvent. In accordance with one embodiment of the invention, such dispersions may be made with or without a high-boiling permanent organic solvent (including those solvents of f ormulas II-V provided that the ratio of these solvents to coupler in the dispersion is 0.50 or less). The resulting organic solution may then be mixed with an aqueous gelatin solution, and the mixture is then passed through a mechanical mixing device suitable for high-shear or turbulent mixing generally suitable for preparing photographic emulsified dispersions, such as a colloid mill, homogenizer, microfluidizer, high speed mixer, ultrasonic dispersing apparatus, blade mixer, device in which a liquid stream is pumped at high pressure through an orifice or interaction chamber, Gaulin mill, blender, etc., to form small particles of the organic phase suspended in the aqueous phase. more than one type of -device may be used to prepare the dispersions. The auxiliary organic solvent is then removed by evaporation, noodle washing, or membrane dialysis. The dispersion particles preferably have an average particle size of less than 2 microns, generally from about 0.02 to 2 microns, more preferably from about 0.02 to 0.5 micron. These methods are described in detail in U.S. Patents 2,322,027, 2,787,544, 2,801,170, 2,801,171, 2,949,360, and 3,396,027.

Examples of suitable auxiliary solvents which can be used in the present invention include: ethyl acetate, isopropyl acetate, butyl acetate, ethyl propionate, 2-ethoxyethylacetate, 2-(2-butoxyethoxy) ethyl acetate, dimethy1formamide, 2-methyl tetrahydrofuran, triethylphosphate, cyclohexanone, butoxyethyl acetate, methyl isobutyl ketone, methyl acetate, 4-methyl-2-pentanol, diethyl carbitol, 1,1,2- trichloroethane, 1,2-dichloropropane, and the like. Preferred auxiliary solvents included ethyl acetate and 2-(2-butoxyethyoxy) ethyl acetate.

In accordance with preferred embodiments of the invention, the coupler of Formula I is dispersed without any high-boiling organic solvent to form a coupler dispersion substantially free of permanent organic solvent. For the purposes of this invention, "substantially free of permanent organic solvent", "nosolvent", and like tern are intended to denote the absence of permanent solvents beyond trace or impurity levels. Such no solvent dispersions have been found to unexpectedly provide improved performance with respect to crystallization problems in comparison to dispersions having low solvent levels.

The aqueous phase of the coupler dispersions of the invention preferably comprise gelatin as a hydrophilic colloid. This may be gelatin or a modified gelatin such as acetylated gelatin, phthalated gelatin, oxidized gelatin, etc. Gelatin may be base-processed, such as lime-processed gelatin, or may be acid-processed, such as acid processed ossein gelatin. Other hydrophilic colloids may also be used, such as a water-soluble polymer or copolymer including, but not limited to poly(vinyl alcohol), partially hydrolyzed poly(vinylacetate-co-vinyl alcohol), hydroxyethyl cellulose, poly(acrylic acid), poly(l-vinylpyrrolidone), poly(sodium styrene sulfonate), poly(2- acrylamido-2methane sulfonic acid), polyacrylamide. Copolymers of these polymers with hydrophobic monomers may also be used.

A surfactant may be present in either the aqueous phase or the organic phase or the dispersions can be prepared without any surfactant present.

Surfactants may be cationic, anionic, zwitterionic or non-ionic. Ratios of surfactant to liquid organic solution typically are in the range of 0.5 to 25 wt.% for forming small particle photographic dispersions. a preferred embodiment of the invention, an anionic surfactant is contained in the aqueous gelatin solution. Particularly preferred surfactants which are employed in the present invention include an alkali metal salt of an alkarylene sulfonic acid, such as the sodium salt of dodecyl benzene sulfonic acid or sodium salts of isopropy1naphthalene sulfonic acids, such as mixtures of di-isopropyl- and tri-isopropylnaphthalene sodium sulfonates; an alkali metal salt of an alkyl sulfuric acid, such as sodium dodecyl sulfate; or an alkali metal salt of an alkyl sulfosuccinate, such as sodium bis ethylhexyl) succinic sulfonate.

The dispersions of couplers in accordance with the embodiments of the invention may contain more than one cyan coupler of Formula I, although it is not necessary that more than one coupler be employed to obtain the advantages of the invention. Preferred embodiments of the invention use dispersions of a single cyan coupler of Formula I substantially free of other cyan dye forming couplers. By "substantially free" is meant the absence of other cyan dye forming couplers beyond trace or impurity levels.

The high-boiling organic solvents represented by formulas 11-V are described below.

In Formula II, R4 and R5 may be the same or different, each is an alkoxycarbonyl group containing not more than 8 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, benzyloxycarbonyl, etc.; and m is an integer from 1 to 10, preferably from 4 to 8.

Representative examples of the high-boiling organic solvents according to formula II are shown below:

fl ii-1 11-2 H9C40- C-C8H le-C- 0C4H g fl H17C,O-C-C,BH,,-0-0COH 17 0 0 11 11 H9C4HCCH 20-C-C7H,-C-OCH 2CHC,,Hg 1 1 11-3 "2H 5 '2 r' 5 fl 11-4 H5C 20- C- C6H 12- C- OC 2H 5 11-5 0 11 0 11 H9C90-C- L;4md--C-OC,,Hg 0 11 0 11 11-6 H17C80-C ---0 --OCBH 17 11-7 11-8 fl fl H17 C80-C- C2H-C-OC$H 17 0 0 11 11 H17CeO.-C-CH:-C- OCSH 17 In formula III, the alkyl or alkenyl group represented by R6 may be substituted or unsubstituted, and R7 and R8 are individually selected from hydrogen and the group of moieties from which R6 is selected, provided that the total number of carbon atoms contained in R6, R7, and R8 is at least 10. In a preferred embodiment, at least one of R7 and R8 is hydrogen, and more preferably both of R7 and R8 are hydrogen.

Representative examples of compounds 20 represented by Formula III are given below:

iii-l 111-2 rt-C11H230H rr-Cl2H2SOH 111-3 111-4 111-5 rr-C,.H.30H CH3CH(OH)(CH 2)9CH3 CH3(CH2)7CH CH(CH2)80H 111-6 (CH3)2C CHCH2CH2C(CH3)CHCH2CH2C(CH3)(OH)CH CH2 111-7 111-8 111-9 III-10 C8H17 i HCH20H C6H 13 Clo H21 CHCH 20H 1 C8H 17 (CH3)2CHCH2CH(OH)CH 2CH2CH(CH2)3CH3 1 C2H 5 C7HISCH--=CH(CH2)60H In formula IV, the groups represented by R9 and R10 are hydrogen or straight chain or branched alkyl groups, with the requirements that at least one of R9 or R10 is not hydrogen, the total number of carbon atoms in R9 plus R10 is from 9 to 20, and R10 is in the para or a meta position with respect to the phenolic hydroxyl group.

Representative examples of the compounds represented by Formula IV are given below:

IV- 1 iv-2 IV-3 IV-4 H25 C 12-1 0H mixed isomers SH11A t-Hl,CS -C OH i H19C-0-0H SH,,-n n-H, C5 OH 1 C mixed isomers IV- 5 iv-6 H31 C 15 /O-OH H 3 n-H 21 C,)-C OH In formula V, the group Rll represents an aliphatic group, an aromatic group, or a heterocyclic group, and R12 represents a hydrogen atom, a hydroxy group, an alkoxy group, or an aliphatic group. Such 10 Rll and R12 groups may be further substituted or unsubstituted Representative examples of the compounds represented by Formula V are given below:

V-1 V-2 0 0C2H OCH 2CHC 4Hg-n 0H V-3 0 11 HC6 OCH 2 -C) 1 In a preferred embodiment, the cyan coupler of Formula I is dispersed as previously described without any high-boiling organic solvent, and then later combined with a separate dispersion of highboiling solvent of formulas II-V in an aqueous coating solution.

Aqueous dispersions of high-boiling solvents of formulas II-V can be prepared similarly to the coupler dispersion, e.g. , by adding the solvent to an aqueous medium and subjecting such mixture to high shear or turbulent mixing as described above. The aqueous medium is preferably a gelatin solution, and surfactants and auxiliary solvents may also be used as described above. In a preferred embodiment, a hydrophobic additive is dissolved in the solvent to prevent particle growth as described in U.S. Patent No. 5,468, 604. The mixture is then passed through a mechanical mixing device such as a colloid mill, homogenizer, microfluidizer, high speed mixer, ultrasonic dispersing apparatus, etc. to form small particles of the organic solvent suspended in the aqueous phase. If an auxiliary solvent is employed, it is then subsequently removed by evaporation, noodle washing, or membrane dialysis. These methods are described in detail in the aforementioned references on dispersion making. The solvent dispersion may be a "blank" dispersion which does not contain any additional photographically useful compounds, or the solvent may be part of a photographically useful compound dispersion.

An aqueous coating solution in accordance with the present invention may then be prepared by combining a cyan coupler dispersion with the separate dispersion of the high-boiling organic solvent of formulas II-V. Other ingredients may also be contained in this solution such as silver halideemulsions, dispersions or solutions of other photographically useful compounds, additional gelatin, or acids and bases to adjust the pH. These ingredients may then be mixed with a mechanical device at an elevated temperature (e.g., 30 to 50OC) for a short period of time (e.g., 5 min to 4 hours) prior to coating. In accordance with one embodiment of the invention, the coupler and solvent dispersions are combined in a coating solution such that the weight ratio of high boiling organic solvent of formulas II-V to coupler of formula I in such solution is from 0.1 to 20 0.5, more preferably from 0.1 to 0.35, and most preferably from 0.2 to 0.3. It is an unexpected advantage of the invention that the particular high boiling solvents provide relatively higher coupler reactivity for couplers of formula I at low levels of coupler solvent in comparison to other conventional high boiling solvents. When used at lower ratios than specified above, coupler reactivity is generally not increased to as high a level as is desired. When used at higher ratios, the advantages associated with reduced coupler solvent levels are undesirably compromised.

With the present invention, it is possible to produce a silver halide light-sensitive photographic material which employs specific phenolic cyan couplers with a minimal level of high-boiling organic solvent to reduce coated dry thickness while maintaining high coupler reactivity to obtain desirable dye densities upon processing the photographic material and avoiding coupler crystallization problems exhibited by low solvent dispersions of these couplers.

Photographic elements comprising coupler dispersions.in accordance with the 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 an alternative format, the emulsions sensitive to each of the three primary regions of the spectrum can be disposed as a single segmented layer.

A typical multicolor photographic element comprises a support bearing a cyan dye image-forming unit comprised of at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler, a magenta dye image-forming unit comprising at least one greensensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler, and a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dyeforming coupler. The element can contain additional layers, such as filter layers, interlayers, antihalation layers, overcoat layers, subbing layers, and the like.

If desired, the photographic element can be used in conjunction with an applied magnetic layer as described in Research Disclosure, November 1992, Item 34390. It is also specifically contemplated to use dispersions according to the invention in combination with technology useful in small format film as described in Research Disclosure, June 1994, Item 36230. Research Disclosure is published by Kenneth Mason Publications, Ltd., Dudley House, 12 North Street, Emsworth, Hampshire P010 7DQ, ENGLAND.

In the following discussion of suitable materials for use in the emulsions and elements that can be used in conjunction with this photographic element, reference will be made to Research Disclosure, September 1994, Item 36544, available as described above, which will be identified hereafter by the term "Research Disclosure." The Sections hereafter referred to are Sections of the Research Disclosure, Item 36544.

The silver halide emulsions employed in these photographic elements can be either negative-working or positive-working. Suitable emulsions and their preparation as well as methods of chemical and spectral sensitization are described in Sections I, and III-IV.

Vehicles and vehicle related addenda are described in Section II. Dye image formers. and modifiers are described in Section X. Various additives such as UV dyes, brighteners, luminescent dyes, antifoggants, stabilizers, light absorbing and scattering materials, coating aids, plasticizers, lubricants, antistats and matting agents are described, for example, in Sections VI-IX. Layers and layer arrangements, color negative and color positive features, scan facilitating features, supports, exposure and processing can be found in Sections XI-XX.

in addition to the cyan couplers of Formula I included in the dispersions of the invention, other photographic couplers may also be included in elements of the invention. Couplers that form cyan dyes upon reaction with oxidized color developing agents are described in such representative patents and publications as: U.S. Patent Nos. 2,367,531; 2,423,730; 2,474,293; 2,772, 162; 2,895,826; 3,002,836; 3,034,892; 3,041,236; 4,333,999; 4,883,746 and "Farbkuppler - Eine Literature Ubersicht," published in Agfa Mitteilungen, Band III, pp. 156-115 (1961). Preferably such couplers are phenols and naphthols that form cyan dyes on reaction with oxidized color developing agent. Also preferable are the cyan couplers described in, for instance, European Patent Application Nos. 544,322; 556,700; 556,777; 565,096; 570,006; and 574,948. Especially preferred embodiments of the inveniton include the use of a cyan coupler of Formula I as the principle cyan dye forming image coupler.

Couplers that form magenta dyes upon reaction with oxidized color developing agent which can be incorporated in elements of the invention are described in such representative patents and publications as:

U.S. Patent. Nos. 2,600,788; 2,369,489; 2,343,703; 2,311,082; 2,908,573; 3,062,653; 3,152,896; 3,519,429 and "Farbkuppler - Eine Literature Ubersicht," published in Agfa Mitteilungen, Band III, pp. 126-156 (1961). Preferably such couplers are pyrazolones, pyrazolotriazoles, or pyrazolobenzimidazoles that form magenta dyes upon reaction with oxidized color developing agents. Preferred couplers include 1H pyrazolo [5,1-c]-1,2,4-triazoles and 1H-pyrazolo [1,5 b]-1,2,4-triazoles. Examples of 1H-pyrazolo [5,1-c] 1,2,4-triazole couplers are described in U.K. Patent Nos. 1,247,493; 1,252,418; 1,398,979; U.S. Patent Nos.

4,443,536; 4,514,490; 4,540,654; 4,590,153; 4,665,015; 4,822,730; 4,945,034; 5,017,465; and 5,023,170.

Examples of 1H-pyrazolo [1,5-bl-1,2,4-triazoles can be found in European Patent applications 176,804; 177,765; U.S Patent Nos. 4,659,652; 5,066,575; and 5,250,400.

Especially preferred are pyrazolone couplers, such as described in U.S. Patent 4,853,319.

Couplers that form yellow dyes upon reaction with oxidized color developing agent and which are useful in elements of the invention are described in such representative patents and publications as: U. S. Patent Nos. 2,875,057; 2,407,210; 3,265,506; 2,298,443; 31048,194; 3,447, 928; 4,022,620; 4,443,536 and " Farbkuppler - Eine Literature Ubersicht, " published in Agfa Mitteilungen, Band III, pp. 112-126 (1961). Such couplers are typically open chain ketomethylene compounds. Also preferred are yellow couplers such as described in, for example, European Patent Application Nos. 482,552; 510,535; 524,540; 543,367; and U.S.

Patent No. 5,238,803.

To control the migration of various components coated in a photographic layer, including couplers, it may be desirable to include a high molecular weight hydrophobe or "ballast" group in the component molecule. Representative ballast groups include substituted or unsubstituted alkyl or aryl groups containing 8 to 40 carbon atoms. Representative substituents on such groups include alkyl, aryl, alkoxy, aryloxy, alkylthio, hydroxy, halogen, alkoxycarbonyl, aryloxcarbonyl, carboxy, acyl, acyloxy, amino, anilino, carbonamido (also known as acylamino), carbamoyl, alkylsulfonyl, arysulfonyl, sulfonamido, and sulfamoyl groups wherein the substituents typically contain 1 to 40 carbon atoms. Such substituents can also be further substituted. Alternatively, the molecule can be made inunobile by attachment to polymeric backbone.

It may be useful to use a combination of couplers any of which may contain known ballasts or coupling-off groups such as those described in U.S. Patents 4,301,235; 4,853,319 and 4,351,897.

It is also contemplated that the materials and processes described in an article titled '"Typical and Preferred Color Paper, Color Negative, and Color Reversal Photographic Elements and Processing, a published in Research Disclosure, February 1995, Volume 370 may also be advantageously used with the dispersions of the invention.

The invention materials may further be used in combination with a photographic element containing image-modifying compounds such as "Developer Inhibitor- Releasing" compounds (DIR's). DIR's useful in conjunction with the compositions of the invention are known in the art and examples are described in U.S.

Patents 3,137,578; 3,148,022; 3,148,062; 3,227,554; 3,384,657; 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; 41500,634; 4,579,816; 4,607,004; 4,618,571; 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; 4,956,269; 4,959,299; 4,966,835; 4,985,336 as well as in patent publications GB 1,560,240; GB 2, 007, 662; GB 2, 032,914; GB 2, 099, 167; DE 2, 842, 063, DE 2, 937, 127; DE 3, 636, 824; DE 3, 644, 416 as well as the following European Patent Publications: 272,573; 335,319; 336,411; 346, 899; 362, 870; 365,252; 365,346; 373,382; 376,212; 377,463; 378,236; 384,670; 396,486; 401, 612; 401, 613. Such compounds are also disclosed in " Deve 1 oper- Inhibi tor-Re leasing (DIR) Couplers for Color Photography, " C.R. Barr, J.R. Thirtle and P.W. Vittum in Photographic Science and Engineering, Vol. 13, p. 174 (1969).

Especially useful for use with this invention are tabular grain silver halide emulsions. Suitable tabular grain emulsions can be selected from among a variety of conventional teachings, such as those of the following: Research Disclosure, Item 22534, January 1983; U.S. Patents 4,439,520; 4, 414,310; 4,433,048; 4,643,966; 4,647,528; 4,665,012; 4,672,027; 4,678,745; 4,693,964; 4,713,320; 4,722,886; 4,755,456; 4,775,617; 4,797,354; 4,801, 522; 4,806,461; 4,835,095; 4,853,322; 4,914,014; 4,962,015; 4,985,350; 5, 061,069; 5,061,616; and 5,320,938.

The emulsions can be surface-sensitive emulsions, i.e., emulsions that form latent images primarily on the surfaces of the silver halide grains, or the emulsions can form internal latent images predominantly in the interior of the silver halide grains. The emulsions can be negative-working emulsions, such as surface- sensitive emulsions or unfogged internal latent image-forming emulsions, or direct-positive emulsions of the unfogged, internal latent image- forming type, which are positive-working when development is conducted with uniform light exposure or in the presence of a nucleating agent. Specifically contemplated and preferred are Se and Ir doped tabular emulsions as described in U.S. Patent 5,164,292. Usage of the invention in combination with thin layers as described in U.S. Patent 5,322,766 is also specifically contemplated and preferred.

The emulsions can be spectrally sensitized with any of the dyes known to the photographic art, such as the polymethine dye class, which includes the cyanines, merocyanines, complex cyanines and merocyanines, oxonols, hemioxonols, styryls, merostyryls and streptocyanines. In particular, it would be advantageous to use the low staining sensitizing dyes disclosed in U.S. Patent Nos.

5,316,904, 5,292,634, 5,354,651, and EP Patent Application 93/203193.3, in conjunction with elements of the invention.

Photographic elements can be exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image and can then be processed to form a visible dye image. Processing to form a visible dye image includes the step of contacting the element with a color developing agent to reduce developable silver halide and oxidize the color developing agent. oxidized color developing agent in turn reacts with the coupler to yield a dye.

The following examples are given to illustrate the invention in greater detail. Unless otherwise specified, all percentages and ratios are based on weight.

Example 1

30g of cyan coupler C-1 was dissolved in 30g of di-n-butyl phthalate (DBP) and 60g of ethyl acetate at 75C. This oil phase solution was then combined with an aqueous phase solution consisting of 40g gelatin, 32g of a 10% solution of Alkanol-XC (Dupont), and 308g of distilled water. This mixture was then passed through a Gaulin colloid mill five times followed by removal of ethyl acetate by rotary evaporation. Distilled water was then added back to form Dispersion A which consisted of 6% coupler, 8% gel. Dispersions B through G were similarly prepared with various levels of DBP as described in Table 1. These dispersions were kept in cold storage for 26 weeks and were than held for 6 hours at 45'C and then examined for crystallization by optical microscopy. Results are summarized in Table I below. Microscopic examination showed that only the dispersion containing no coupler solvent provided good resistance to crystal formation after extended cold storage followed by melt holding at elevated temperature.

1 When these dispersions were held at 45'C for extended times, the coupler crystallization was so severe that the entire dispersion became a solid mass. The time required for this solidification to occur is another indicator of dispersion stability, and is also indicated in Table I. These results clearly show that the no solvent dispersion has markedly improved melt hold stability compared with the solvent-containing dispersions.

Table I

Dispersion Couple Solvent/CoupLer Microscopic Appearance Time to Solidify A C-I 1.00 Many large and small 22 hr crystals B c D E F G CA CA CA C-1 CA CA 0.50 Severe crystallization 0.00 Few small crystals 1.25 Many large and small crystals Many large and small crystals 0.25 18 hr 123 hr 33 hr 21 hr 0.75 Severe crystallization 21 hr 1.00 Many large and small 39 hr crystals Example 2

Dispersions H and I were prepared like Dispersions A and C, respectively (with and without DBP). These dispersions were then diluted 1:1 with 8% gelatin to form coating solutions consisting of 3% coupler and 8% gel. 500g of each coating solution was held for 24 hours at 45'C and then passed through a Grade 24 glass-fiber depth filter (Hollingworth and Vose) under pressure (5 psi). The time required for the coating solution to pass through the filter is an indication of the stability of dispersion making up the coating solution. More stable dispersions filter through more rapidly than less stable dispersions. Filterability of the coating solution was evaluated by measuring the weight of coating solution passing through the filter as a function of time. The results for two repeated trials, illustrated in Fig 1, show that the coating solutions containing the no-solvent cyan coupler dispersion passed through the filter much more rapidly than the solution with the solventcontaining dispersion.

Example 3

30g of cyan coupler C-12 was dissolved in 90g of ethyl acetate at 700C. This oil phase solution was then combined with an aqueous phase solution consisting of 30g gelatin, 30g of a 10% solution of Alkanol-XC (Dupont), and 320g of distilled water. This mixture was then passed through a Gaulin colloid mill five times followed by removal of the ethyl acetate by rotary evaporation. Distilled water was then added back to form Dispersion J which consisted of 6% coupler, 6% gel. Dispersions K and L were similarly prepared with DBP present in the oil phase at the levels given in Table II. These dispersions were kept in cold storage for 1 week and were then held for 4 hours at 450C and were subsequently examined for crystallization by microscopy. These dispersions were also held at 45C for longer times to determine the time needed for solidification to occur. Results are summarized below:

Table II

DisMrsion Couple Solvent/CgUpler MicroscQpic6Zearance TimetoSolidif j C-12 0.0 No Crystallization 10 hours K C-12 0.5 Severe Crystallization 4 hours L C-12 1.0 Many, fine needle- 7 hours shaped crystals The results also.show that the no solvent dispersion has improved melt hold stability compared to the solvent-containing dispersions.

Example 4

Dispersions J and L were diluted 1:2 with 6% gelatin to form coating solutions consisting of 2% coupler and 6% gel. 500g of each coating solution was held f or 6 hours at 450C and then tested f or filterability as described in Example 2. The results f or two repeated trials, shown in Fig 2, again demonstrate that the coating solution containing the no-solvent cyan coupler dispersion was more filterable than the solvent-containing dispersion.

Example 5

Dispersions M, N, and 0 were prepared like Dispersions J, K, and L of Example 3, respectively, except that cyan coupler C-9 was substituted for cyan coupler C-12. These dispersions were kept in cold storage for 2 weeks and were then held for 40 hours at 450C and were subsequently examined for crystallization by microscopy. Results are summarized in Table III below:

Table Ill

Dispersion Couple Solvent/Couple Microscopic Appearance m C-9 0.0 Few small crystals N C-9 0.5 Severe crystallization 0 C-9 1.0 No crystallization Again, the no solvent dispersion was considerably more stable than the low solvent 30 dispersion of the prior art.

Example 6

Dispersions AA through 00 were prepared as described in Example 3 using the photographic comparison compounds, coupler solvents and incubation conditions described in Table IV. Results of microscopic evaluations are given below:

Table IV

DBP DBP DBP DBP DBP DBP Dispersion AA BB cc DD EE FF GG HH 11 ji KK LL MM NN 00 Compound COMP-1 Comp-A COMP-1 Comp-2 Comp-2 Comp-2 Comp-3 Comp-3 Comp-3 Comp-4 Comp-4 Comp-4 Comp-5 Comp-5 Comp-5 DBP dibutylphthalate TCP tricresylphospbate Solvent/ Storage Hold Time Solvent Compound Time @ 4PC 0.0 DBP 0.5 DBP 1.0 0.0 0.5 1.0 0.0 0.5 1.0 0.0 0.5 1.0 0.0 0.5 1.0 Micreiscopic: Appearance Soy= crystallization Very few small crystals No crystallization Severe crystallization No crystallization No crystallization Severe crystallization No crystallization No crystallization Many plate crystals Few plate crystals No crystallization Severe crystallization Several small crystals Very few small crystals TCP TCP 2 weeks 2 weeks 2 weeks 2 weeks 2 weeks 2 weeks 2 weeks 2 weeks 2 weeks 1 week 1 week 1 week 1 week 1 week 1 week 0 hours 0 hours 0 hours 0 hours 0 hours 0 hours 20 hours 20 hours 20 hours 24 hours 24 hours 24 hours 24 hours 24 hours 24 hours These results clearly demonstrate that dispersions containing no coupler solvent are substantially more crystal prone than their solvent- containing counterparts for a wide variety of photographically useful compounds that have a tendency to crystallize in dispersions.

OR CH3 1 C-CH2-CO19-t CH =3 1 113 t-CP9-CE2-C L;JM3 05 COMP-1 I CN C1130 " CO2C3B7-n Comp-2 OR COM (C112) 4-0-P-C5Ell-t C5Ell-t Coinp-3 OR cl COCE-0 CSEI.J.-t 1 1 %..;2215 -P- CH3 C!sEll-t 1 cl Comp-4 ci-' - N-N - 1 NHCO-1 0 il C Comp-5 COCE2-0-P-C5Ell-t C5Ell-t Example 7 Photographic Sample 101 (comparative control) A color photographic recording material for color negative development was prepared by applying the following layers in the given sequence to a support of cellulose triacetate. The side of the support to be coated had been prepared by gelatin subbing, and the reverse side of the support comprised dispersed carbon pigment in a non-gelatin binder (rem jet coating) that was soluble in basic aqueous solutions, and which served to provide a removable black antihalation backing with antistatic properties. The quantities of silver halide are given in g of silver/m2. The quantities of other materials are given in g/m2. The cyan dye-forming coupler C-1 employed in the low and high sensitivity red- sensitive layers was dispersed in the general manner of the comparative control dispersion A in dispersion Example 1, with a ratio of high boiling solvent di-n-butylphthalate to coupler of 1.0. The various compounds used in the photographic examples are identified following the examples.

Layer 1: Low Sensitivity Red-Sensitive Layer This layer comprised a blend of a lower sensitivity, red-sensitized, silver iodobromide emulsion (3.0% iodide, 0.58 micrometers diameter) and a higher sensitivity, red-sensitized silver iodobromide emulsion (4.0% iodide, 0.86 micrometers diameter) Lower sensitivity emulsion Higher sensitivity emulsion DIR coupler D-1 Bleach accelerator coupler BAR-1 Cyan dye-forming coupler C-1 HBS-1 HBS-2 HBS-3 TAI Gelatin 1.356 0.581 0.031 0.021 0.288 0.124 0.288 0.021 0.031 2.523 Layer 2: High Sensitivity Red-Sensitive Layer Red sensitized silver iodobromide emulsion [6.0 mol % iodide, average grain diameter 1.14 micrometers).

Emulsion DIR coupler D-2 Cyan dye-forming magenta colored coupler CM-1 Cyan dye-forming coupler C-1 HBS-2 HBS-4 TAI Gelatin 0.969 0.076 0.028 0.093 0.093 0.150 0.016 1.388 Layer 3: Interlayer Compensatory printing density yellow dye MM-1 Oxidized developer scavenger DOXS-1 Compensatory printing density magenta dye MD-1 Gelatin 0.059 0.095 0.024 0.947 Layer 4: Low Sensitivity Green-Sensitive Layer This layer comprised a blend of lower sensitivity, green-sensitized silver iodobromide emulsion [3.0 mol % iodide, average grain diameter 0.44 micrometers] and higher sensitivity, green-sensitized silver iodobromide emulsion [6.0 mol % iodide, average grain diameter 0.77 micrometers].

Lower sensitivity emulsion Higher sensitivity emulsion DIR coupler D-3 magenta dye-forming yellow colored coupler MM-2 magenta dye-forming coupler M-1 magenta dye-forming coupler M-2 oxidized developer scavenger DOXS-2 HBS-1 TAI Gelatin 0.162 1.165 0.022 0.135 0.236 0.101 0.015 0.481 0.022 1.822 Layer 5: High Sensitivity Green-Sensitive Layer Green-sensitized silver iodobromide emulsion [3.0 mol % iodide, average grain diameter 0.81 micrometers].

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 developer scavenger DOXS-2 HBS-1 TAI Gelatin Layer 6: Yellow Filter Layer Compensatory printing density yellow dye MM- 1 Yellow filter dye YD-1 oxidized developer scavenger DOXS-1 Gelatin 0.012 0.152 0.014 1.250 0.091 0.154 0.118 0.947 Layer 7: Low Sensitivity Blue-Sensitive Layer This layer comprised a blend of lower sensitivity, blue-sensitized silver iodobromide emulsion [3.0 mol. % iodide, average grain diameter 0.56 micrometers] and higher sensitivity, blue-sensitized silver iodobromide emulsion [3.0 mol. % iodide, average grain diameter 0.76 micrometers] Lower sensitivity emulsion Higher sensitivity emulsion DIR coupler D-10 Yellow dye-forming coupler Y-1 Oxidized developer scavenger DOXS-2 HBS-2 TAI Gelatin 0.182 0.182 0.009 0.725 0.010 0.372 0.006 1.557 Layer 8: High Sensitivity Blue-Sensitive Layer Blue-sensitized silver iodobromide emulsion [3.0 mol. % iodide, average grain diameter 1.07 micrometers] Emulsion DIR coupler D-4 Yellow dye-forming coupler Y-1 oxidized developer scavenger DOXS-2 HBS-2 TAI Gelatin Layer 9: Ultraviolet Filter Layer Dye UV-1 Dye UV-2 Unsensitized silver bromide Lippmann emulsion HBS-5 Gelatin 0.450 0.039 0.133 0.019 0.106 0.001 0.965 0.022 0.114 0.215 0.136 0.861 Layer 10: Protective Overcoat Layer Polymethylmethacrylate matte beads Soluble polymethylmethacrylate matte beads Silicone lubricant Gelatin 0.009 0.161 0.057 0.873 This film was hardened at coating with 1.80% by weight of total gelatin of hardener H-1. Surfactants, coating aids, soluble absorber dyes and stabilizers were added to the various layers of this sample as is commonly practiced in the art.

Sample 102 (invention) A color photographic recording material for color negative development was prepared exactly as in Sample 101 above, except where noted below. The cyan dye-forming coupler C-1 employed in the low and high sensitivity red-sensitive layers was dispersed in the general manner of the inventive example C in dispersion Example 1, without the presence of a high boiling solvent.

Layer 1: Low Sensitivity Red-Sensitive Layer Bleach accelerator coupler BAR-1 Cyan dye-forming coupler C-1 HBS-1 HBS-2 HBS-3 Gelatin Changes 0.019 0.262 0.124 0.000 0.019 2.477 Layer 2: High Sensitivity Red-Sensitive Layer Changes 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 Changes Magenta dye- forming coupler M-1 Magenta dye-forming coupler M-2 HBS-1 Gelatin 0.198 0.084 0.453 1.781 Duplicate samples of photographic recording materials Sample 101 and 102 were individually exposed for 1/50 of a second to white light from a tungsten light source of 3200 K color temperature through a graduated 0 3.0 density step tablet to determine their speed and gamma. The samples were then procssed using a color negative process, the KODAK ECN-2 process as described by the "Manual for Processing Eastman Notion Picture Film", Publication H-24.07, Eastman Kodak Company, Rochester, NY. This motion picture film color negative process and other color negative processes such as the color negative amateur film process C-41 are described in the British Journal of Photography Annual of 1988 at pages 196-198 (KODAK is a trademark of the Eastman Kodak Company, USA).

Following processing and drying, Samples 101 and 102 were subjected to Status M densitometry, and the duplicate sample density data were averaged. The photographic performance of the recording materials is compared below in Table V.

Table V

Sample D-min ER Speed Ganma Density at 0.20 log H 101 (control) Red 0.131 471 0.545 1.37 Green 0.554 473 0.625 1.93 Blue 0.957 483 0.654 2.45 102 (invention) Red 0.129 471 0.523 1.38 Green 0.552 474 0.624 1.92 Blue 0.956 483 0.642 2.48 The photographic data show that the inventive high boiling solvent-free dispersion of cyan dye forming coupler C-1 can result in essentially identical sensitometric performance following direct substitution for the comparative control dispersion employing di-nbutylphthalate in a weight ratio 1.0 to C-1 in the color negative recording material of Example 1.

Example 8 Photographic Sample 201 (comparative control) A color photographic recording material for color negative development was prepared by applying the following layers in the given sequence to a transparent support of cellulose triacetate. The side of the support to be coated had been prepared by gelatin subbing. The quantities of silver'halide are given in g of silver/m2. The-quantities of other materials are given in g/m2. The cyan dye-forming coupler C-1 employed in the low, medium and high sensitivity redsensitive layers was dispersed in the general manner of the comparative control dispersion A in dispersion Example 1, with a ratio of high boiling solvent di-nbutylphthalate to coupler of 1.0.

Layer 1: Antihalation Layer Black colloidal silver sol (0.151 g/m2). UV_ 1 UV-2 Oxidized developer scavenger DOXS3 Compensatory printing density cyan dye CD-1 Compensatory printing density magenta dye MD-2 Compensatory printing density yellow dye MM1 Compensatory printing density yellow dye YD-2 HBS-1 HBS-5 Disodium salt of 3,5-di-sulfocatechol Gelatin 0.075 0.075 0.162 0.020 0.042 0.088 0.008 0.426 0.151 0.270 2.441 Layer 2: Low Sensitivity Red-Sensitive Layer This layer comprised a blend of a lower sensitivity, red-sensitized tabular silver iodobromide emulsion [1.3% iodide, average grain diameter 0.53 micrometers and thickness 0.09 micrometers thick] and a higher sensitivity, red-sensitized tabular silveriodobromide emulsion [4.1% iodide, average grain diameter 1.04 micrometers and thickness 0.09 micrometers].

Lower sensitivity emulsion Higher sensitivity emulsion Bleach accelerator coupler BAR-1 Cyan dye-forming coupler C-1 Cyan dye-forming magenta colored coupler CM-1 Oxidized developer scavenger DOXS-2 HBS-2 HBS-3 TAI Gelatin 0.495 0.431 0.038 0.517 0.027 0.010 0.517 0.038 0.015 1.775 Layer 3: Medium Sensitivity Red-Sensitive Layer Red-sensitized tabular silver iodobromide emulsion [4.1 mol % iodide, average grain diameter 1.39 micrometers and thickness 0.12 micrometers].

Emulsion DIR coupler D-5 Cyan dye-forming magenta colored coupler CM-1 Cyan dye-forming coupler C-I HBS-2 HBS-4 TAI Gelatin 0.700 0.011 0.022 0.215 0.215 0.022 0.011 1.786 Layer 4: High Sensitivity Red-Sensitive Layer Red-sensitized, tabular silver iodobromide emulsion [4.1 mol % iodide, average grain diameter 2.93 micrometers and thickness 0. 13 micrometers].

Emulsion DIR coupler D-5 DIR coupler D-6 Cyan dye-forming magenta colored coupler CM-1 Cyan dye-forming coupler C-1 HBS-1 HBS-2 HBS-4 TAI Gelatin Gelatin Layer 5: Interlayer 1.076 0.020 0.048 0.032 0.140 0.194 0.140 0.041 0.010 1.711 1.292 Layer 6: Low Sensitivity Green-Sensitive Layer This layer comprised a blend of lower sensitivity, green-sensitized tabular silver iodobromide emulsion [1.3 mol % iodide, average grain diameter 0.53 micrometers and thickness 0.09 micrometers] and higher sensitivity, green-sensitized tabular silver iodobromide emulsion [4.1 mol % iodide, average grain diameter 1.04 micrometers and thickness 0.09 micrometers].

Lower sensitivity emulsion Higher sensitivity emulsion Magenta dyeforming yellow colored coupler MM-2 Magenta dye-forming coupler M-4 Oxidized developer scavenger DOXS-2 HBS-1 TAI Gelatin Layer 7: Medium Sensitivity Green-Sensitive Layer Green-sensitized tabular silver iodobromide emulsion [4.1 mol % iodide, average grain diameter 1.23 micrometers and thickness 0.12 micrometers].

Emulsion DIR coupler D-5 Magenta dye-forming yellow colored coupler MM-2 Magenta dye-forming coupler M-4 Oxidized developer scavenger DOXS-2 HBS-1 HBS-4 TAI Gelatin 0.969 0.024 0.065 0.070 0.019 0.186 0.048 0.014 1.399 Layer 8: High Sensitivity Green-Sensitive Layer Green-sensitized, tabular silver iodobromide emulsion [4.1 mol % iodide, average grain diameter 2.19 micrometers and thickness 0.13 micrometers].

Emulsion DIR coupler D-3 DIR coupler D-7 Magenta dye-forming yellow colored coupler MM-2 Magenta dye-forming coupler M-4 oxidized developer scavenger DOXS-2 HBS-1 HBS-2 TAI Gelatin Layer 9: Yellow Filter Layer Yellow filter dye YD-1 Gelatin 0.969 0.011 0.011 0.054 0.058 0.016 0.176 0.011 0.012 1.291 0.108 1.292 Layer 10: Low Sensitivity Blue-Sensitive Layer This layer comprised a blend of lower sensitivity, blue-sensitized tabular silver iodobromide emulsion [1.3 mol % iodide, average grain diameter 0.53 micrometers and thickness 0.09 micrometers], medium sensitivity, tabular blue-sensitized silver iodobromide emulsion [4.1 mol. % iodide, average grain diameter 0.80 micrometers and thickness 0.09 micrometers] and higher sensitivity, tabular blue-sensitized silver iodobromide emulsion [6.0 mol % iodide, average grain diameter 0.96 micrometers and thickness 0.26 micrometers] Lower sensitivity emulsion medium sensitivity emulsion Higher sensitivity emulsion DIR coupler D-8 Yellow dye-forming coupler Y-1 Yellow dye- forming coupler Y-2 Bleach accelerator coupler BAR1 Cyan dye-forming coupler C-1 oxidized developer scavenger DOXS-2 HBS-2 HBS-3 TAI Gelatin 0.269 0.172 0.549 0.065 0.280 0.700 0.003 0.027 0.005 0.931 0.003 0.016 2.519 Layer ll: High Sensitivity Blue-Sensitive Layer This layer comprised a blend of lower sensitivity, blue-sensitized silver iodobromide emulsion [9.0 mol % iodide, average grain diameter 1.06 micrometers] and high sensitivity, tabular blue-sensitized silver iodobromide emulsion [4.1 mol % iodide, average grain diameter 3.37 micrometers and thickness 0.14 micrometers] Low sensitivity emulsion High sensitivity emulsion Yellow dye-forming coupler Y-1 Yellow dye-forming coupler Y-2 DIR coupler D-8 Bleach accelerator coupler BAR-1 Cyan dye-forming coupler C-1 oxidized developer scavenger DOXS-2 HBS-2 HBS-3 TAI Gelatin 0.226 0.570 0.080 0.200 0.048 0.005 0.029 0.001 0.317 0.005 0.013 1.580 Layer 12: Ultraviolet Filter Layer Dye UV- 1 Dye UV-2 Unsensitized silver bromide Lippmann emulsion HBS-5 Gelatin Layer 13: Protective Overcoat Layer Polymethylmethacrylate matte beads Soluble polymethylmethacrylate matte beads Silica gel particles Silicone lubricant Gelatin 0.108 0.108 0.215 0.215 0.699 0-005 0.054 0.108 0.039 0.888 This film was hardened at coating with 1.75% by weight of total gelatin of hardener H-2. Surfactants, coating aids, soluble absorber dyes, antifoggants, stabilizers, antistatic agents, biocides, and other addenda chemicals were added to the various layers of this sample as is commonly practiced in the art.

Sample 202 (invention) A color photographic recording material for color negative development was prepared exactly as in Sample 201 above, except where noted below. The cyan dye-forming coupler C-1 einployed in the high sensitivity red- sensitive layer was dispersed in the general manner of the inventive example C in dispersion Example 1, without the presence of high boiling solvent HBS-2.

Layer 4: High Sensitivity Red-Sensitive Layer Changes HBS-2 0.000 Sample 203 (invention) A color photographic recording material for color negative development was prepared exactly as in Sample 201, except where noted below. The cyan dyeforming coupler C-1 employed in the high sensitivity red-sensitive layer was dispersed in the general manner of the inventive example C in dispersion Example 1, without the presence of a high boiling solvent. A separate dispersion of HBS-2 was added to the liquid coating solution to provide an equal coverage by weight to that of cyan dye-forming coupler C-1.

Sample 204 (invention) A color photographic recording material for color negative development was prepared exactly as Sample 202, except where noted below. The redsensitized tabular silver iodobromide emulsion of Layer 4 comprised 3.1 mol % iodide, with an average grain diameter 2.42 micrometers and thickness 0.12 micrometers. This emulsion comprised 1.0 mol% lower iodide than the emulsion employed in Sample 202. The lower iodide emulsion was prepared as described in U.S. Patent 5,164,292.

46- Sample 205 (invention) A color photographic recording material for color negative development was prepared exactly as Sample 202, except where noted below. The red sensitized tabular silver iodobromide emulsion of Layer 4 comprised 2.0 mol % iodide, with an average grain diameter 3.07 micrometers and thickness 0.12 micrometers. This emulsion comprised 2.1 mol% lower iodide than the emulsion employed in Sample 202. The lower iodide emulsion was prepared as described in U.S.

Patent 5.,164,292.

Sample 206 (invention) A color photographic recording material for color negative development was prepared exactly as Sample 202, except where noted below. DIR coupler D-5 was not included in Layer 4.

Layer 4: High Sensitivity Red-Sensitive Layer Changes DIR coupler D-5 HBS-4 0.000 0.000 Sample 207 (invention) A color photographic recording material for color negative development was prepared exactly as Sample 202, except where noted below. Layer 4 additionally comprised bleach accelerator releasing compound BAR-1.

Layer 4: High Sensitivity Red-Sensitive Layer Chnages Bleach accelerator coupler BAR-1 0.011 HBS-2 0.000 HBS-3 0.011 Sample 208 (invention) A color photographic recording material for color negative development was prepared exactly as Sample 207 above, except Layer 4 comprised bleach accelerator releasing compound BAR-1 in a higher amount.

Layer 4: High Sensitivity Red-Sensitive Layer Changes Bleach accelerator coupler BAR-1 HBS-2 HBS-3 0.027 0.000 0.027 Sample 209 (invention) A color photographic recording material for color negative development was prepared exactly as Sample 202, except where noted below. Layer 4 additionally comprised a development accelerating compound, CHEM-1.

Layer 4: High Sensitivity Red-Sensitive Layer Changes Development accelerator compound CHEM-1 0.007 HBS-2 0.000 Samples 201-209 were individually exposed for 1/500 of a second to white light from a tungsten light source of 3200 K color temperature that was filtered by a Daylight Va filter to 5500 K through a graduated 0 - 4.0 density step tablet to determine their speed and gamma. The samples were then processed using a color negative process, the Kodak C-41 process, as described by the 1988 Annual of the British Journal of Photography, pages 196 - 198. Another description of the use of the C-41 Flexicolor Process can be found in "Using Kodak Flexicolor Chemicals", Publication Z-131, Eastman Kodak Company, Rochester, NY. (Kodak is a trademark of the Eastman Kodak Company, USA).

Following processing and drying, Samples 201- 209 were subjected to Status M densitometry. The photographic performance of the recording materials is compared below in Table VI.

Table V1

Red-Light Sensitive Unit Perfomance Gradient Gnmmn Meter Density at Sample D-min IR Speed Low Lowmid GAMMA.50 log H 201 (comparison) 0.294 348 0.556 0.623 0.612 2.27 202 (invention) 0.296 344 0.555 0.604 0.593 2.21 203 (invention) 0.291 347 0.563 0.614 0.613 2.27 204 (invention) 0.309 343 0.557 0.637 0.635 2.27 205 (invention) 0.283 347 0.570 0.626 0.625 2.26 206 (invention) 0.296 346 0.633 0.660 0.640 2.32 207 (invention) 0.297 347 0.591 0.630 0.615 2.25 208 (invention) 0.305 346 0.619 0.650 0.655 2.29 209 (invention) 0.308 347 0.535 0.571 0.570 2.19 The photographic data for Sample 202 show that the inventive high boiling solvent-free dispersion of cyan dye-forming coupler C-1 can provide nearly identical sensitometric performance following direct substitution for the comparative control dispersion employing di-n-butylphthalate in a weight ratio 1.0 to C-1 in the high sensitivity red-sensitive layer of color negative recording material of Example 2. The photographic data for Sample 203 show that the inventive high boiling solvent-free, improved stability dispersion of cyan dye-forming coupler C-1 can be combined with a dispersion of HBS-2 in a weight ratio of 1.0 during the preparation of the liquid coating solution to provide identical sensitometric response.

The photographic data for Samples 204 - 205 show that the inventive high boiling solvent-free dispersion of cyan dye-forming coupler C-1 can be combined with silver halide grains that comprise lower iodide content to preserve sensitivity and increase the gamma response of the photographic unit, while the coverage of high boiling solvent is reduced affording thinner layers.

The photographic data for Sample 206 show that the gamma and density response of the photographic unit comprising the inventive high boiling solvent-free dispersion of cyan dye-forming coupler C-1 can be increased by a reduction in the level of development inhibiting releasing coupler employed in the layer. The photographic data for Samples 207 and 208 show that the inventive high boiling solvent-free dispersion of cyan dyeforming coupler C-1 can be combined with bleach accelerating releasing compound which provides increased layer developability and increases the gamma and maximum density of the red light sensitive unit. The photographic data for Sample 209 show that the inventive high boiling solvent-free dispersion of cyan dye-forming coupler C-1 can be employed with a development accelerating polymeric chemical to provide improved speed.

Example 9

Photographic Sample 301 (comparative control) A color photographic recording material for color negative development identical to Photographic Sample 201 was prepared. This film was hardened at coating with 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.

Sample 302 (invention) A color photographic recording material for color negative development was prepared exactly as for Sample 301 above, except where noted below. The cyan dye-forming coupler C-1 employed in the high sensitivity red-sensitive layer (Layer 4) and the medium sensitivity red-sensitive layer (Layer 3) was dispersed in the general manner of the inventive -50 example C in dispersion Example 1, without the presence of a high boiling solvent.

Layer 3: Medium Sensitivity Red-Sensitive Layer Changes HBS-2 0.000 Layer 4: High Sensitivity Red-Sensitive Layer Changes HBS-2 0.000 Sample 303 (invention) A color photographic recording material for color negative development was prepared exactly as Sample 301, except where noted below. The cyan dyeforming coupler C-1 employed in the high sensitivity red-sensitive layer (Layer 4) and the medium sensitivity red- sensitive layer (Layer 3) was dispersed in the general manner of the inventive example C in dispersion Example 1, without the presence of a high boiling solvent. A separate dispersion of HBS-2 was added to the liquid coating solutions of both layers to provide an equal coverage by weight to that of cyan dye-forming coupler C-1.

Sample 304 (invention) A color photographic recording material for color negative development was prepared exactly as Sample 301, except where noted below. The cyan dyeforming coupler C-1 employed 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 dispersed in the general manner of the inventive example C in dispersion Example 1, without the presence of a high boiling solvent. A separate dispersion of HBS-2 was added to the liquid coating solutions of all three layers to provide an equal coverage by weight to that of cyan dye-forming coupler C- 1.

Sample 305 (invention) A color photographic recording material for color negative development was prepared exactly as Sample 301, except where noted below. The cyan dye forming coupler C-1 employed in the high sensitivity red-sensitive layer (Layer 4) and the medium sensitivity red-sensitive layer (Layer 3) was dispersed in the general manner of the inventive example C in dispersion Example 1, without the presence of a high boiling solvent. The coverages of coupler C-1 were increased significantly.

Layer 3: Medium Sensitivity Red-Sensitive Layer Changes Cyan dye-forming coupler C-1 HBS-2 0.312 0.000 Layer 4: High Sensitivit Red-Sensitive Layer Changes CY Cyan dye-forming coupler C-1 HBS-2 0.183 0.000 Sample 306 (invention) A color photographic recording material for color negative development was prepared exactly as Sample 305, except where noted below. The development inhibitor releasing coupler D-5 in Layers 3 and 4 was replaced with D-9 in equimolar amounts. D-5 had been dispersed with HBS-4, however, while D-9 was dispersed with HBS-2. Accordingly, the coverage amounts for these solvents was also changed, but the overall solvent level was maintained relative to Sample 305.

The photographically useful group of D-9 comprising switch and inhibitor moieties released by the parent coupler has a higher tendancy to migrate out of the originating layer before releasing the inhibitor fragment relative to the photographically useful group of D-5, which in turn causes development retardation.

Layer 3: Medium Sensitivity Red-Sensitive Layer Changes Cyan dyeforming coupler C-1 DIR coupler D-5 DIR coupler D-9 HBS-2 HBS-4 0.312 0.000 0.011 0.022 0.000 Layer 4: High Sensitivity Red-Sensitive Layer Cyan dye-forming coupler C- 1 DIR coupler D-5 DIR coupler D-9 HBS-2 HBS-4 Changes 0.183 0.000 0.020 0.041 0.000 Samples of photographic recording materials Samples 301-306 were individually exposed for 1/5Q0 of a second to white light from a tungsten light source of 3200 K color temperature that was filtered by a Daylight Va filter to 5500 K through a graduated 0 - 4.0 density step tablet to determine their speed and gamma. The samples were then processed using the Kodak C-41 process.

Following processing and drying, Samples 301- 306 were subjected to Status M densitometry. The photographic performance of the recording materials is compared below in Table VII.

Table VII Red-Light Sensitive Unit Perfbimance Gradient Gamma Meter Density at D-min IR Speed Low Lowmid GAMMA.50 log H 0.286 342 0.552 0.623 0.630 2.26 0.294 340 0.473 0.494 0.505 1.96 0.300 341 0.497 0.580 0.610 2.19 0.290 342 0.501 0.586 0.618 2.20 0.298 341 0.488 0.507 0.520 2.01 0.293 343 0.504 0.545 0.570 2.10 Sample 301 (comparison) 302 (invention) 303 (invention) 304 (invention) 305 (invention) 306 (invention) The photographic data for Sample 302 show that the inventive high. boiling solvent-free dispersion of cyan dye-forming coupler C-1 provides reduced gamma and density formation performance following direct substitution for the comparative control dispersion employing di-n-butylphthalate in a weight ratio 1.0 to C-1 in the high and medium sensitivity red-sensitive layers of color negative recording material of Example 3. The photographic data for Sample 303 show that the inventive high boiling solvent-free, improved stability dispersion of cyan dye-forming coupler C-1 can be combined with a dispersion of HBS-2 in a weight ratio of 1.0 during the preparation of the liquid coating solution for both layers to provide nearly identical sensitometric response. The photographic data for Sample 304 show that the inventive high boiling solvent-free, improved stability dispersion of cyan dye-forming coupler C-1 can be combined with a dispersion of HBS-2 in a weight ratio of 1.0 during the preparation of the liquid coating solution for all three red-sensitive layers comprising coupler C-1 to provide identical nearly sensitometric response. The photographic data for Sample 305 show that the inventive high boiling solvent-free dispersion of cyan dye-forming coupler C-1 can be employed in higher laydowns in the absence of HBS-2 to improve the gamma response of the photographic unit, while the coverage of high boiling solvent is reduced affording thinner layers. The photographic data for Sample 306 show that the gamma and density response of the photographic unit comprising the inventive high boiling solvent-free dispersion of cyan dye-forming coupler C-1 can be increased by changing the properties of development inhibiting releasing coupler employed in the layer to select a compound that has higher interlayer than intralayer inhibition.

Example 10

A no-solvent coupler dispersion was prepared as follows. 3300 g of cyan coupler C-1 was dissolved in 6600 g of ethyl acetate at 710C. This oil phase solution was then combined with an aqueous phase solution consisting of 4400 g gelatin, 3520 g of a 10% solution of Alkanol-XC (Dupont) surfactant and 37,180 g of distilled water. This mixture was then passed through a Crepaco homogenizer one time at a pressure of 1500 psi followed by removal of ethyl acetate by evaporation. Distilled water was then added back to form Dispersion P which consisted of 6% coupler, 8% gel.

A high boiling solvent dispersion was prepared as follows. 4 g of Irganox1076 (Ciba-Geigy) hydrophobic additive was dissolved in 400 g of dibutylphthalate at 500C, then combined with an aqueous solution consisting of 400 g gelatin, 300 g of a 10% solution of Alkanol-XC (Dupont), 7.2 g of a 0.7% solution of Kathon LX (Rohm, and Haas) biocide, and 3488.8 g of distilled water, also at 500C. This mixture was then pre-mixed using a Silverson mixer for 5 min at 5000 rpm, then passed through a Crepaco homogenizer one time at 5000 psi to form Dispersion Q which consisted of 8% solvent, 8% gel.

Dispersions of other high-boiling solvents were prepared like Dispersion Q except that 400 g of dibutylphthalate was replaced with 400 g of another high boiling solvent as outlined in Table VIII below.

55- Table VIII

Dispersion High-Boiling Solvent Q U dibutylphthalate tricresylphosphate dibutylsebacate (formula II-1) oleyl alcohol (formula 111-5) phenylethylbenzoate (formula V-1) A coating solution was prepared as follows. 36.7 g of Dispersion P was added to 13.8 g of Dispersion Q with 12.6 g of 35% gelatin and 40.2 g of distilled water. The mixture was heated to 400C for 1 hour with stirring to form coating solution QQ which consisted of 2.2% coupler, 1.1% solvent, and 8.4% gel.

Coating solutions containing dispersions of other high-boiling solvents were also similarly prepared as outlined in Table IX below. Coating solution PP, which contained no added solvent, was also included as a control.

Coupling rate constants (k) for the reaction of coupler with oxidized color developing agent CD-4 were measured for these coating solutions using an aqueous competition test with sulfite ion as described in Cols. 22-23 of U.S. Pat. No. 5,089,380. Results are reported in units of m-1 sec-1 and are included in Table IX.

Table IX

Coating Dispersions Coupler Solvent Coupler Solution Reactivity (k) pp p 540 QQ P, Q dibutylphthalate 3620 RR P, R tricresylphosphate 1104 ss P, S Formula 11-1 5000 (Invention) dibutylsebacate TT P, T Formula 111-5 5519 (Invention) oleyl alcohol uu P, U Formula V-1 5538 (Invention) phenylethylbenzoate These results clearly demonstrate that the solvents of the present invention provide higher coupler reactivity than the solvents employed in the prior art when used at low levels according to the method of the present invention.

EXAMPLE 11

Sample 401 (comparative control) A color photographic recording material for color negative development was prepared by applying the following layers in the given sequence to a transparent support of cellulose triacetate. The side of the support to be coated had been prepared by gelatin subbing. The quantities of silver halide are given in g of silver/m2. The quantities of other materials are given in g/m2. The cyan dye-forming coupler C-1 employed in the red- sensitive layer was dispersed with 20 a ratio of high boiling solvent HBS- 2, di-nbutylphthalate, to coupler of 1.0.

Layer 1: Antihalation Layer uv-l UV-2 oxidized developer scavenger DOXS-4 Compensatory printing density cyan dye CD-2 Compensatory printing density magenta dye MD-2 Compensatory printing density yellow dye MM-1 HBS-2 HBS-1 HBS-5 Disodium salt of 3,5-disulfocatechol Gelatin Black colloidal silver sol Layer 2: Red-Sensitive Layer This layer comprised a blend of a lower sensitivity, red-sensitized tabular silver iodobromide emulsion 0.038 0.038 0.108 0.016 0.043 0.097 0.237 0.172 0.060 0.270 2.441 0.151 (1.3% iodide, average grain diameter 0.53 micrometers and thickness 0.09 micrometers thick) and a higher sensitivity, red-sensitized tabular silver iodobromide emulsion (4.1% iodide, average grain diameter 1.04 micrometers and thickness 0.09 micrometers). Lower sensitivity emulsion Higher sensitivity emulsion Bleach accelerator coupler BAR-1 Cyan dye- forming coupler C-1 Cyan dye-forming magenta colored coupler CM-1 Oxidized developer scavenger DOXS-2 HBS-2 HBS-3 TAI Gelatin Layer 3: Ultraviolet Filter Layer Dye UV-1 Dye UV-2 Unsensitized silver bromide Lippmann emulsion HBS-5 Gelatin Layer 4: Protective Overcoat Layer Polymethylmethacrylate matte beads Soluble polymethylmethacrylate matte beads Silicone lubricant Gelatin 0.409 0.441 0.038 0.538 0.027 0.010 0.538 0.038 0.015 1.722 0.108 0.108 0.215 0.172 0.699 0.005 0.054 0.039 0.888 This film was hardened at coating with 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 402 (comparative control) A color photographic recording material for color negative development was prepared exactly as Sample 401 above, except where noted below. The cyan dye-forming coupler C-1 employed in the red-sensitive layer of Sample 401 was dispersed in the general manner of example P in dispersion Example 10, without the presence of a high boiling solvent.

HBS-2 Layer 2: Red-Sensitive Layer Changes Photographic Sample 403 (comparative control) 0.000 A color photographic recording material for color negative development was prepared exactly as Sample 402, except where noted below. A separate dispersion of HBS-2 dispersed in the general manner of dispersion Q of Example 10 was added to the liquid coating solution of the red-sensitive layer, Layer 2, comprising coupler C-1 dispersed in the general manner of dispersion P in Example 10 to provide a 25% coverage by weight to that of cyan dye-forming coupler C-1.

HBS2 Layer 2: Red-Sensitive Layer Changes Photographic Sample 404 (comparative control) 0.135 A color photographic recording material for color negative development was prepared exactly as Sample 402, except where noted below. A separate dispersion of HBS-2 dispersed in the general manner of dispersion Q of Example 10 was added to the liquid coating solution of layer 2 comprising coupler C-1 dispersed in the general manner of dispersion P in Example 10 to provide 50% coverage by weight to that of cyan dye-forming coupler C-1.

HBS-2 Layer 2: Red-Sensitive Layer Changes Photographic Sample 405 (comparative control) 0.269 A color photographic recording material for color negative development was prepared exactly as Sample 402, except where noted below. A separate dispersion of HBS-2 dispersed in the general manner of dispersion Q of Example 10 was added to the liquid coating solution of layer 2 comprising coupler C-1 dispersed in the general manner of dispersion P in Example 10 to provide equal coverage by weight to that of cyan dye-forming coupler C-1.

HBS-2 Layer 2: Red-Sensitive Layer Changes Photographic Sample 406 (invention) 0.538 A color photographic recording material for color negative development was prepared exactly as Sample 402, except where noted below. A separate dispersion of high boiling solvent HBS-9 (dibutylsebacate of formula II- 1) dispersed in the general manner of dispersion S of Example 10 was added to the liquid coating solution of layer 2 comprising coupler C-1 dispersed in the general manner of dispersion P in Example 10 to provide 25% coverage by weight to that of cyan dye-forming coupler C-1.

HBS-9 HBS-2 Layer 2: Red-Sensitive Layer Changes 0.129 0.0 Photographic Sample 407 (invention) A color photographic recording material for color negative development was prepared exactly as Sample 402, except where noted below. A separate dispersion of HBS-9 dispersed in the general ma=er of dispersion S of Example 10 was added to the liquid coating solution of layer 2 comprising coupler C-1 dispersed in the general manner of dispersion P in Example 10 to provide 50% coverage by weight to that of cyan dye-forming coupler C-1.

HBS-9 HBS-2 Layer 2: Red-Sensitive Layer Changes 0.269 0.0 Photographic Sample 408 (comparative control) A color photographic recording material for color negative development was prepared exactly as Sample 402, except where noted below. A separate dispersion of HBS-9 dispersed in the general marmer of dispersion S of Example 10 was added to the liquid coating solution of layer 2 comprising coupler C-1 dispersed in the general manner of dispersion P in Example 10 to provide equal coverage by weight to that of cyan dye-forming coupler C-1.

HBS-9 HBS-2 Layer 2: Red-Sensitive Layer Changes 0.538 0.0 Samples of photographic recording materials Sample 401-408 were individually exposed for 1/50 of a second to white light from a tungsten light source of 32000 K color temperature that was filtered by a Daylight Va filter to 55000 K and a KODAK WRATTEN GELATIN Filter (#9) through a graduated 0-4.0 density step tablet to determine their speed and gamma. The samples were then processed using a color negative process, the Kodak C-41 process, as described by the 1988 Annual of the British Journal of Photography, pages 196-198. Another description of the use of the

C-41 Flexicolor Process can be found in "Using KODAK FLEXICOLOR Chemicals", Publication Z-131, Eastman Kodak Company, Rochester, NY. (KODAK is a trademark of the Eastman Kodak Company, U.S.A.). Following processing and drying, Samples 401- 408 were subjected to Status

M densitometry. The photographic performance of the recording materials is compared below in Table X.

Table X

Red-Light Sensitive Unit Performance MODEL G Solvent/C-1 Gradient Layer 2 Ratio- in Meter Gamma Den. at Den. at Dispersions Layer 2 (Ratio of -0.9 logH 0.3 logH HBS-9/HB5-2) Sample 401 C-1 in 1.0 1.45 1.29 2.01 (control) HBS-2 402 C-1 as P 0 1.02 1.02 1.67 (control) 403 C-1 as P + 0.25 1.22 1.17 1.94 (control) HBS-2 as Q 404 C-1 as P + 0.50 1.35 1.27 1.97 (control) HBS-2 as Q 405 C-1 as P + 1.0 1.48 1.34 1.98 (control) HBS-2 as Q 406 C-1 as P + 0.25 1.34 1.24 1.98 (invention) HBS-9 as S (1.10) 407 C-1 as P + 0.50 1.40 1.31 2.02 (invention) HBS-9 as S (1.04) 408 C-1 as P + 1.0 (control) HBS-9 as S 1.47 1.35 2.05 (0.99) The photographic data for Sample 402 show that the high boiling solvent- free dispersion of cyan dye-forming coupler C-1 provides much lower gamma and upperscale density formation performance following direct substitution for the comparative control dispersion employing HBS-2, di-n- butylphthalate, in a weight ratio 1.0 to C-1 in the red-sensitive layer of the color negative recording material of Example 401.

The photographic data for Sample 403 and 404 show that the comparative high boiling solvent of the art, HBS-2, when combined with the solvent-free dispersion of cyan dye-forming coupler C-1 in a weight ratio of 0.25-0.50 during the preparation of the liquid coating solutions, still gives reduced density formation response. Comparative control Sample 405 gives essentially the same result as Sample 401, indicating that method of combining the solvent-free dispersion of coupler C-1 with the dispersion of high boiling solvent HBS-2 in the liquid coating solution of the red-sensitive layer yields about the same performance as making a conventional dispersion of C-1 and HBS-2 at the normal ratio of 1.0. Under identical conditions of usage at the lower solvent-to-coupler ratios in Samples 406 and 407, the inventive combination of solvent HBS-9 dispersed in the manner of dispersion S of Example 10 and coupler C1 dispersed solvent-free in the manner of dispersion P give increased gamma response and density formation 30 relative to the respective controls, 403 and 404. Under the usual conditions of solvent-to-coupler ratio of 1.0 however, the combination of HBS-9 and C-1 is observed to function equivalently to that with HBS-2. The benefit of the invention is thus seen to appear at a solvent-to-coupler ratio by weight of about 0.5, and the improvement increases as the ratio decreases, as noted in Table X by the ratio of relative gamma performance for the HBS-9 films compared to the corresponding HBS-2 f ilms. The gamma ratio is about unity at the usual solvent-to-coupler ratio of 1.0, and a performance advantage of fully 10% is gained by using HBS-9 at the solvent- to-coupler ratio of 0.25, matching the performance of a twofold higher level of HBS-2. In this fashion, the improved crystallization stability of the solvent-free dispersion of C-1 is enjoyed, while the reduced solvent load afforded by the use of the inventive high boiling solvents with C-1 allows for reduced materials 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 applying the following layers in the given sequence to a transparent support of cellulose triacetate. The side of the support to be coated had been prepared by gelatin subbing. The quantities of silver halide are given in g of silver/m2. The quantities of other materials are given in q/M2. The cyan dye-forming coupler C-1 employed in the low, medium, and high sensitivity redsensitive layers was dispersed with a ratio of high boiling solvent HBS-2, di-n-butylphthalate, to coupler of 1.0.

Layer 1: Antihalation Layer uv- 1 UV-2 Oxidized developer scavenger DOXS-3 Compensatory printing density cyan dye CD-1 Compensatory printing density magenta dye MD-2 Compensatory printing density yellow dye MM-1 Compensatory printing density yellow dye YD-2 0.075 0.075 0.162 0.020 0.042 0.088 0.008 HBS-1 HBS5 Disodium salt of 3,5-disulfocatechol Gelatin Black colloidal silver sol Layer 2: Low Sensitivity Red-Sensitive Layer This layer comprised a blend of a lower sensitivity, red-sensitized tabular silver iodobromide emulsion (1.3% iodide, average grain diameter 0.53 micrometers 0.426 0.151 0.270 2.441 0.151 and thickness 0.09 micrometers thick) and a higher sensitivity, red- sensitized tabular silver iodobromide emulsion (4.1% iodide, average grain diameter 1.04 micrometers and thickness 0.09 micrometers). Lower sensitivity emulsion Higher sensitivity emulsion Bleach accelerator coupler BAR-1 Cyan dyeforming coupler C-I Cyan dye-forming magenta colored coupler CM-1 Oxidized developer scavenger DOXS-2 HBS-2 HBS-3 TAI Gelatin 0.495 0.431 0.038 0.517 0.027 0.010 0.517 0.038 0.015 1.775 Layer 3: Medium Sensitivity Red-Sensitive Layer Redsensitized tabular silver iodobromide emulsion (4.1 mol % iodide, average grain diameter 1.39 micrometers and thickness 0.12 micrometers). Emulsion DIR coupler D-5 Cyan dye- forming magenta colored coupler CM-1 Cyan dye-forming coupler C-1 HBS-2 HBS-4 TAI Gelatin Layer 4: High Sensitivity Red-Sensitive Layer Red-sensitized, tabular silver iodobromide emulsion (4.1 mol % iodide, average grain diameter 2.93 micrometers and thickness 0.13 micrometers).

0.700 0.011 0.022 0.215 0.215 0.022 0.011 1.786 Emulsion DIR coupler D-5 DIR coupler D-6 Cyan dye-forming magenta colored coupler CM-1 Cyan dye-forming coupler C-1 HBS-1 HBS-2 HBS-4 TAI Gelatin Gelatin 1.076 0.020 0.048 0.032 0.139 0.194 0.139 0.041 0.010 1.711 Layer 5:1nterlayer Layer 6: Low Sensitivity Green-Sensitive Layer This layer comprised a blend of lower sensitivity, green-sensitized tabular silver iodobromide emulsion (1. 3 mol % iodide, average grain diameter 0. 53 1.292 micrometers and thickness 0.09,micrometers) and higher sensitivity, green-sensitized tabular silver iodobromide emulsion (4.1 mol % iodide, average grain diameter 1.04 micrometers and thickness 0.09 micrometers). Lower sensitivity emulsion Higher sensitivity emulsion Magenta dye-forming yellow colored coupler MM-2 Magenta dye-forming coupler M-4 oxidized developer scavenger DOXS-2 HBS-1 TAI Gelatin 0.581 0.312 0.065 0.269 0.023 0.345 0.014 1.723 Layer 7: Medium Sensitivity Green-Sensitive Layer Green-sensitized tabular silver iodobromide emulsion (4.1 mol % iodide, average grain diameter 1.23 micrometers and thickness 0.12 micrometers). Emulsion DIR coupler D-5 Magenta dye-forming yellow colored coupler MM-2 Magenta dye-forming coupler M-4 oxidized developer scavenger DOXS-2 HBS-1 0.969 0.024 0.065 0.070 0.019 0.186 HBS-4 TAI Gelatin Layer 8: High Sensitivity Green-Sensitive Layer 0.048 0.014 1.399 Green-sensitized, tabular silver iodobromide emulsion (4.1 mol % iodide, average grain diameter 2.19 micrometers and thickness 0.13 micrometers) Emulsion DIR coupler D-3 DIR coupler D-7 Magenta dye-forming yellow colored coupler MM-2 Magenta dye- forming coupler M-4 Oxidized developer scavenger DOXS-2 HBS-1 HBS-2 TAI Gelatin Layer 9: Yellow Filter Layer Yellow filter dye YD-1 Gelatin Layer 10: Low Sensitivity Blue-Sensitive Layer This layer comprised a blend of lower sensitivity, blue-sensitized tabular silver iodobromide emulsion (1.3 mol % iodide, average grain diameter 0.53 micrometers and thickness 0.09 micrometers), medium 0.969 0.011 0.011 0.054 0.058 0.016 0.176 0.011 0.012 1.291 0.108 1.292 sensitivity, tabular blue-sensitized silver iodobromide emulsion (4.1 mol % iodide, average grain diameter 0.80 micrometers and thickness 0.09 micrometers) and higher sensitivity, tabular blue-sensitized silver iodobromide emulsion (6.0 mol % iodide, average grain diameter 0.96 micrometers and thickness 0.26 micrometers). Lower sensitivity emulsion medium sensitivity emulsion Higher sensitivity emulsion DIR coupler D-8 Yellow dye-forming coupler Y-1 Yellow dye-forming coupler Y-2 Bleach accelerator coupler BAR-1 Cyan dye-forming coupler C-1 Oxidized developer scavenger DOXS-2 0.269 0.172 0.549 0.065 0.280 0.700 0.003 0.027 0.005 HBS-2 HBS3 TAI Gelatin Layer ll: High Sensitivity Blue-Sensitive Layer This layer comprised a blend of lower sensitivity, 0.931 0.003 0.016 2.519 blue-sensitized silver iodobromide emulsion (9.0 mol % iodide, average grain diameter 1.06 micrometers) and higher sensitivity, tabular blue-sensitized silver iodobromide emulsion (4.1 mol % iodide, average grain diameter 3.37 micrometers and thickness 0.14 micrometers). Low sensitivity emulsion High sensitivity emulsion Yellow dye-forming coupler Y-1 Yellow dye-forming coupler Y-2 DIR coupler D-8 Bleach accelerator coupler BAR-1 Cyan dye-forming coupler C-1 oxidized developer scavenger DOXS-2 HBS-2 HBS-3 TAI Gelatin 0.226 0.570 0.080 0.200 0.048 0.005 0.029 0.001 0. 317 0.005 0.013 1.580 Layer 12: Ultraviolet Filter Layer Dye UV-1 Dye UV-2 Unsensitized silver bromide Lippmann emulsion HBS-5 Gelatin Layer 13: Protective Overcoat Layer Polymethylmethacrylate matte beads Soluble polymethylmethacrylate matte beads Silica gel particles Silicone lubricant Gelatin 0.108 0.108 0.215 0.215 0.699 0.005 0.054 0.108 0.039 0.888 This film was hardened at coating with 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 502 (comparative control) A color photographic recording material for color negative development was prepared exactly as Sample 501 above, except where noted below. The cyan dye-forming coupler C-1 employed in the red-sensitive layers 2, 3, and 4 was dispersed in the general manner of example P in dispersion Example 10, without the presence of a high boiling solvent.

Layer 2: Low Sensitivity Red-Sensitive Layer Changes HBS-2 0.000 Layer 3: Medium Sensitivity Red-Sensitive Layer Changes HBS-2 0.000 Layer 4: High Sensitivity Red-Sensitive Layer Changes HBS-2 0.000 Photographic Sample 503 (comparative control) A color photographic recording material for color negative development was prepared exactly as Sample 502, except where noted below. A separate dispersion of HBS-1 dispersed in the general manner of dispersion R of Example 10 was added to the liquid coating solutions of layers 2, 3, and 4 comprising coupler C-1 dispersed in the general manner of dispersion P in Example 10 to provide an equal coverage by weight to that of cyan dye-forming coupler C-1.

Layer 2: Low Sensitivity Red-Sensitive Layer Changes HBS-1 0.517 HBS-2 0.0 Layer 3: Medium Sensitivity Red-Sensitive Layer Changes HBS-1 HBS-2 0.215 0.0 Layer 4: High Sensitivity Red-Sensitive Layer Changes HBS-1 HBS-2 0.334 0.0 Photographic Sample 504 (comparative control) A color photographic recording material for color negative development was prepared exactly as Sample 502, except where noted below. A separate dispersion of HBS-2 dispersed in the general manner of dispersion Q of Example 10 was added to the liquid coating solutions of layers 2, 3, and 4 comprising coupler C-1 dispersed in the general manner of dispersion P in Example 10 to provide 25% coverage by weight to that of cyan dye-forming coupler C-1.

Layer 2: Low Sensitivity Red-Sensitive Layer Changes HBS-2 0.129 Layer 3: Medium Sensitivity Red-Sensitive Layer Changes HBS-2 0.054 Layer 4: High Sensitivity Red-Sensitive Layer Changes HBS2 0.035 Photographic Sample 505 (comparative control) A color photographic recording material for color negative development was prepared exactly as 25 Sample 502, except where noted below. A separate dispersion of HBS-2 dispersed in the general manner of dispersion Q of Example 10 was added to the liquid coating solutions of layers 2, 3, and 4 comprising coupler C-1 dispersed in the general manner of 30 dispersion P in Example 10 to provide 50% coverage by weight to that of cyan dye-forming coupler C-1.

Layer 2: Low Sensitivity Red-Sensitive Layer Changes HBS-2 0.258 Layer 3: Medium Sensitivity Red-Sensitive Layer Changes HBS-2 0.108 Layer 4: High Sensitivity Red-Sensitive Layer Changes HBS-2 0.070 Photographic sample 506 (comparative control) A color photographic recording material for color negative development was prepared exactly as Sample 502, except where noted below. A separate dispersion of HBS-2 dispersed in the general manner of dispersion Q of Example 10 was added to the liquid coating solutions of layers 2, 3, and 4 comprising coupler C-1 dispersed in the general manner of dispersion P in Example 10 to provide equal coverage by weight to that'of cyan dye-forming coupler C-1.

Layer 2: Low Sensitivity Red-Sensitive Layer Changes HBS-2 0.517 Layer 3: Medium Sensitivity Red-Sensitive Layer Changes HBS-2 0.215 Layer 4: High Sensitivity Red-Sensitive Layer Changes HBS-2 0.139 Photographic Sample 507 (invention) A color photographic recording material for color negative development was prepared exactly as Sample 502, except where noted below. A separate dispersion of high boiling solvent HBS-6 (formula III 5) dispersed in the general manner of dispersion T of Example 10 was added to the liquid coating solutions of layers 2, 3, and 4 comprising coupler C-1 dispersed in the general manner of dispersion P in Example 10 to provide 25% coverage by weight to that of cyan dyeforming coupler C-1.

Layer 2: Low Sensitivity Red-Sensitive Layer Changes HBS-6 HBS-2 0.129 0.0 Layer 3: Medium Sensitivity Red-Sensitive Layer Changes HBS-6 I-IBS-2 0.054 0.0 Layer 4: High Sensitivity Red-Sensitive Layer Changes HBS-6 HBS-2 0.035 0.0 Photographic Sample 508 (invention) A color photographic recording material for color negative development was prepared exactly as Sample 502, except where noted below. A separate dispersion of HBS-6 dispersed in the general manner of dispersion T of Example 10 was added to the liquid coating solutions of layers 2, 3, and 4 comprising coupler C-i dispersed in the general manner of dispersion P in Example 10 to provide 50% coverage by 20 weight to that of cyan dye- forming coupler C-1.

Layer 2: Low Sensitivity Red-Sensitive Layer Changes HBS-6 HBS-2 0.258 0.0 Layer 3: Medium Sensitivity Red-Sensitive Layer Changes HBS-6 HBS-2 0.108 0.0 HBS-6 HBS-2 Layer 4: High SeLsitivity Red-Sensitive Layer Changes 0.070 0.0 Photographic Sample 509 (invention) A color photographic recording material for color negative development was prepared exactly as Sample 502, except where noted below. A separate dispersion of high boiling solvent HBS-7 (formula V-1) dispersed in the general manner of dispersion U of Example 10 was added to the liquid coating solutions of layers 2, 3, and 4 comprising coupler C-1 dispersed in the general manner of dispersion P in Example 10 to provide 25% coverage by weight to that of cyan dye- forming coupler C-1.

HBS-7 HBS-2 Layer 2: Low Sensitivity Red-Sensitive Layer Changes 0.129 0.0 Layer 3: Medium Sensitivity Red-Sensitive Layer Changes HBS-7 HBS-2 0.054 0.0 Layer 4: High Sensitivity Red-Sensitive Layer Changes HBS-7 HBS-2 0.035 0.0 Photographic Sample 510 (invention) A color photographic recording material for color negative development was prepared exactly as Sample 502, except where noted below. A separate dispersion of HBS-7 dispersed in the general manner of dispersion U of Example 10 was added to the liquid coating solutions of layers 2, 3, and 4 comprising coupler C-1 dispersed in the general manner of dispersion P in Example 10 to provide 50% coverage by weight to that of cyan dye-forming coupler C-1.

Layer 2: Low Sensitivity Red-Sensitive Layer Changes HBS-7 HBS-2 0.258 0.0 HBS-7 HBS-2 Layer 3: Medium Sensitivity Red-Sensitive Layer Changes 0.108 0.0 Layer 4: High Sensitivity Red-Sensitive Layer Changes HBS-7 HBS-2 is 0.070 0.0 Photographic Sample 511 (invention) A color photographic recording material for color negative development was prepared exactly as Sample 502, except where noted below. A separate dispersion of. high boiling solvent HBS-8 (formula IV-1) 10 was added to the liquid coating solutions of layers 2, 3, and 4 comprising coupler C-1 dispersed in the general manner of dispersion P in Example 10 to provide 25% coverage by weight to that of cyan dye-forming coupler C-1.

Layer 2: Low Sensitivity Red-Sensitive Layer Changes HBS-8 HBS-2 0.129 0.0 Layer 3: medium Sensitivity Red-Sensitive Layer Changes HBS-8 HBS-2 0.054 0.0 Layer 4: High Sensitivity Red-Sensitive Layer Changes HBS-8 HBS-2 0.035 0.0 Photographic Sample 512 (invention) A color photographic recording material for color negative development was prepared exactly as 25 Sample 502, except where noted below. A separate dispersion of HBS-8 was added to the liquid coating solutions of layers 2, 3, and 4 comprising coupler C-1 dispersed in the general manner of dispersion P in Example 10 to provide 50% coverage by weight to that of 30 cyan dye-forming coupler C-1.

Layer 2: Low Sensitivity Red-Sensitive Layer Changes HB5-8 0.258 HBS-2 0.0 Layer 3: Medium Sensitivity Red-Sensitive Layer Changes HBS-8 0.108 HBS-2 0.0 Layer 4: High Sensitivity Red-Sensitive Layer Changes HBS-8 HBS-2 0.070 0.0 Photographic Sample 513 (invention) A color photographic recording material for color negative development was prepared exactly as Sample 502, except where noted below. A separate dispersion of high boiling solvent HBS-9 (formula II-1) dispersed in the general manner of dispersion S of Example 10 was added to the liquid coating solutions of layers 2, 3, and 4 comprising coupler C-1 dispersed in the general manner of dispersion P in Example 10 to provide 25% coverage by weight to that of cyan dyeforming coupler C-1.

Layer 2: Low Sensitivity Red-Sensitive Layer Changes HBS-9 HBS-2 0.129 0.0 Layer 3: Medium Sensitivity Red-Sensitive Layer Changes HBS-9 HBS-2 0.054 0.0 Layer 4: High Sensitivity Red-Sensitive Layer Changes HBS-9 HBS-2 0.035 0.0 Photographic Sample 514 (invention) A color photographic recording material for color negative development was prepared exactly as Sample 502, except where noted below. A separate dispersion of HBS-9 dispersed in the general manner of dispersion S of Example 10 was added to the liquid coating solutions of layers 2, 3, and 4 comprising coupler C-1 dispersed in the general manner of dispersion P in Example 10 to provide 50%. coverage by weight to that of cyan dye- forming coupler C-1.

Layer 2: Low Sensitivity Red-Sensitive Layer Changes HBS-9 HBS-2 0.258 0.0 Layer 3: Medium Sensitivity Red-Sensitive Layer Changes HBS-9 HBS-2 0.108 0.0 Layer 4: High Sensitivity Red-Sensitive Layer Changes HBS-9 HBS-2 0.070 0.0 Samples of photographic recording materials Sample 501-514 were individually exposed for 1/500 of a second to white light from a tungsten light source of 32000 K color temperature that was filtered by a Daylight Va filter to 55000 K through a graduated 0-4.0 density step tablet to determine their speed and gamma. The samples were then processed using the color negative process, the KODAY, C-41 process, as described by the 1988 Annual of the British Journal of Photography, pages 196-198. Following processing and drying, Samples 501-514 were subjected to Status M densitometry. The photographic performance of the recording materials is compared below in Table XI.

Table XI Red-Light Sensitive Unit Performance Solvent/C-1 Low-mid Density Sample Layer 2, 3, & 4 Ratio In Scale at Dispersions Layers 2-4 Gamma.5 log H 501 C-1 dispersed 1.0 0.62 2.30 (control) in HBS-2 502 C-1 dispersed 0 0.35 1.49 (control) as P 503 C-1 as P + 1.0 0.47 1.82 (control) HBS-1 as R 504 C-1 as P + 0.25 0.44 1.69 (control) HBS-2 as Q 505 C-1 as P + 0.50 0.50 1.89 (control) HBS-2 as Q 506 C-1 as P + 1.0 0.60 2.19 (control) HBS-2 as Q 507 C-1 as P + 0.25 0.56 2.04 (invention) HBS-6 as T 508 C-1 as P + 0.50 0.68 2.41 (invention) HBS-6 as T 509 C-1 as P + 0.25 0.45 1.72 (invention) HBS-7 as U 510 C-1 as P + 0.50 0.53 1.97 (invention) HBS-7 'as U 511 C-1 as P + 0.25 0.50 1.84 (invention) HBS8 512 C-1 as P + 0.50 0.59 2.14 (invention) HBS-8 513 C1 as P + 0.25 0.51 1.92 (invention) HBS9 as S 514 C-1 as P + 0.50 0.63 2.20 (invention) HBS-9 as S The photographic data for Sample 502 show that the high boiling solvent-free dispersion of cyan dye-forming coupler C-1 provides much lower gamma and upperscale density formation performance following direct substitution for the comparative control dispersion employing HBS-2, di-n-butylphthalate, in a weight ratio 1.0 to C-1 in the high, medium, and low sensitivity red- sensitive layers of color negative recording material of Example 501. The photographic data for Sample 503 show that the comparative high boiling solvent of the art, HBS-1, when combined with the solvent-free dispersion of cyan dye-forming coupler C-1 in a weight ratio of 1.0 during the preparation of the liquid coating solutions, gives an inferior sensitometric response. Comparative control examples 504 and 505 reveal that significantly reduced gamma and upperscale density formation performance follow diminution of the HBS-2 levels from the comparative control dispersion employing HBS-2 in a weight ratio 1.0 to C-1 in the high, medium, and low sensitivity red-sensitive layers of color negative recording material of Example 501. Comparative control Example 506 gives essentially the same result as Example 501, indicating that the method of combining the solventfree dispersion of coupler C-1 with the dispersion of high boiling solvent HBS-2 in the liquid coating solutions of the slow, medium, and fast red-sensitive layers yields about the same performance as making a conventional dispersion of C-1 and HBS-2 at the normal ratio of 1.0.

All of the inventive Examples, 507-514, employing the high boiling solvents HBS-6, HBS-7, HBS8, or HBS-9 at ratios of 0.25 or 0.50 of solvent to coupler, produce superior photographic performance in the aggregate of the gamma position and maximum density of the present characteristic curve relative to the solvent of the art HBS-2 under identical conditions of usage. In fact, solvents HBS-6, HBS-8, and HBS-9 in combination with C-1 give equivalent or superior gamma and density formation performance at a solvent/C-1 weight ratio of 0.50 as does HBS-2 at the usual ratio of 1.0 in comparative control Example 506.

HBS-1 tricresylphosphate HBS-2 di-n-butylphthalate HBS-3 N,N-diethyllauramde HBS-4 N-n-butylacetanilide HBS-5 1,4-cyclohexylenedimethylenebis(2ethylhexanoate) HBS-6 oleyl alcohol (formula 111-5) HBS-7 phenylethylbenzoate (fomula V-1) HBS-8 p-dodecylphenol (formula IV-1) HBS-9 di-n-butylsebecate (formula II-1) OH D-1 D-2 C ONH S N'kN- H 1 1 C6 5 N N OH CONH-P 0 N02 H 2 S-l 0C14H29-n 0C14 H2.-n N-N N-N 1 -;k'2-C\: -OCH3 0 H D-3 t-CHll-p-OCHCNH-C-N-N 1 - 1 1 k.;2H5 CsHil-t S NN 0 0 cl 11 11 - D-4 (CH3) 3CCCHCNH- NHS02C,,H33-n H2NC2H5 cc =C-S-- N02 N-N 1 112U2C,,H,-n D-5 0 H Isz ONH-P 0C.4H2.-n 0 fN02 C H 2 S-<1 1,-N OH D-6 ., 1 -CONH-b C- NJ''N- C 2 H 5 N7-N cl 0C,.H.9-n D-7 NJ""N-CH--CONH--0 C02CHCO2C.2H2.-n L 1 J2 C02C6H5 CH3 cl C4Hg-t 1 LOCHCONH- D-8 1 - C2H5 0 NHSO.C H33-n N SCONCH2 N-N U 2 L: 3 k-'7-n NO2 OH D-9 0C12H2.-n CONH- 0 CH3 CH2CO2C3H7-n 1 CH2S N-N D-10 cm- 1 c 0 0 t-C4H9 N-6 1 _ NHS H -n 0 02C16 33 H CH2N (C2H.) CO NO OH 2 S 1 / -CH2 N-:--N 1 OCH, C5H11-t -CONH (CH2) 40- C-- / 0 N OHNHCOCH -- CJ - 11 3 N i HO, S SO,H OH BAR- 1 CONH (CH2) 4 0- SH11-t # C5H11-t SCH2CH2CO2H M-1 M-2 M-3 cl IQ cl - Cl.5 0 HCO'AHCOCH2 1 t-HI, c "" Cr>H11-t cl cl H C 0.' HCOCHC2H5 1 U t-H11C5-, C H -n 1 12 25 CHO-G-NHS0 2 N-N--i C H c 1 H H 0 C C5H11-t M-4 mm- 1 MM-2 c 1 1 c 1 cl N-N Ot:5NH--0 S &NHCOCHC2H5 1 U NHCOC.3H27 C5HI,-T C5H11-t C5H11-t H 1 t-C5H,,-- o-CHCONH CH30-0-N=N;jNHCO 0 cl cl c 1 c 1 c 1-C- 0 0 1 - cl N NHCOCHO OH --Q- N- CH3 1 C.2H2.-n C4Hg-t OCH3 cl Y-1 CH30 COCHCONH- 0:: l 0 N C2H50 CH2C6H5 Y-2 YD-1 YD-2 t-C4H9 0 0 cl C02C12H25 0 0 C2H50 CH2-0 NHS02C4H.-n 1 W H 0 co>-C 0 cl uv-l NC cl N NHCO-, C 1 0 CH N (C2H5) 2 -",C 6 H 13 Y"' 1 C N L 6 113 C02C12H2.-n NHCOCH 20 1 -CSH11-t C5H11-t UV-2 CH30-CC-CH=C (CN) C02C3H7 0 CD-1 CD-2 MD- 1 H 3 c CONR N N..I c 2 HS 2 H 4 OH t-H 11 c 5 1 0C12H25 0 1 1 NHCONH-C-CN n-C 4 H 9- CHCONH 1 N CH 3 N-C 2 H5 1 c H t Ukt 2 Uki 2 OH OH CONH (CH2) 40-P-C5H11 H11C5 N= & COCH3 cl mD-2 DOXS-1 DOXS-2 cl NHCO-9 cl 0 N HO-O-OH CH3 1 N(C2H5)C2H40H CH (CH3) (CH2) 9CH3 CH (CH3) (CH2) 9CH3 OH HO S 1 HC.6H33-n 1 c'- r' 3 OH OH DOXS-3 H S 0 0C12H2.-n 1 NHS02--0C12H25 - n NHCOCH20 1 -CSH11-t USH11-t 0 DOXS-4 C.H17-n OH H 0 -" 0 C.H17-n H-1 bis(vinylsulfonyl) methyl ether H-2 bis(vinylsulfonyl) methane CHEM-1 Poly(2,2'-thiodiethylene glutarate) TAI 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene

Claims (15)

What is claimed is:

1. A silver halide color photographic light sensitive element comprising a support bearing a hydrophilic colloid layer comprising a phenolic cyan coupler of Formula I and a high-boiling organic solvent of formula 11, 111, IV or V:

OH 0 R3 NHC(NH)nRj Formula I R2CRN:1 11 0 X wherein Rl and R2 each represent an aliphatic-group, an aromatic group, or a heterocyclic group, R3 represents a hydrogen atom, a halogen atom, an aliphatic group, or an acylamino group, X represents a hydrogen atom or a group capable of being released upon a coupling reaction with oxidation product of a developing agent, and n represents 0 or 1; Ri-- (CH 2)-F- Rs Formula 11 wherein R4 and R5 each represent an alkoxycarbonyl group containing not more than 8 carbon atoms, and m is an integer from 1 to 10; T7 RC-V-OH Formula Ill R, wherein R6 represents an alkyl group or an alkenyl group, and R7 and R8 are individually selected from hydrogen and the group of moieties from which R6 is selected, provided that the total number of carbon atoms contained in R6, R7, and R8 is at least 10; R9 OH R, / Formula IV wherein R9 and RIO are hydrogen or straight chain or branched chain alkyl groups, at least one of R9 or RIO being a straight chain or branched chain alkyl group, the total number of carbon atoms in R9 plus RIO being from 9 to 20, and RIO being in the para or meta position with respect to the phenolic hydroxyl group; fl 6OR 11 1 R12 Formula V wherein R11 represents an aliphatic group, an aromatic group, or a heterocyclic group, and R12 represents a hydrogen atom, a hydroxy group, an alkoxy group, or an aliphatic group; wherein the weight ratio in said hydrophilic colloid layer of the weight of high-boiling organic solvent of formula II, III, IV and V relative to the weight of coupler of formula I is from 0.1 to 0.5.

2. An element according to Claim 1, wherein the high-boiling organic solvent is of Formula II.

3. An element according to Claim 1, wherein the high-boiling organic solvent is of Formula III.

4. An element according to Claim 1, wherein the high-boiling organic solvent is of Formula IV.

5. An element according to Claim 1, wherein the high-boiling organic solvent is of Formula V.

6. An element according to any of the above claims, wherein n is 1.

7. An element according to claim 1, wherein Rl is an aryl group, R2 is an alkyl group substituted with an aryloxy group, R3 is a hydrogen atom, X is a hydrogen atom, n is 1, and the high-boiling organic solvent is selected from the group consisting of dibutylsebacate, undecyl alcohol, oleyl alcohol, pdodecylphenol, and phenylethylbenzoate.

8. An element according to any of the above claims, wherein the weight ratio in said hydrophilic colloid layer of high-boiling organic solvent of formula 11, 111, IV and V relative to coupler of formula I is from 0.1 to 0.35.

9. An element according to any of the above claims, wherein the cyan coupler is of the following structure:

OH 0 11 C5Ell-t NECNE-0-M 0 t-HIJCS-C OCECNHt k 1;421-q-n

10. A method of making a silver halide color photographic light sensitive material according to any of the above claims, comprising:

(a) preparing a first dispersion of a phenolic cyan coupler of Formula I dispersed in an aqueous medium; (b) preparing a second dispersion of a highboiling organic solvent having Formula II, III, IV, V or combinations thereof dispersed in an aqueous medium; (c) combining said first and second dispersions in an aqueous coating solution, wherein the weight ratio in said coating solution of high-boiling organic solvent of formula II, III, IV and V relative to coupler of formula I is from 0.1 to 0.5; and (d) coating said coating solution on a photographic support.

11. A method according to Claim 10, wherein the first dispersion comprises cyan coupler of Formula I dispersed in an aqueous gelatin solution substantially free of permanent organic solvent.

12. A method of making a dispersion comprising particles of a phenolic cyan photographic coupler resistant to undesirable crystal growth dispersed in an aqueous medium; comprising dissolving a coupler of Formula I as defined in claim 1 in an auxiliary solvent, dispersing the auxiliary solvent and dissolved coupler in an aqueous gelatin solution substantially free of permanent organic solvent, and removing the auxiliary solvent from the dispersion.

13. A method according to Claim 12, wherein n in formula I is 1.

14. A method according to Claim 12 or 13, wherein the dispersion comprises a single cyan coupler of Formula I substantially free of other cyan dye forming couplers.

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15. A method according to any one of claims 12, 13, or 14, wherein the cyan coupler is of the following structure:

OH 0 11 C5H11-t NECNE-0-M 0 1 11:11, l:f t-HIICS- OCKCNE - 1 1.;V19-n