JPH08101477A - Coating composition for aqueous photograph - Google Patents

Abstract

PROBLEM TO BE SOLVED: To lower the viscosity of the gelatin containing fused material for photograph, which contains the photographic additive. SOLUTION: This composition, which is soluble in the mixture of gelatin and water, or water and a water miscible organic solvent, and which gives undesirable high viscosity to the gelatin solution and which contains the solution containing the hydrophobic group contained compound charged with the negative ion. Therefore, the composition is made to contain a sufficient quantity of cyclodextrin for lowering the viscosity of the solution.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to a method of preparing photographic elements, and more particularly to controlling the viscosity of photographic melts.

[0002]

Photographic elements generally comprise at least one light-sensitive layer on a support. Color photographic elements generally have at least one layer sensitive to blue light, at least one layer sensitive to green light, and at least one layer sensitive to red light. Color photographic elements also typically have various other layers such as subbing layers, interlayers, antihalation layers and the like. Generally, each layer of the photographic element is applied to a suitable support at the same time as the other layers in the coating process.

In traditional photographic coatings, in each layer a photographic coating composition containing emulsions, dispersions, and / or other photographic additives is applied from an aqueous solution containing a hydrophilic colloid such as gelatin. To do. Usually, the coating is performed at about 35 ° C to about 50 ° C. Generally, photographic emulsions and dispersions are prepared, chill set, and stored until needed for coating. At that time, it is cooled to about 35 ° C to about 50 ° C to provide a chill-cured emulsion or dispersion to provide a fluid coating composition often referred to as a "melt", "coating melt" or "photographic melt". Melts the body.

Generally, in the field of photographic technology, there are mainly two types of coating methods for photographic materials. One is the bead coating process. Russell et al., U.S. Pat. No. 2,762
1,417, Beguin U.S. Pat. No. 2,681,294
And Ishizaki U.S. Pat. No. 4,525,392 describe the simultaneous application of multiple layers of photographic material by a bead coating process and an apparatus for carrying out the method.

Another major method is the curtain coating process. Greiller US Patent 3,63
2,374, and Koepke et al., U.S. Pat. No. 4,569,
The specification of 863 describes an apparatus and process for curtain coating. It is well known that adjusting and controlling the viscosity of each layer melt can improve the layer thickness uniformity of the finished coating product. It is also known that sub-optimal layer viscosities can lead to various undesired layer thicknesses when flowing on the slides of the coating hopper or on non-horizontal web paths after application.

Masking coupler, oxidized developing agent scavenger, filter dye, optical brightener, ultraviolet absorber,
Some additives, such as dye transfer dyes, can lead to very high viscosities and non-uniform coatings when mixed with melts containing hydrophilic colloids. Generally those photographic additives are molecules with large hydrophilic groups, such as --SO _3- (ie sulfonate) groups, --SO.
₄ = solubilized with one or more fully ionized anionic groups, such as (i.e., sulfate) or COO- (i.e., carboxy) groups. These substances are usually sufficiently water-soluble or about 5-20% in water containing 5-20% by weight of water-miscible co-solvents such as methanol, ethanol, propanol, isopropanol, acetone, methyl ethyl ketone, ethyl acetate. Dissolves to the extent of weight percent. Also, such substances behave similarly in the presence of hydrophilic colloids.

Certain amphipathic additives, such as polyalkylene oxide block oligomers or polymers, when added to melts containing methionized viscosity-increasing photographic additives, produce moderate melt viscosities. Can be seen from the description of US Pat. No. 3,409,435. The amphipathic additives disclosed in this patent specification are
-BA, BAAB, AB, (AB) _n- G-
(BA), or (BA) _n- G- (AB)
(Wherein G is a bonded organic component and n is 1 to 3), and a block oligomer compound composed of a hydrophobic polyoxypropylene block (A) and a hydrophilic polyoxyethylene block (B) bonded as described above. Is.

Another example of such an amphipathic additive is On.
U.S. Pat. No. 3,860,425 and Visconte et al. U.S. Pat. No. 5,300,418. However, such prior art materials containing a large number of polyalkylene oxide groups have a photographic (sensitometric) effect which is not good in some photographic products. The sugar surfactants discussed in US Pat. No. 5,300,418 to Visconte et al. Have no adverse photographic effects, but they and the outer amphiphiles are surface active. Therefore, the viscosity cannot be lowered without lowering the surface tension of the melt.

One way to reduce the high viscosity of the melt is to dilute it with water. However, that method increases the water load on the dryer and is not desirable under the high speed coating conditions used in high volume film and paper manufacturing. Therefore, dilution is not always the preferred method.

[0010]

Accordingly, during the manufacture of photographic paper and film products, no excessive dryer wet load is applied and does not adversely or substantially affect the desired sensitometric effect of the photographic element. There is a need for a photographic melt (consisting of the photographic additives described above) that is sufficiently viscous and has a suitable concentration of hydrophilic colloids so that it does not give up. Furthermore, in order to avoid undesired layer thickness non-uniformities during the coating process caused by surface tension driven flow, the surface tension (flow conditions) of each layer of a simultaneously applied multilayer pack (as taught in the aforementioned patent specification). Since the relative value of (including the dynamic surface tension below) is important, it is desirable to be able to reduce the viscosity without reducing the surface tension.

High photographic gelatin-containing melts containing hydrophobic group-containing photographic additives which are water-soluble or are charged with anions rendered water-soluble with the aid of water-miscible organic cosolvents. It is an object of the present invention to reduce the viscosity.

[0012]

One aspect of the present invention is:
An aqueous solution containing gelatin and an anionically charged compound containing a hydrophobic group which is soluble in gelatin and (a) water or a mixture of water and a water-miscible organic solvent and (b) imparts an undesirably high viscosity to the aqueous gelatin solution. An aqueous photographic coating composition comprising the composition further comprising cyclodextrin in an amount sufficient to reduce the viscosity of the solution.

Another aspect of the present invention is (i) gelatin, (ii) (a) soluble in water or a mixture of water and a water-miscible organic solvent, and (b) undesirably high in aqueous gelatin solution. It consists of a photographic element bearing on a support a layer containing a (iii) cyclodextrin, which contains an anionically charged hydrophobic group which imparts viscosity.

Another aspect of the present invention is (a) soluble in water or a mixture of water and a water-miscible organic solvent,
And (b) a method of reducing the viscosity of an anion-charged aqueous gelatin solution containing a compound containing a hydrophobic group, which imparts an undesirably high viscosity to the aqueous gelatin solution, the amount being sufficient to reduce the viscosity of the solution. And adding cyclodextrin to the aqueous solution.

Yet another aspect of the present invention is that anions which are (a) soluble in water or a mixture of water and a water-miscible organic solvent, and (b) impart an undesirably high viscosity to aqueous gelatin solutions. A method for reducing the viscosity of a charged aqueous gelatin solution containing a hydrophobic group-containing compound,
Cyclodextrin is added to the aqueous solution in an amount sufficient to reduce the viscosity of the solution without reducing the surface tension of the composition.

[0016]

DETAILED DESCRIPTION OF THE INVENTION The present invention is generally soluble in coating layers of photographic elements and in hydrophilic colloids and (a) water or mixtures of water with water-miscible organic solvents, and (B) providing a melt containing an anionically charged, hydrophobic group-containing compound that imparts an undesirably high viscosity to the aqueous gelatin solution, and cyclodextrin in an amount effective to reduce the viscosity of the solution. This is achieved by adding to the aqueous solution.

Examples of hydrophilic colloids are water-soluble polymers, gelatin, gelatin derivatives, cellulose esters,
Casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid and maleic anhydride copolymers and mixtures thereof are included. Cellulose esters include hydroxypropyl cellulose, carboxymethyl cellulose and hydroxyethyl cellulose. The latex polymer includes vinyl chloride copolymer, vinylidene chloride copolymer, acrylic ester copolymer, vinyl acetate acetate copolymer and butadiene copolymer.
Gelatin is most preferred among them.

The amount of hydrophilic colloid in the solution is preferably about 2 to about 20% by weight, based on the weight of the solution. Anionic charged hydrophobic group-containing additives include sodium dodecyl sulphate, sodium octyl sulphate, sodium decyl sulphate, sodium tetradecyl sulphate, the sodium or potassium salt of octadecyl hydroquinone sulphate, or compounds of the formula:

[0019]

Embedded image

Is included. The anionically charged hydrophobic group-containing compound is preferably present in the solution in an amount of about 0.1 to about 10% by weight, based on the weight of the solution. According to the invention, the viscosity of the aqueous hydrophilic colloid solution is reduced by the addition of cyclodextrin.

Cyclodextrins are torus-shaped cyclic oligosaccharides formed by 6, 7 or 8 glucopyranose units by (1-4) bonds (α-, β-, and γ-cyclodextrin, respectively). be called). Cyclodextrins have the following structural formula:

[0022]

Embedded image

(Where n is defined as follows) The donut shape of cyclodextrin is specifically shown in FIG. In FIG. 1, the cyclodextrin molecule is represented as a torus (1) with a cavity (2) of diameter d. Cyclodextrins are defined as follows: α-cyclodextrin: n = 6, d = 0.45 nm (4.5 Å) β-cyclodextrin: n = 7, d = 0.70 nm (7.0 Å) ) Γ-Cyclodextrin: n = 8, d = 0.85 nm (8.5 angstroms) Cyclodextrin is a donut-shaped solid structure with well-defined cavities as shown in FIG. It can be thought of as a "molecular bucket."
Apolar (hydrophobic) that fits into the cyclodextrin cavity without forming a covalent bond because the cavity is hydrophobic
It is known to form various inclusion complexes in aqueous or solid state with molecules. In addition, polar compounds and certain inorganic ions associated with cyclodextrins have been found (Takisawa, N .; Shirahama, K;
Tanaka, I., "Colloid and Polymer Science" 271 (19
93), 495-503; Bender, KL; Komiyama, M. "Cycl
odextrin Chemistry ", Springer-Verlag, Berlin .; S
aenger, W., "Angew Chem. Int. Ed. Engl." 19 (198
0) 344; Kaifer, AE, "Advances in Supramolecul
ar Chemistry '', Volume 2, Pages 1-24, 1992, JAI Press In
c .; Satake, I; Ikenoue, T; Takeshita, T. "Bull.
Chem Soc. Jpn. ", 58 (1985) 2746; Schlenk, H; San
d, D., "J. Am. Chem Soc.", 83 (1961) 2312). Without wishing to be limited by any theory, it is believed that the cyclodextrin traps the anionically charged hydrophobic group-containing additive within the donut-like structure cavity of the cyclodextrin. Since cyclodextrins are not surface active, they reduce their viscosity without reducing the surface tension of the gelatin melt.

The cyclodextrin is added in an amount that effectively reduces the viscosity of the melt. Preferably, the molar ratio of cyclodextrin to the anionically charged hydrophobic group-containing additive is 1 to about 6, more preferably 1 to about 4, and most preferably about 3 to about 4. The cyclodextrin is generally added after the photographic emulsion or dispersion has been heated to form the coating melt. As mentioned above, the viscosity of one layer of a multilayer coating depends on the viscosity of adjacent layers.

The photographic compositions or melts of this invention can be used in any of the methods and combinations known in the art. The materials of this invention are typically coated as a layer on a support to form part of a photographic element. The photographic element can be a single color element or a multicolor element. Multicolor elements contain image dye-forming units sensitive to each of the three primary regions of the spectrum. Each unit can contain a single emulsion layer or multiple emulsion layers sensitive to a given region of the spectrum. These layers of the element, including the layers of the image-forming units, can be arranged in various orders as known in the art. In another format, emulsions sensitive to each of the three primary regions of the spectrum can be arranged as a single segmented layer.

A typical multicolor photographic element comprises a cyan dye image-forming unit comprising at least one red-sensitive silver halide emulsion layer in combination with at least one cyan dye-forming coupler, at least one magenta dye-forming coupler. Yellow dye image forming comprising a magenta dye image-forming unit comprising at least one green-sensitive silver halide emulsion layer in combination and at least one blue-sensitive silver halide emulsion layer in combination with at least one yellow dye-forming coupler. It consists of a support that carries the unit. The element can include additional layers such as filter layers, interlayers, overcoat layers, subbing layers and the like.

If desired, the photographic elements may be replaced by Research Disclosure, Item 343.
90, November 1992, (Kenneth Mason Publication Ltd., Du
dleyAnnex, 12a North Street, Emsworth, Hampshire P
It may also be used in combination with a coated magnetic layer as described in O10 7DQ, published by England). In the following discussion of suitable materials for use in the emulsions and photographic elements of this invention, Research Disclosure, Item 308119,
December 1989 (Sold by the above publishers,
"Research Disclosure").
The section referred to hereinafter is the section of Research Disclosure.

The silver halide emulsions used in the elements of this invention can be either negative or positive working. Suitable emulsions and their preparation and chemical and spectral sensitization methods are described in Sections I-IV. Color materials and development modifiers are described in Sections V and XXI
Explained. Vehicles are described in Section IX and are used in various types of optical brighteners, antifoggants, stabilizers, light absorbing and scattering materials, hardeners, coating aids, plasticizers, lubricants, and matting agents. Additives are, for example, Section V
, VI, VIII, X, XI, XII, and XVI. Manufacturing methods are described in Sections XIV and XV, other layers and supports in Sections XIII and XVII, processing methods and agents in Sections XIX and XX, and exposure procedures in Section XVIII.

Coupling-off groups are well known in the art. The groups can determine the chemical equivalent weight of the coupler (ie, whether it is a two-equivalent or four-equivalent coupler) or can change the reactivity of the coupler. These groups, after being released from the coupler, include, for example, dye formation, hue adjustment, development acceleration or development inhibition, bleach acceleration or bleach inhibition, electron transfer acceleration,
By carrying out functions such as color correction, the layer coated with the coupler or other layers of the photographic recording material can be advantageously influenced.

The presence of hydrogen at the coupling position results in a four equivalent coupler, and the presence of another coupling-off group usually results in a two equivalent coupler. Representative classes of such coupling-off groups include, for example, chloro, alkoxy, aryloxy, hetero-oxy, sulfonyloxy, acyloxy, acyl, heterocyclyl, sulfonamide, mercaptotetrazole, benzothiazole, mercaptopropionic acid. , Phosphonyloxy, arylthio, and arylazo. These coupling-off groups are described in the art, eg, US Pat. 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 the United Kingdom. Patent Nos. 1,466,728 and 1,531,
No. 927, No. 1,533,039, British Patent Application Publication Nos. 2,006755, 2,017,704.

US Pat. Nos. 2,772,162 and 2,
895, 826, 3,002, 836, 3,0
34,892, 2,474,293, 2,42
3,730, 2,367,531, 3,04
No. 1,236, No. 4,883,746, and "Farbkupplereine Literaturubersicht", Agfa Mitte.
Illuminen, Band III, pp. 156-175 (1961), and representative couplers described in representatives and sensitizers which produce cyan dyes in reaction with oxidized color developing agents. Can be contained in. Preferably,
Such couplers are phenols and naphthols which react with oxidized color developing agents to form cyan dyes.

Couplers that react with oxidized color developing agents to form magenta dyes are described in US Pat. No. 2,600,
No. 788, No. 2,369,489, No. 2,343,7
03, 2, 311, 082, 3, 152, 896
Issue 3, Issue 3,159,429, Issue 3,062,653
No. 2,908,573 and "Farbkupplere"
ine Literaturubersicht ”, published by Agfa Mitteilungen,
Band III, pp. 126-156 (1961), in representative patent specifications and publications. Preferably, such couplers are pyrazolones, pyrazolotriazoles, or pyrazolobenzimidazoles that react with oxidized color developing agents to form magenta dyes.

Couplers that react with oxidized color developing agents to form yellow dyes are: US Pat.
057, 2,407,210, 3,265,5
06, 2,298,443, 3,048,194
No. 3,447,928 and “Farbkupplerein
e Literaturubersicht ", published by Agfa Mitteilungen, Ba
nd III, pages 112-126 (1961), in representative patent specifications and publications. Such couplers are typically open chain ketomethylene compounds.

US Pat. Nos. 4,301,235, 4,
It is effective to use a combination of known couplers capable of having a ballast or a coupling-off group, as described in the specifications of 853,319 and 4,351,897. European Patent No. 213,490
No. 58,172,647, U.S. Pat. No. 2,982.
No. 3,608, German patent application No. 2,706,117
No., British Patent No. 1,530,272, Japanese Patent Application No. A-113935, US Patent No. 4,070,191.
No. 4,273,861 and German Patent Application No. 2,643,965, the couplers are also combined with "wrong" colored couplers. (For adjusting the interlayer correction level, for example) and with color masking couplers in color negative applications. The masking coupler can be shifted or blocked.

The photographic elements can also contain materials which accelerate or improve processing steps such as bleaching or fixing to improve image quality. European Patent No. 1933
89, 301,477, U.S. Pat. No. 4,163,6
69, 4,865,956 and 4,923,7
Bleach accelerator releasing couplers such as those described in the '84 application are useful. Further, a composition related to a nucleating agent, a development accelerator or a precursor thereof (UK Patent No. 2,029).
97,140, 2,131,188, each specification);
Electron transfer agents (U.S. Pat. Nos. 4,859,578, 4,
No. 912,025); antifoggants such as hydroquinone, aminophenol, amine, gallic acid, and color mixture preventing agents; catechol; ascorbic acid; hydrazide; sulfonamidephenol; and noncolor-forming couplers. For example, with color negative elements,
The materials of the present invention may be replaced or supplemented with the materials of the elements having the following top to bottom layers on the support: (1) one or more containing UV absorber (s) Overcoat layer (2) "Coupler 1": 4-chloro-3-((2- (4
-Ethoxy-2,5-dioxo-3- (phenylmethyl) -1-imidazolidinyl) -3- (4-methoxyphenyl) -1,3-dioxopropyl) amino) -benzoic acid, high sensitivity including dodecyl ester Yellow layer, and "Coupler 2": 2-[[5-[[4- [2-
[[[2,4-bis (1,1-dimethylpropyl) phenoxy] acetyl] amino] -5-[(2,2,3
3,4,4,4-heptafluoro-1-oxobutyl)
Amino] -4-hydroxyphenoxy] -2,3-dihydroxy-6-[(propylamino) carbonyl] phenyl] thio] -1,3,4-thiadiazol-2-yl] thio] -propanoic acid, methyl ester and "Coupler 3": 1-((dodecyloxy) carbonyl) ethyl (3-chloro-4-((3- (2-chloro-
4-((1-Tridecanoylethoxy) carbonyl) anilino) -3-oxo-2-((4) (5) (6)-
(Phenoxycarbonyl) -1H-benzotriazol-1-yl) propanoyl) amino)) benzoate,
Two-layer yellow pack having a slow yellow layer containing the same compound together with (3) an intermediate layer containing fine metallic silver.

(4) Three-layer magenta pack "Coupler 4": 3-((2- (2,4-bis (1,1
-Dimethylpropyl) phenoxy) -1-oxobutyl) amino) -N- (4,5-dihydro-5-oxo-
1- (2,4,6-trichlorophenyl) -1H-pyrazol-3-yl) -benzamide, "Coupler 5": 3-((2- (2,4-bis (1,1
-Dimethylpropyl) phenoxy) -1-oxobutyl) amino) -N- (4 ', 5'-dihydro-5'-oxo-1'-(2,4,6-trichlorophenyl)
(1,4'-bi-1H-pyrazole) -3'-yl)-
Bezamide, "Coupler 6": (6-(((3- (dodecyloxy))
Propyl) amino) carbonyl) -5-hydroxy-1
-Naphthalenyl) -carbamic acid 2-methylpropyl ester, "coupler 7": ((2-((3-(((3- (dodecyloxy) propyl) amino) carbonyl) -4-hydroxy-8-((( 2-Methylpropoxy) carbonyl) amino) -1-naphthalenyl) oxy) ethyl) thio) -acetic acid, and “Coupler 8”: 3-((2- (2,4-bis (1,1
-Dimethylpropyl) phenoxy) -1-oxobutyl) amino) -N- (4,5-dihydro-4-((4-
Methoxyphenyl) azo) -5-oxo-1- (2,
4,6-Trichlorophenyl) -1H-pyrazole-3
-Yl) -benzamide, a highly sensitive magenta layer, "Coupler 9": 2-propenoic acid butyl ester in a weight ratio of 1: 1: 2, styrene, and N- [1- (2,4,6).
-Trichlorophenyl) -4,5-dihydro-5-oxo-1H-pyrazol-3-yl] -2-methyl-2-
Ternary copolymer containing propenamide "Coupler 10": N- (4-chloro-3-((4-
((4-((2,2-dimethyl-1-oxopropyl)
Amino) phenyl) azo) -4,5-dihydro-5-oxo-1- (2,4,6-trichlorophenyl) -1H
-Pyrazol-3-yl) amino) phenyl) -tetradecanamide, and a three-layer magenta pack having a medium-speed magenta layer and a low-speed magenta layer, which additionally contain couplers 3 and 8, respectively. 6) High-sensitivity cyan layer containing couplers 6 and 7, coupler 6 and “coupler 11”: 5- (acetylamino) -3-((4- (2-((3-(((3- (2 Four
-Bis (1,1-dimethylpropyl) phenoxy) propyl) amino) carbonyl) -4-hydroxy-1-naphthalenyl) oxy) ethoxy) phenyl) azo) -4
-Hydroxy-2,7-naphthalenedisulfonic acid, a three-layer cyan pack having a medium-speed cyan layer containing a disodium salt, and a low-speed cyan layer containing couplers 2 and 6 (7) Undercoat layer containing coupler 8 (8) Antihalation Layer In color paper format, the photographic element can comprise the following top to bottom layers on a support: (1) one or more overcoats (2) "Coupler 1 : 2- (2,4-bis (1,1-
Dimethylpropyl) phenoxy) -N- (3,5-dichloro-2-hydroxy-4-methylphenyl) -butanamide, "Coupler 2": 2- (2,4-bis (1,1-dimethylpropyl) phenoxy) -N- (3,5-dichloro-
2-Hydroxy-4-acetamide, and UV stabilizer: 2- (5-chloro-2H-benzotriazol-2-yl) -4,6-bis (1,1-dimethylethyl) -phenol; 2- (2H -Benzotriazol-2-yl) -4- (1,1-dimethylethyl) -6-
(1-methylpropyl) -phenol; and 2- (2H
Cyan layer containing (benzotriazol-2-yl) -4,6-bis (1,1-dimethylpropyl) -phenol, and poly (t-butylacrylamide) dye stabilizer (3) Intermediate layer.

(4) "Coupler 3": 2, 2 ', 3,
3'-tetrahydro-3,3,3 ', 3'-tetramethyl-5,5', 6,6'-tetrapropoxy-1,1 '
2- [2,4-bis (1,1-dimethylpropyl) phenoxy] -N- [2- (7-chloro-6-methyl-1H) with -Spirobi (1H-indene)
-Pyrazolo [1,5b] [1,2,4] triazole-
Magenta layer containing 2-yl) propyl] -octanamide (5) Intermediate layer (6) "Coupler 4": N- (5-((2- (2,4-
Bis (1,1-dimethylpropyl) phenoxy) -1-
Oxobutyl) amino) -2-chlorophenyl) -α-
(2,2-Dimethyl-1-oxopropyl) -4-ethoxy-2,5-dioxo-3- (phenylmethyl) -1
In a yellow layer reversal medium containing imidazolidine acetamide, the photographic element may comprise the following top to bottom layers on a support: (1) one or more overcoat layers; Sensitized silver halide-containing layer (3) "Coupler 1": 4- (1-(((2-chloro-
5-((dodecylsulfonyl) amino) phenyl) amino) carbonyl) -3,3-dimethyl-2-oxobutoxy) -benzoic acid, a highly sensitive yellow layer containing 1-methylethyl ester; coupler 1 and coupler 2: 4. -Chloro-3-[[2- [4-ethoxy-2,5-dioxo-
3- (Phenylmethyl) -1-imidazolidinyl]-
4,4-Dimethyl-1,3-dioxopentyl] amino] -benzoic acid, a medium-sensitivity yellow layer containing dodecyl ester; a three-layer yellow pack having a low-sensitivity yellow layer containing coupler 2 (4) Intermediate layer ( 5) Fine particle silver layer (6) Intermediate layer (7) "Coupler 3": N- [1- (2,5-dichlorophenyl) -4,5-dihydro-5-oxo-1H-pyrazol-3-yl]- 2-Propenoic acid with 2-methyl-2-propenamide, butyl ester, polymer, "Coupler 4": 3-((2- (2,4-bis (1,1
-Dimethylpropyl) phenoxy) -1-oxobutyl) amino) -N- (4,5-dihydro-5-oxo-
1- (2,4,6-trichlorophenyl) -1H-pyrazol-3-yl) -benzamide, and "coupler 5": 3-(((2,4-bis (1,1-dimethylpropyl) phenoxy). Acetyl) amino) -N
-(4,5-dihydro-5-oxo-1- (2,4,6
-Trichlorophenyl) -1H-pyrazol-3-yl) -benzamide, and stabilizer: 2,2 ', 3,3'-tetrahydro-3,3,3.
3 ', 3'-tetramethyl-5,5', 6,6'-tetrapropoxy-1,1'-spirobi (1H-indene)
High- and medium-speed magenta layers containing: coupler 4,
Three-layer magenta pack having a slow magenta layer containing 5 and the same stabilizer (8) One or more intermediate layers which may contain fine grain unsensitized silver halide (9) "Coupler 6": 2- (2- Cyanophenoxy)
Highly sensitive cyan layer containing -N- (4-((2,2,3,3,4,4,4-heptafluoro-1-oxobutyl) amino) -3-hydroxyphenyl) -tetradecanamide; "Coupler 7 : N- (4-((2- (2,4-bis (1,1-dimethylpropyl) phenoxy) -1-oxobutyl) amino) -2-hydroxyphenyl) -2,
2,3,3,4,4,4-heptafluoro-butanamide, and "Coupler 8": 2- (2,4-bis (1,1-dimethylpropyl) phenoxy) -N- (4-((2 , 2,
3,3,4,4,4-heptafluoro-1-oxobutyl) amino) -3-hydroxyphenyl) -hexanamide, a medium speed cyan layer; and slow cyan layers containing couplers 6, 7 and 8. (10) One or more intermediate layers which may contain fine grain non-sensitized silver halide (11) Antihalation layer It can also be used with a filter dye layer consisting of colloidal silver sol or yellow and / or magenta filter dyes, either as a particle dispersion. Furthermore, they are called "smearing".
Couplers (eg, US Pat. No. 4,366,237,
European Patent No. 96570, US Patent No. 4,420,55
No. 6, and No. 4,543,323). Also,
The composition may be blocked or applied in a protected form as described in, for example, Japanese Patent Application No. 61-258249 or US Pat. No. 5,019,492.

The photographic elements can contain image-modifying compounds such as "Development Inhibitor Releasing" compounds (DIR's). DIR compounds useful in connection with the compositions of the present invention are well known in the art and examples thereof include US Pat. Nos. 3,137,578 and 3,148,
No. 022, No. 3,148,062, No. 3,227,5
No. 54, No. 3,384,657, No. 3,379,52
No. 9, No. 3,615, 506, No. 3,617, 291
Issue No. 3,620,746 Issue 3,701,783
Issue No. 3,733,201 Issue 4,049,455
No. 4,095,984, No. 4,126,459
No. 4,149,886, 4,150,228
No. 4,211,562, No. 4,248,962
Nos. 4,259,437 and 4,362,878
No. 4,409,323, 4,477,563
Issue 4,782,012, Issue 4,962,018
Issue 4,500,634, Issue 4,579,816
Issue 4,607,004, Issue 4,618,571
Issue No. 4,678,739 Issue No. 4,746,600
Issue No. 4,746,601 No. 4,791,049
No. 4,857,447, 4,865,959
No. 4, No. 4,880,342, No. 4,886,736
Nos. 4,937,179 and 4,946,767.
Issue No. 4,948,716 Issue No. 4,952,485
Nos. 4,956,269 and 4,959,299
No. 4,966,835, 4,985,336
And British Patent Nos. 1,560,240 and 2,0
07,662, 2,032,914, 2,09
9,167, German Patent No. 2,842,063,
No. 2,937,127, No. 3,636,824, No. 3,644,416, and next European Patent No. 272.
573, 335319, 336411, 3
46899, 362870, 365252,
No. 365346, No. 373382, No. 376212
Nos. 377463, 378236, 3846
No. 70, No. 396486, No. 401612, No. 40
1613.

These compounds are also available in Photographic Sci
ence and Engineering, Vol. 13, 174 (1969) CRB
It is disclosed in "Color Photographic Development Inhibitor Releasing Couplers" by Arr, JR Thirtle and PW Vittum. Also,
Research Disclosure, 1979
November, can be used to obtain a reflective color print as described in Item 18716. The material of the present invention is combined with an epoxy solvent (EP 164961) on a pH adjusted support as described in US Pat. No. 4,917,994; nickel complex stabilizer (US Patent Nos. 4,346,165; 4,54
0,653 and 4,906,559); ballasts as described in U.S. Pat. No. 4,994,359 to reduce sensitivity to polyvalent cations such as calcium. With chelating agents; and with stain reducing compounds as described in US Pat. No. 5,068,171. Other compounds useful in combination with the present invention have the following accession numbers by Derwent Abstracts
It is disclosed in Japanese Patent Publication No. That is: 90-072,629, 90-072,630; 9
0-072,631; 90-072,632; 90-0
72,633; 90-072,634; 90-077,
822; 90-078,229; 90-078,23.
0; 90-079,336; 90-079,337; 9
0-079,338; 90-079,690; 90-0
79, 691; 90-080, 487; 90-080,
488; 90-080, 489; 90-080, 49
0; 90-080, 491; 90-080, 492; 9
0-080,494; 90-085,928; 90-0
86,669; 90-086,670; 90-087,
360; 90-087, 361; 90-087, 36
2; 90-087, 363; 90-087, 364; 9
0-088,097; 90-093,662; 90-0
93, 663; 90-093, 664; 90-093,
665; 90-093,666; 90-093,66
8; 90-094, 055; 90-094, 056; 9
0-103,409; 83-62,586; 83-0
It is 9,959.

Particularly useful in the photographic elements of this invention are tabular grain silver halide emulsions. Particularly contemplated tabular grain emulsions have 50% of the total projected area of the emulsion grains.
0.3 μm (0.5 μm for blue-sensitive emulsions)
m) and a mean tabularity (T) of greater than 25 (preferably greater than 100) [where the term "tabularity" is T = ECD / t ² , where ECD is tabular grain Of μ
is the average equivalent circular diameter represented by m, and t is μ of the tabular grain.
is used in the art and is used in the art].

The effective average ECD of a photographic emulsion is about 10 μm.
m (as a matter of fact, it rarely exceeds about 4 μm)
Up to the range. Larger ECD's provide higher photographic speed and granularity, so it is generally preferred to use the smallest tabular grain ECD's suitable for achieving the desired speed requirements. Emulsion tabularity decreases markedly with reductions in tabular grain thickness. It is generally preferred that the desired tabular grain projected area be satisfied by thin (t <0.2 μm) tabular grains. To achieve the lowest levels of granularity, the desired tabular grain projected area is preferably filled with ultrathin (t <0.06 μm) tabular grains. The tabular grain thickness is
It is typically thin, up to 0.02 μm. However, thinner tabular grain thicknesses are contemplated. For example, U.S. Pat.
No. 672,027 (Daubendiek et al.) Reports a 3 mol% iodide tabular grain silver bromoiodide emulsion having a grain thickness of 0.017 μm.

As noted above, tabular grains thinner than a specified thickness account for at least 50 percent of the layer projected area of the grain.
To maximize the benefits of high tabularity, tabular grains satisfying the previously mentioned thickness criteria generally account for the most conveniently attainable percentage of the total grain projected area of the emulsion. preferable. For example, in a preferred emulsion,
Tabular grains satisfying the thickness criteria above account for at least 70 percent of total grain projected area. In the highest performance tabular grain emulsions, tabular grains satisfying the thickness criteria above account for at least 90 percent of total grain projected area.

Suitable tabular grain emulsions can be selected from among a variety of conventional teachings as in the following references:
That is, Research Disclosure, Item 22534,
January 1983; and U.S. Pat. No. 4,439,520
Issue No. 4,414,310 Issue No. 4,433,048
No. 4,643,966, No. 4,647,528
Issue No. 4,665,012, No. 4,672,027
No. 4,687,745, 4,693,964
Issue No. 4,713,320 Issue No. 4,722,886
Nos. 4,755,456 and 4,775,617
No. 4,797,354, 4,801,522
Issue No. 4,806,461 Issue No. 4,835,095
No. 4,853,322, 4,914,014
No. 4,962,015, 4,985,350
Nos. 5,061,069, and 5,061,61
No. 6 is each specification. Furthermore, European Patent No. 543,395
The use of the {100} silver chloride emulsions described in the publication is also particularly conceivable.

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

Suitable tabular grains are shown below: Research Disclosure, Item 22534, December 1983, (Kenn
eth Mason Publication Ltd., Dudley Annex, 12a Nort
H Street, Emsworth, Hampshire PO10 7DQ, England), U.S. Pat. Nos. 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. Nos. 4,853,322, 4,914,014, 4,962,015, 4,985,350, 5,061,069 and 5,061,616. One can choose from a wide variety of conventional techniques in the specification.

The emulsion can be a surface sensitive emulsion (ie, an emulsion that produces a latent image primarily on the surface of the silver halide grains), or an emulsion that primarily produces an internal latent image inside the silver halide grains. be able to. These emulsions are either negative-working emulsions such as surface sensitive emulsions or unfogged internal latent image forming emulsions, or positive fog internal latent images which are positive when developed with uniform exposure or in the presence of nucleating agents. It can be a production type direct positive emulsion.

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

With negative-working silver halide, the processing step described above produces a negative image. 19 of the listed photographic elements
1988 British Journal of Photography Annual, p. 191
The known C-41 color process described in Nos. 198 to 198 can be used. This element, if applicable, is described in the British Journal of Photography Annual, 1988, pp. 198-19.
It may be processed by a color printing process such as Eastman Kodak Company's RA-4 described in item 9. To obtain a positive (ie, reversal) image, develop with a non-color-developing agent before the color-developing step, develop the exposed silver halide (but do not produce a dye), then homogenize this element. Fog to make unexposed silver halide developable. Alternatively, a positive image can be obtained using a direct positive emulsion.

Preferred color developing agents are p
-Phenylenediamines: 4-amino-N, N-
Diethylaniline hydrochloride, 4-amino-3-methyl-
N, N-diethylaniline hydrochloride, 4-amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) aniline sesquisulfate hydrate, 4-amino-3-methyl-N- Ethyl-N- (β-hydroxyethyl) aniline sulfate, 4-amino-3-β- (methanesulfonamide) ethyl-N, N-diethylaniline hydrochloride, and 4-amino-N-ethyl-N- ( 2-Methoxyethyl) -m-toluidine di-p-toluenesulfonic acid.

Development is generally followed by the usual steps of bleaching, fixing, or bleach-fixing, followed by the steps of removing silver or silver halide, washing and drying. Unless otherwise stated, by referring to the entire specification and claims of the present application, etc., to consider that a group containing a substitutable hydrogen (eg, alkyl, amine, aryl, alkoxy, heterocycle, etc.) is the same. It is understood that the referenced substituents include the unsubstituted form of the substituents as well as the forms substituted with any photographically useful substituents. Usually, the substituents have less than 30 carbon atoms and typically less than 20 carbon atoms.

[0051]

The following example illustrates the reduction in viscosity of the coating melt by the addition of cyclodextrin. Examples 1-6 Gelatin, water and sulfonated oxidative color developing agent scavengers (SC-) having the following structural formulas (a) and (b):
A solution of the isomer mixture of 1) was prepared in the proportions given in Table I.

[0052]

[Chemical 4]

[0053]

[Table 1]

Example 1 is a melt containing no SC-1,
2 gelatin aqueous solutions containing 10.1 wt% gelatin
It has a viscosity of 3.1 cP RBT (rolling ball time). When SC-1 was mixed with the melt (0.21% by weight based on the weight of the solution), the viscosity was 44.5c.
Rise to P. However, when compound α-cyclodextrin hydrate (manufactured by Aldrich Chemical Company) was added to the melt in increasing amounts, this melt (Example 3, Example 3, It can be seen that the viscosity of 4 and 5) is substantially reduced.

Examination of the surface tension shows that the addition of α-cyclodextrin to water does not reduce its surface tension (ie remains about 72 mN / m as measured by the Wilhemy plate method). In FIG. 2, SC-1 [SC-1
(A) surface tension of 31% and SC-1 (b) consisting of 69%] is, in the case of 5 × 10 ^-4 M SC-1 solution, about 0.
It can be seen to drop to 043 N / m (43 dynes / cm). About 5 × 10 ⁻⁵ M (log [SC-1] = − 4.
The steep inflection point on the curve in 3) is the critical micelle concentration of SC-1. Since this is a typical behavior of a surfactant molecule, SC-1 is a surfactant (ie an amphiphile).

In FIG. 3, the aqueous solution of α-cyclodextrin
Liquid (10^-3Increase the amount of SC-1 added to M)
And the molar concentration of SC-1 is that of α-cyclodextrin.
After approaching the number, it is seen that the surface tension drops.
You. The coupling constant, assuming a 1: 1 type of coupling
Is about 990M^-1Is. Comparing FIG. 2 and FIG. 3, α
-5x10 without cyclodextrin^-FourMSC-1's
Surface tension is about 0.043 N / m (43 dynes / cm)
But 10 ^-3In the presence of M α-dextrin
Remarkably high [0.069 N / m (69 dynes / c
m)]. From another point of view,
Adds α-cyclodextrin to the SC-1 solution
Then, the surface tension of the solution rises compared to the case without SC-1
Is consistent with the conclusion that

[0057]

INDUSTRIAL APPLICABILITY According to the present invention, diluting a photographic coating composition with an undesirably large amount of water, or sugar-based surfactants (to reduce the surface tension of the composition, as taught in the prior art, And / or the viscosity of the photographic coating composition can be adjusted without the addition of nonionic surfactants, which can cause undesirable sensitometric changes in the resulting photographic element.

[Brief description of drawings]

FIG. 1 Morphology of cyclodextrin molecules.

FIG. 2 Hydrophobic group-containing compound (SC
-1) A graph showing the surface tension of the aqueous solution.

FIG. 3 is a graph showing the effect of adding α-dextrin to an aqueous solution of SC-1.

[Explanation of symbols]

 1 ... Torus 2 ... Cavity

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Gary William Visconte New York, USA 14626, Rochester, Cedar Hill Drive 20 (72) Inventor Chris Ganjemi United States, New York 14622, Rochester, Angelus Drive 103 (72) Inventor Edwin Garcia United States, New York 14617, Rochester, Mount Airy Drive 28

Claims (2)

[Claims] 1. Gelatin and (a) soluble in water or a mixture of water and a water-miscible organic solvent, and (b).
A composition comprising an aqueous solution containing an anionically charged hydrophobic group-containing compound that imparts an undesirably high viscosity to an aqueous gelatin solution, said composition further in an amount sufficient to reduce the viscosity of said solution. Aqueous photographic coating composition containing cyclodextrin. 2. The anionically charged compound containing a hydrophobic group is sodium dodecyl sulfate, sodium octyl sulfate, sodium decyl sulfate, sodium tetradecyl sulfate, sodium or potassium salt of octadecylhydroquinone sulfate, or a compound of the following formula: [Chemical 1] The photographic coating composition according to claim 1.