JPH03123345A - Production of positive image forming photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce mottles in densities after development processing by controlling the viscosity of a coating fluid within a specified range and forming one or more hydrophilic colloidal layers. CONSTITUTION:This photosensitive material is produced by forming one or more hydrophilic colloidal layers (photographic emulsion layers), (for example, all the hydrophilic colloidal layers but the first) containing silver halide grains (A) on a reflective support. At that time, the coating fluid to be used has a viscosity of 50 - 200cp, and it is preferred to use nonprefogged internal latent image type silver halide grains as the particles A, and to develop it in the presence of a nucleating agent and to form a direct positive color image.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a method for producing a positive image-forming photographic material having a reflective support.Specifically, the present invention relates to a method for producing a positive image forming photographic material having a reflective support. The present invention relates to a method for producing a positive image forming photographic material.

[Conventional technology]

Photographic light-sensitive materials are classified into negative-type light-sensitive materials that produce a positive image from a negative image, and positive-type light-sensitive materials that produce a positive image from a positive image.
In order to directly obtain a positive image from an object or a printed positive image, a positive image forming photographic material having a reflective support is used.

As a reflective support for such a positive image-forming photographic material, paper or the like is coated with a hydrophobic resin (e.g., polyethylene terephthalate, cellulose triacetate) containing a dispersed light-reflecting substance (e.g., titanium oxide, zinc oxide). Hydrophobic resin containing a dispersed light-reflecting substance is used. In such cases, thin reflective supports are preferred for use in order to avoid bulk when filing such photographic papers that have been reproduced.

When such a thin reflective support is used, disturbing density unevenness often occurs in the image on the photographic paper after processing.
Improvements were desired.

Conventionally, in the production of photographic light-sensitive materials, uniform coating was required when coating a coating solution on a support to form a photographic emulsion layer, etc.
No. 5214, the bottom layer of the coating is thinned to about 1
The coating layer is formed by using a low viscosity coating composition in the range of ~8 centipoise and coating the layer immediately above the bottom layer with a relatively high viscosity coating composition in the range of about 10 to 100 centipoise. In this method, the coating composition forming the bottom layer has a low viscosity so that the surface of the web is wetted and does not cause coating defects.
Alternatively, it acts as a shield for the upper layer.

In addition, JP-A-63-11934 discloses that at least the bottom layer of a silver halide emulsion layer or other hydrophilic colloid layer is coated with a sulfonic acid group, a sulfate ester group, or a carboxylic acid group in the hydrophilic colloid layer and the side chain. group, and its limiting viscosity (
(η) 0. We have proposed a method for manufacturing silver halide photographic materials by containing a polymer compound having a lN5all (30°C) of 0.4 to 1.8 and applying it at a rate of 80+w/min to 300s/min. , for example poly[p
-sodium styrene sulfonate] (η) -1,0
It has been shown that a photographic material in the form of a film can be produced using a coating solution having a viscosity of 50 to 8 Qcp by adding the above-mentioned compound, and it has been shown that coating unevenness can be eliminated by this method.

Furthermore, when manufacturing photographic paper with an uneven pattern such as silk grain, it is necessary to apply the coating solution to a support with an uneven surface at high speed using a speed coating method using a slide hopper or the like. It is easy to cause a situation in which the coating material does not fully penetrate into the unevenness of the surface of the support (the higher the application speed, the more likely this situation will occur), so in order to solve the problem of not being able to increase the production speed, Now, when a support having an uneven surface is continuously run at high speed and a coating liquid is applied to the surface of the support by forming a bead, the coating liquid of the layer directly in contact with the surface of the support is coated once. The viscosity is ~15 cp.This is because by lowering the viscosity of the coating liquid, it improves the dynamic wettability between the support and the coating liquid, and completely coats the uneven surface of the support. By allowing the coating liquid to penetrate, so-called repellency failures are prevented from occurring.

On the other hand, when using the above-mentioned thin reflective support, disturbing density unevenness occurs in images on photographic paper after processing.
In No. 49, the photosensitive material has at least one of a photosensitive silver halide emulsion layer for forming a cyan image and a photosensitive silver halide emulsion layer for forming a magenta image.

[Problem to be solved by the invention]

When such a thin reflective support is used, it is thought that unevenness of the reflective support causes density unevenness to occur during development, particularly in low density areas on the image. However, even if such a thin reflective support is used, in the case of a negative-tone photosensitive material, the problem of density unevenness will hardly occur in such low-density areas because the amount of exposure is small because it is a negative type. .

On the other hand, in the case of a positive image-forming photographic light-sensitive material, it is necessary to increase the amount of exposure due to the characteristics of the light-sensitive material, so density unevenness becomes noticeable. In particular, even in positive image-forming photographic materials, density unevenness is not a problem when a film support is used because there is no unevenness, but when a reflective support is used, in addition to the problem of unevenness, light rays are reflected by the reflective support. The image is raised, and since the underlying support is white, density unevenness becomes noticeable.

An object of the present invention is to provide a method for producing a positive image-forming photographic material using a reflective support, which has improved density unevenness after development.

[Means to solve the problem]

The above-mentioned object of the present invention is to provide a method for producing a positive image-forming photographic material having at least one photographic emulsion layer containing silver halide grains on a reflective support. It has been found that this can be achieved by a method for producing a positive image-forming photographic material, which is characterized in that the viscosity of the coating liquid forming the image is from 50 centipoise to 200 centipoise.

The viscosity of the coating liquid used to form the hydrophilic colloid layer in the present invention is from 50 centipoise to 200 centipoise, preferably from 70 centipoise to 150 centipoise. The viscosity is at .8m/sec, measured using a B-type viscometer (
Manufactured by Tokyo Keiki: Model BL) Rotor 1lhl, rotation speed 3O
It can be measured under rpm conditions.

In the present invention, the viscosity of the coating solution is set within the range of the present invention, and the coating solution is coated onto a reflective support to form at least one hydrophilic colloid layer. It is preferable to form at least one hydrophilic colloid layer that is present in the second layer or more, and the formation is preferably carried out on a photographic emulsion layer that is present in the second or more layers than the reflective support. is preferable, and even better results are obtained if the method is applied to all the photographic emulsion layers present in the 2nd J!1 layer or more from the reflective support. is most preferred.

Alternatively, in the present invention, the coating liquid has a viscosity of 10
It is preferable to use a hydrophilic colloid of 0 to 150 centipoise to form a hydrophilic colloid layer that is present at the second layer or higher than the reflective support.

The viscosity of the coating liquid used to form the 11th layer (lowermost layer) can be 15 to 200 centipoise.

The viscosity of the coating liquid used in the present invention can be set within the range of the present invention by selecting components in the coating liquid and adjusting their concentrations.

In particular, the viscosity is adjusted by binders or protective colloids, thickeners. It is also regulated by plasticizers, surfactants, etc.

In conventional coating, the viscosity of the coating solution is kept low to prevent uneven coating due to thin layer coating, high speed coating, and simultaneous multilayer coating. Improvements were being made with activators, etc. Regarding these, JP-A-63-11934 and JP-A-61
-146370, 63-184748, 60-
No. 255172 and No. 52-115214 are disclosed. However, even if the viscosity is increased, as long as the viscosity of the coating solution is within the range of the present invention, there will be no particular problem in coating properties, and the problems of the present invention can be solved.

As the binder or protective colloid that can be used in the present invention, gelatin is advantageously used, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate, dextran, and starch derivatives; Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polyvinylimidazole, polyvinylpyrazole, and the like.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin may be used, and gelatin hydrolysates or enzymatically decomposed products may also be used.

Among these, it is preferable to use dextran and polyacrylamide together with gelatin.

Examples of plasticizers that can be used in the present invention include polyols such as trimethylolpropane, bentanediol, butanediol, ethylene glycol, glycerin, and sorbitol.

Thickeners that can be used in the present invention include, for example, the aqueous polymer having a sulfuric ester group described in Japanese Patent Publication No. 36-21574, dextran and its sulfuric ester described in Japanese Patent Publication No. 35-11989, JP-A-53 -186
No. 87, No. 57-109947, No. 63-11934
A polymer having a sulfonic acid group, a carboxylic acid group, a sulfuric acid ester group, or a phosphoric acid group in its side chain, as described in Japanese Patent Publication No. 58367
Colloidal silica described in No. 68, U.S. Pat. No. 3,767.
Examples include polysaccharides described in No. 410.

Preferred thickeners include polystyrene sulfonate,
Examples include polyacrylates, polyvinyl phosphates, 2-acrylamido-2-methylpropanesulfonates, polyacrylates, polyethylenesulfonates, gluoxylates, and copolymers of these polymers. The repeating units to be copolymerized may be different anionic units, or may be units of polystyrene, polyvinyl alcohol, etc.

The surfactant that can be used in the present invention can be used for various purposes such as coating aid, antistatic, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast, sensitization). be done.

As a surfactant, for example, saponin (steroid type)
, alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides, silicones nonionic surfactants such as polyethylene oxide adducts), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, 1-alkyl carboxylates, Alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, such as polyoxyethylene alkyl phosphates;
Amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines,
Amphoteric surfactants such as amine oxides: alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium containing aliphatic or heterocyclic rings. Cationic surfactants such as salts;
Fluorine-containing surfactants such as perfluoroalkyl borates, perfluoroalkyl phosphates, perfluoroalkyl sulfonates, and perfluoroalkyl carboxylates can be used.

These include Ryohei Oda et al.'s "Surfactants and Their Applications" (Maki Shoten, 1964), Hiroshi Horiguchi's "New Surfactants" (Sankyo Publishing ■, 1975), and "Matsuku Cations Detergent and Emulsifier". ' (Matsufucation Divisions, MC Publishing Company 1985') (rMc Cut
Cheon's Detergents &
IEmulsifiers” (Mc CuLcheo
n Division+3+ MC Publishing
gCo.

1985) ), IronEasy Product Research and Development (r! EC)
Product Re5erch and De
(1962゜9)
, Oil Chemistry Jl (12) (1963) p653
, JP 60-76741, JP 62-172343, JP 62-173459, JP 62-215272,
No. 53-21922, No. 52-25087, No. 60
-109548, 61-41143, 62-2
No. 93241, Special Publication No. 56-1617, No. 47-93
No. 03, British Patent No. 1503218, US Patent No. 42
It is described in No. 92402, etc.

The hydrophilic colloid layer used in the present invention includes colloidal silica, barium strontium sulfate, polymethyl methacrylate, methyl methacrylate-methacrylic acid copolymer, and methyl methacrylate-styrene sulfonic acid described in JP-A-63-216046. Copolymer, JP-A-61-2301
A so-called matting agent made of particles containing fluorine groups as described in No. 36 can be used.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other constituent layers. For example, aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), active vinyl compounds (1,3,5
-) lyacryloyl-hexahydro-3-triazine,
1.3-vinylsulfonyl-2-propatol, etc.),
Active halogen compounds (such as 2,4-dichloro-6-hydroxy-5-lyazine), mucohalogen acids (such as mucochloric acid and mucophenoxychloric acid), and the like can be used alone or in combination.

The present invention can be applied to various positive color photosensitive materials. Positive-working silver halide color light-sensitive materials include color reversal silver halide light-sensitive materials that utilize color reversal development processing, internal latent image type silver halide grain emulsions that have not been fogged in advance, and are processed in the presence of a nucleating agent. In addition to direct positive-type silver halide color photographic materials that undergo color development, there are also silver dye bleaching-type silver halide color photographic materials that bleach dyes using silver oxidation catalysts.

Furthermore, the present invention can also be applied to positive black and white photographic materials with negative light. , JP-A-59-208540, JP-A-60
-260039, B/W direct positive photographic light-sensitive materials (for example, phototypesetting light-sensitive materials), and the like.

Furthermore, the present invention can also be used for color diffusion transfer photosensitive materials.

Color reversal silver halide photosensitive materials that utilize color reversal development generally use a negative silver halide emulsion and undergo various processes such as black and white development, water washing, reversal, color development, water washing or adjustment, desilvering, water washing, stabilization, etc. A positive image is formed in the process.

Excluding special methods, the methods used to create positive images using conventionally known direct positive silver halide photographic materials can be mainly divided into two types, considering their practical usefulness. can.

One type uses a silver halide emulsion that has been coupled in advance and obtains a positive image directly after development by destroying the capri nucleus (latent image) in the exposed area using solarization or the Burschel effect. It is something.

The other type uses an internal latent image type silver halide emulsion that has not been fogged in advance, and after image exposure, performs capri processing, or performs surface development while performing fog processing to directly obtain a positive image. .

The above-mentioned internal latent image type silver halide photographic emulsion is a type of silver halide photographic emulsion in which photosensitive nuclei are mainly located inside the silver halide grains, and a latent image is mainly formed inside the grains upon exposure. means.

Various techniques are known in this technical field. For example, U.S. Pat. No. 2,592.250, U.S. Pat.
．． No. 588.982, No. 3.317.322, No. 3,
761.266, 3,761.276, 3,7
The main ones are those described in British Patent No. 96.577 and the specifications of British Patent No. 1.151.363, British Patent No. 1.150.553, and British Patent No. 1,011,062.

For details on the direct positive image formation mechanism, see, for example, "The Theory of the Photographic Process J" by T. H. James.
y of the Photographic Pro
cess), 4th edition, Chapter 7, pages 182 to 193, and US Pat. No. 3,761,276.

In other words, due to the surface desensitization effect caused by the so-called internal latent image that resides inside the silver halide by the first image #an light, selective fog nuclei are generated only on the surface of the silver halide grains in the unexposed areas. Then, a photographic image (direct positive image) is created in the unexposed area by applying a normal so-called surface development process.
is thought to be formed.

As mentioned above, as a means for selectively generating fog nuclei, a method of applying a second exposure to the entire surface of the photosensitive layer, which is generally called a "photofogging method" (for example, described in British Patent No. 1.151.
363) and a nucleating agent (U
A method using a creating agent) is known. This latter method is discussed, for example, in ``Research Disclosure'' (Research Disclosure).
Closure) Magazine, Volume 151, k15162 (1
Published in November 1976), 76-78.

The fogging treatment by the "light fogging method" is carried out after imagewise exposure, by developing processing and/or by exposing the entire surface to light during the developing processing.

The imagewise exposed photosensitive material is immersed in a developer solution or a pre-bath of the developer solution, or is taken out from the solution and exposed to light on its entire surface before it dries, but it is most preferable to expose the entire surface in a developer solution. .

The nucleating agent used when applying the "chemical fogging method" can be contained in the light-sensitive material or in the processing solution for the light-sensitive material. Preferably, it can be incorporated into the photosensitive material.

Here, the "nucleating agent" is a substance that acts to directly form a positive image during surface development of an internal latent image type silver halide emulsion that has not been fogged in advance.

In the positive image-forming photographic light-sensitive material of the present invention, the silver halide grains contained in the color reversal photographic light-sensitive material or the photographic emulsion layer are internal latent image type silver halide grains that have not been fogged in advance, and the nucleating agent is The effect is remarkable in photosensitive materials of the type that are directly developed to form positive color images in the presence of .

The nucleating agent may be contained in the photosensitive material or in the processing liquid.

In the present invention, it is preferable to include a nucleating agent in the light-sensitive material.

As the nucleating agent that can be used in the present invention, all compounds conventionally developed for the purpose of nucleating latent silver halide can be used. Nucleating agents may be used in combination of two or more types. To explain in more detail, nucleating agents include, for example, [
Research Disclosure J
h Disclosure) magazine, Na22534 (19
Published in January 1983) pp. 50-54, same magazine, 15162 (
Published in November 1976) pp. 76-77, same magazine, k235
10 (published November 1983), pages 346-352.

These are broadly classified into quaternary heterocyclic compounds, hydrazine compounds, and other compounds.

In the present invention, a quaternary heterocyclic compound represented by the following formula (1) is particularly suitable.

General formula (1) (wherein, Z represents a group of nonmetallic atoms necessary to form a 5- to 6-R heterocycle, Z may be substituted with a substituent, R1 is an aliphatic group, and Qt is a hydrogen atom, an aliphatic group, or an aromatic group. RI and R8 may be substituted with a substituent, and R1 may further be connected to the heterocycle completed by Z to form a ring. However, at least one of the groups represented by R1, R1, and 2 contains an alkynyl group, an acyl group, a hydrazine group, or a hydrazone group, or forms a 6-membered ring with RI and Hz, and has a dihydropyridinium skeleton. Furthermore, some of the substituents of R1, jp and Z (one of which may have a group promoting occlusion to silver halide, Y is a counter ion for charge balance, n is O or l.

More specifically, examples of the heterocycle completed by Z include quinolinium, benzothiazolium, benzimidazolium, pyridinium, acridinium, phenanthridinium, and isoquinolinium nuclei.

Examples of the substituent 2 include an alkyl group, an alkenyl group, an aryl group, an alkynyl group, a hydroxy group, an alkoxy group,
halogen atom, amino group, acyl group, carbamoyl group,
Examples include ureido group, urethane group, hydrazine group, hydrazone group, and imino group.

The aliphatic groups of R1 and R1 are an unsubstituted alkyl group having 1 to 18 carbon atoms and a substituted alkyl group having 1 to 18 carbon atoms in the alkyl portion. Examples of the substituent include those described for the Wt substituent of Z.

The aromatic group represented by C has 6 to 20 carbon atoms,
Examples include phenyl group and naphthyl group. Examples of the substituent include those described as the substituent for Z. C is preferably an aliphatic group, most preferably a methyl group and a substituent methyl group.

Among the groups represented by R1, R8 and 2, one has an alkyl group, an acyl group, a hydrazine group, or a hydrazone group, or R1 and R mushroom form a 6-membered ring, and dihydropyridinium These form a skeleton, and these may be substituted with the groups described above as substituents for the group represented by 2.

It is preferable that at least one of the groups or substituents on the ring represented by R1, R1 and 2 is an alkynyl group or an acyl group, or that R1 and 8-fold are linked to form a dihydropyridinium skeleton. , and more preferably contains a small number of (one) alkynyl group.

Preferred examples of the adsorption-promoting group to silver halide represented by xl include a thioamide group, a mercapto group, and a 5- or 6-membered nitrogen-containing heterocyclic group.

The thioamide group which may be substituted with the substituents mentioned above for Z is preferably an acyclic thioamide group (eg, thiourethane group, thiourido group, etc.).

The mercapto group of
3,4-thiadiazole, etc.) are preferred.

The 5- to 6-membered nitrogen-containing heterocycle represented by x1 is one consisting of a combination of nitrogen, oxygen, sulfur, and carbon, and preferably one that produces iminosilver, such as benzotriazole.

Examples of the counter ion Y for charge balance include bromide ion, chloride ion, iodide ion, p-toluenesulfonate ion, ethylsulfonate ion, perchlorate ion, trifluoromethanesulfonate ion, thiocyanate ion, etc. It will be done.

Specific examples of the nucleation side represented by general formula (1) are given below, but the invention is not limited to these.

(1-1) 5-ethoxy-2-methyl-1-propargylquinolinium bromide (1-2) 2,4-dimethyl-1-propargylquinolinium bromide (r-3) 2-methyl-1-( 3-(2-(4-methylphenyl)hydrazino]butyl 1-quinolinium iosito([-4)3.4-dimethyl-dihydropyrido(2,1
-bl benzothiazolium bromide (1-5) 6-nitoxythiocarbonylamino-2-methyl-1-propargylquinolinium trifluoromethanesulfonate (1-6) 2-methyl-6-(3-phenylthio ureido)-1-propargylquinolinium bromide (1-7)6-(5-benzotriazolecarboxamide)-2-methyl-1-propargylquinolinium
Trifluoromethanesulfonate (1-8) 6- (3
-(2-mercaptoethyl)ureido]-2-methyl-1-propargylquinolinium trifluoromethanesulfonate (1-9)6- (3-(3-(5-mercapto-1,3,4-thiadiazole-2) -ylthio)propylthureido)-2-methyl-1-propargylquinolinium trifluoromethanesulfonate (f-10)6- (5-mercaptotetrazole-1
-yl)-2-methyl-1-propargylquinolinium iositojl-11) l-propargyl-2-(1-propenyl)quinolinium trifluoromethanesulfonate N-12) 6-nitoxythiocarbonylamino-2-(
2-Methyl-1-propenyl)-1-propargylquinolinium trifluoromethanesulfonate (f-13) 1G-propargyl-1,2,3,4
-Tetrahydroacridinium trifluoromethanesulfonate (f-14)? -ethoxythiocarbonylamino-IO
-Propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate (1-15) 6-ethoxythiocarbonylamino l-propargyl-2,3-pentamethylenequinolinium trifluoromethanesulfonate ( 1-16) 7-(3-(5-mercaptotetrazol-1-yl)benzamido)-10-propargyl-
1,2,3,4-tetrahydroacridinium perchlorate (1-17)6-(3-(5-mercaptotetrazol-1-yl)benzamide)-1-propargyl-2
, 3-pentamethylenequinolinium bromide (1-18) 7- (5-mercaptotetrazole-
1-yl)-9-methyl-10-propargyl-1,2
,3,4-tetrahydroacridinium bromide (1-19)? -[3-(N-(2-(5-mercapto-1,3,4-thiadiazol-2-yl)thioethyl]carbamoyl)propanamide]10-propargyl-1,2,3,4-tetrahydroacridinium Tetrafluoroborate (1-20) 6- (5-mercaptotetrazole 1-
yl)-4-methyl-1-propargyl 2,3-pentamethylenequinolinium promide(+-21)7-nitoxythiocarponylamino 10
-Propargyl-1,2-dihydroacridinium trifluoromethanesulfonate (1-22) 7- (5
-Mercaptotetrazol-1-yl)-9-methyl-
IO-propargyl 1,2-dihydroacridinium
Hexafluorolophosphate (1-23) 7- (3-(5-mercaptotetrazol-1-yl)benzamide)-10-propargyl-
1,2-dihydroacridinium bromide In addition, in the present invention, the following general formula (N-n) is used as a nucleating agent:
A hydrazine compound represented by can be used.

General formula (N-n) (wherein Rit represents an aliphatic group, aromatic group, or heterocyclic group, 1 (21 is a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group or amine group; G represents a carbonyl group, sulfonyl group, sulfoxy group, phosphoryl group, or iminomethylene group (NH=C), and R13 and R24 are both hydrogen atoms, or one of them is a hydrogen atom. the other represents any one of an alkylsulfonyl group, an arylsulfonyl group, or an acyl group, provided that Q, Rtt, R1
4 and the hydrazone structure C including the hydrazine nitrogen.
>NN=C) may be formed. Further, the groups described above may be substituted with a substituent if possible. ) Specific examples are given below, but the invention is not limited to these.

(n-1) 1-formyl-2-(4-C3-(2methoxyphenyl)ureido)-phenyl)hydrazine (■-2) 1-formyl-2-(4-(3-(5-mercabutyl) Tetrazol-1-yl)benzamido]phenyl)hydrazine (n-3) 2- (4-(benzotriazole-5-carboxamido)phenyl)-1-formylhydrazine (■-4) 1-formyl-2-+4- ( 1-(N-phenylcarbamoyl)thiosemicarbazide phenyl)
Hydrazine (■-5)■-formyl-2- [4-[3-(3-(
When adding the 2,4-DiLet t-pentylphenoxy)propyl]ureido)phenyl]hydrazine nucleating agent to the processing solution, add it to the developer or JP-A-17835
It may be included in a low pH prebath such as that described in No. 0.

When adding a nucleating agent to the processing solution, the amount used is 1ff.
It is preferably 10-1 to 101 mol, more preferably 10-7 to 10-4 mol per i.

When a nucleating agent is contained in a photographic light-sensitive material, it is used as a solution of a water-miscible organic solvent such as alcohol WI (e.g. methanol, ethanol), esters (e.g. ethyl acetate), ketone 1it (e.g. acetone). Alternatively, if it is water-soluble, it may be added to the hydrophilic colloid solution as an aqueous solution.

When added to a photographic emulsion, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added after chemical ripening is completed.

In the present invention, the nucleating agent may be contained in the hydrophilic colloid layer adjacent to the silver halide emulsion layer, but is preferably contained in the silver halide emulsion layer.

The amount added varies depending on the characteristics of the silver halide emulsion used in practice, the chemical structure of the nucleating agent, and the development conditions, so it can vary over a wide range, but it is about IXl0- per 111 moles in the silver halide emulsion. 'Mole to about lXl
A range of 0-'' molar is practically useful, with 1i! being preferred.
When the nucleating agent is used at about 1XIO-' moles per mole to about 1XIO-3 moles per mole, it is preferred to use a nucleation accelerator to promote the action of the nucleating agent.

A nucleation accelerator is a substance that does not substantially function as a nucleating agent, but is necessary to promote the action of the nucleating agent to increase the maximum density of a direct positive image and/or to obtain a constant direct positive image density. A substance that works to speed up the development time.

Such nucleation accelerators include tetrazaindenes having at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group;
Mention may be made of triazaindenes, pentazaindenes, and the compounds described in JP-A-63-106656, pages 5 to 16.

Specific examples of nucleation accelerators are given below.

1? tot CHgCHtSCIIi ■ 104 R1°.

-34 CIl□GHzN(C1h)z The nucleation accelerator can be contained in the light-sensitive material or in the processing solution, but it is especially useful in internal latent image type silver halide emulsions and other hydrophilic colloid layers in the light-sensitive material. It is preferably contained in a silver halide emulsion (such as an intermediate layer or a protective layer), and particularly preferably in a silver halide emulsion or a layer adjacent thereto.

The amount of nucleation accelerator added is 10 per mole of 1m of halogenation.
-' to 10-'' mole is preferred, more preferably 1o-
5 to 10-'' mole.

In addition, when the nucleation accelerator is added to the processing solution, that is, the developer or its pre-bath, 1 o-s to 10-'
It is preferably mol, more preferably 10-7 to 10-4 mol.

Moreover, two or more kinds of nucleation accelerators can also be used together.

The unfogged internal latent image type silver halide emulsion that can be used in the present invention is a silver halide emulsion in which the surface of the silver halide grains is prefogged (although the halide layer image is mainly formed inside the grains). It is an emulsion containing silver, and more specifically, a silver halide emulsion is deposited on a transparent support at a fixed rate.
jtl cloth and exposed to light for a fixed time of 0.01 to 10 seconds in the following developer A (internal type developer).
When developed at 18°C for 5 minutes, the maximum density measured by a normal photographic density measurement method is that of a silver halide emulsion coated in the same amount and exposed in the same manner as above in the following developer B (surface type developer). Preferred are those having a density that is at least 5 times greater, more preferably at least 10 times greater, than the maximum density obtained when developed at 20° C. for 6 minutes.

Internal developer A Metol 2g Sodium sulfite (
Anhydrous) 90g Hydroquinone 8g Soda carbonate (-water salt) 52.5g KBr
5 gKl
, add 9.5g water
11 Surface developer B Metol 2.581-Ascorbic acid 10 gNaBOg'4H*
O 35g KBr 1g Add water to create an internal type emulsion. Examples of conversion type silver halide emulsions include the conversion type silver halide emulsion described in the specification of US Pat. No. 2,592,250;
U.S. Patent No. 3.761.276, U.S. Patent No. 3,850.63
No. 7, No. 3,923.513, No. 4,035,185
No. 4,395.478, No. 4, 504, 57
No. 0, JP-A-52-156614, JP-A No. 55-1275
No. 49, No. 53-60222, No. 56-22681, No. 59-208540, No. 60-107641,
No. 61-3137, Japanese Patent Application No. 61-3642, Research Disclosure Magazine Somu 2351G (1983
The core/shell type silver halide emulsion described in the patent disclosed in P. 236 (published in January) can be mentioned.

The shapes of the silver halide grains used in the present invention include cubic, octahedral, dodecahedral, and tetradecahedral regular crystals, irregular crystals such as spherical, and length. /Thickness ratio value of 5 or more may be used.
Emulsions having composite forms of these various crystal forms or mixtures thereof may be used.

The composition of silver halide includes silver chloride and silver bromide mixed silver halide, and the silver halide preferably used in the present invention does not contain silver iodide, or even if it contains it, it contains less than 3% mole of salt (
(iodine) silver bromide, (iodine) silver chloride or (iodine) silver bromide.

The average grain size of the silver halide grains is 2μ or less and 0.
It is preferably 1μ or more, but particularly preferably lIJ or less 0
．． The particle size distribution of 15 μ or more may be narrow or wide, but in order to improve graininess and sharpness, it should be within ±40% of the average particle size in terms of particle number or weight, preferably within ±20%. It is preferable to use a so-called "monodisperse" silver halide emulsion in the present invention, which has a narrow grain size distribution in which 90% or more of the total grains are contained in , two emulsion layers with substantially the same color sensitivity but different grain sizes.
More than one type of monodisperse silver halide emulsion or a plurality of grains of the same size but different in sensitivity can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be used in a mixed or layered manner.

The silver halide emulsion that can be used in the present invention can be chemically sensitized inside or on the grains by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination. For detailed specific examples, see Research Disclosure magazine Na17643-111 (197
(Published in December 2008) It is in the patent described on page 23 etc.

Photographic emulsions that can be used in the present invention are spectrally sensitized with photographic sensitizing dyes in a conventional manner.

Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, detailed examples of the above-mentioned dyes and supersensitizers may be used in combination include, for example, Research Disclosure Magazine N [L17643-
IV (issued December 1978), in the patent described on pages 23-24, etc.

The photographic emulsion used in the present invention may contain an antifoggant or a stabilizer for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. For detailed specific examples, please refer to Ebo Research Disclosure Magazine N [117643-
Vl (published December 1978) and B, J, Bi
Written by rr”5 tabilization of Photo
graphic 5ilver Halida Emu
lsions” (FocalPress), 1974
It is listed in annual publications.

A variety of color couplers can be used to form positive color images. Useful color couplers include p-
A compound that generates or releases a dye, preferably a non-diffusible dye, by a coupling reaction with an oxidized product of a phenylenediamine color developer, and is itself a substantially non-diffusible compound. Typical examples of useful color couplers include:
These include naphthol or phenolic compounds, pyrazolones or pyrazolone azole compounds, and open-chain or heterocyclic ketomethylene compounds.

Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention can be found in "Research Disclosure" Magazine 17643 (published December 1978) P2
It is described in the compounds described in Section 5.-ri, Oka No. 18717 (published in November 1979) and Japanese Patent Application No. 32462/1983, and the patents cited therein.

Among them, representative examples of yellow couplers that can be used in the present invention include oxygen atom elimination type and nitrogen atom elimination type yellow m:equivalent couplers. Especially α−
Pivaloylacetanilide couplers are preferred because they provide excellent color fastness, particularly light fastness, while α-benzoylacetanilide couplers provide high color density.

Further, as the 5-pyrazolone magenta coupler that can be preferably used in the present invention, a 5-pyrazolone coupler in which the 3-position is substituted with an arylamino group or an acylamino group (especially a sulfur atom-eliminated two-equivalent coupler) is used.

More preferred are pyrazoloazole couplers, and among them, pyrazolo(5,1-c)(1,2,4) riazoles described in U.S. Pat. No. 3,725.067 are preferred; The imidazo(1,2-b)pyrazoles described in U.S. Pat. No. 4,500,630 are more preferable from the viewpoint of low yellow side absorption of the dye and light fastness, and U.S. Pat. No. 4,540,654 Particularly preferred are pyrazolo(1,5-b)(1,2,4))riazoles described in .

Cyan couplers that can be preferably used in the present invention include:
U.S. Patent Nos. 2,474,293 and 4,052,21
These are naphthol-based and phenol-based couplers described in No. 2 and the like.

It is a phenolic cyan coupler having an alkyl group greater than or equal to an ethyl group at the meta position of the phenol nucleus described in U.S. Pat. It is preferable in this respect.

Colored couplers to correct unnecessary absorption in the short wavelength range of the generated dyes, couplers in which the coloring dye has appropriate diffusivity, non-coloring couplers, DIR couplers that release a development inhibitor along with the coupling reaction, or Couplers that release development accelerators and polymerized couplers can also be used.

Typical amounts of color couplers used range from 0.001 to 1 mole per mole of photosensitive silver halide;
Preferably from 0.01 to 0.5 for yellow couplers.
moles, for magenta couplers 0.003 moles to 0
．． 3 moles, and 0.002 to 0 for cyan couplers.
．． It is 3 moles.

A color enhancer can be used in the present invention for the purpose of improving the color development of the coupler. A typical example of a compound is JP-A No. 6
Examples include those described in No. 2-215272, pages 374-391.

The coupler of the present invention is dissolved in an organic solvent with a high boiling point and/or a low boiling point, and is added to an aqueous solution of gelatin or other hydrophilic colloid by high-speed stirring using a homogenizer, mechanical pulverization using a colloid mill, or using ultrasonic waves. The emulsified fraction is formed using the technique described above and added to the emulsion layer. In this case, it is not necessary to use a high boiling point organic solvent, but
It is preferable to use the compounds described on page.

The coupler of the present invention is disclosed in JP-A-62-215272 No. 468.
It can be dispersed in a hydrophilic colloid by the method described on pages 1 to 475.

The photosensitive material produced according to the present invention contains hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers,
Typical examples of zero-color capri inhibitors and color mixture inhibitors that may contain sulfonamide phenol derivatives are disclosed in Japanese Patent Application Laid-Open No. 62-1999.
No. 215272, pages 600-630.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
Hindered phenols, mainly 6-hydroxychromans, 5-hydroxycoumarans, spirocoumarones, p-alkoxyphenols, and bisphenols;
Representative examples include gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Further, metal complexes such as (biszaritylaldoximato)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

The photosensitive material of the present invention contains dyes to prevent irradiation and halide, ultraviolet absorbers, plasticizers, optical brighteners, matting agents, air fog preventive agents, antistatic agents, slippery improvers, etc. I can do things. Representative examples of these additives are
rch Disclosure) Magazine N1117643
Sections Vl-XI (published December 1978) p25-2
7, and 1B716 (issued in November 1979)
It is described on pages 647-651.

It is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support of the invention.

A multilayer, multicolor photographic material usually has a small number of each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as necessary. The preferred order of layer arrangement is red sensitivity, green sensitivity, and blue sensitivity from the support side, or green sensitivity, red sensitivity, and blue sensitivity from the support side.Furthermore, each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities. A non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity.
Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

Furthermore, when the photosensitive material of the present invention is used for color diffusion transfer, a dye developer can be used as a coloring material.
The coloring material itself is alkaline (in the developer) and non-diffusible (
It is advantageous to use a type of colorant that is non-migratory) but releases a diffusible dye (or its precursor) as a result of development. These diffusible dye-releasing coloring materials (DRR compounds) include couplers and redox compounds that release diffusible dyes, and these are applied using the color diffusion transfer method (wet method).
It is useful not only as a coloring material for heat-developable sensitive materials (dry method) as described in, for example, JP-A No. 58-58543.

The "reflective support" used in the present invention is one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Examples include those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate film,
There are polystyrene films, vinyl chloride resins, and the like, and these supports can be appropriately selected depending on the purpose of use.

As a light-reflecting substance, it is best to thoroughly knead a white pigment in the presence of a surfactant, and also coat the surface of the pigment particles with 2 to 4
It is preferable to use one treated with a dihydric alcohol.

The present invention is particularly effective in the case of paper coated with polyethylene or polyethylene, and is particularly effective in the case of thin paper supports of 50 to 150 mm.

In the present invention, the coating method for applying a layer on the reflective support is not particularly limited, and examples include bar coating, roll coating, knife coating, flow coating (curtain coating), and gravure coating. Conventional techniques such as coating methods, spray coating methods, dip coating methods and extrusion coating methods can be mentioned.

Coating methods for these layers may include either individual coating or simultaneous multilayer coating. Coating methods for simultaneous multilayer coating of two or more photographic constituent layers include extrusion coating using a hopper and curtain coating described in U32681294. Flow coating and slide hopper coating are preferred.

The photographic light-sensitive material according to the present invention may be subjected to development treatment depending on the type of light-sensitive material, such as development treatment to form a silver image (black and white development treatment), development treatment to form a color image by coupling reaction (color development treatment). Development processing that forms a color image using a reversal method (reversal color development processing), Development processing that forms a color image by bleaching dyes (silver dye bleaching method), Development processing that forms an image by diffusing and transferring silver or dye. (diffusion transfer method) is performed.

The black-and-white development process includes the usual method described in "Research Disclosure" magazine Nα17643, section XIX-XX4, and includes, for example, a development process, a fixing process, and a water washing process. After the development process, a stop process may be performed, and when a stabilization process is performed after the fixing process, the water washing process may be omitted. Further, the developing agent or its precursor may be incorporated into the photosensitive material, and the developing process may be performed using only an alkaline solution, or the developing process may be performed using a lithium developer as the developing solution.

Examples of the color development process include the usual methods described in "Research Disclosure" magazine Nα17643, pages 28-29, and "Research Disclosure" magazine Nα18716, 615 left column to right column, such as color development process, bleaching A processing process, a fixing process, and a washing process are performed. Instead of the bleaching process using a bleaching solution and the fixing process using a fixing solution, a bleach-fixing process using a bleach-fixing solution can be performed, or the bleaching process, fixing process, and bleach-fixing process can be optionally performed. May be combined in this order. A stabilization step may be performed instead of the water washing step, or a stabilization step may be performed after the water washing step.

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, an adjustment process, a supplementary process, etc. may be performed. An intermediate water washing step may be provided.

As the color reversal development process, a black and white development process, a water washing or rinsing process, a reversal process, and a color development process are performed within the film. As the reversal process, a reversal bath containing a fogging agent may be used, a light reversal process may be used, or the fogging agent may be included in the color developing solution and the reversal process may be omitted.

When the photosensitive material of the present invention is a black and white photosensitive material, a positive image can be directly obtained by developing it using a surface developer. A surface developer is one in which the development process is substantially induced by latent images or fog nuclei on the surface of silver halide grains.

Various known developing agents can be used to develop black and white light-sensitive materials. That is, polyhydroxybenzenes such as hydroquinone, 2-chlorohydroquinone, 2-methylhydroquinone, catechol, pyrogallol, etc.; aminophenols such as p-aminophenol, N-methyl-p-aminophenol,
2.4-diaminophenol, etc.; 3-pyrazolidones, such as 1-phenyl-3-pyrazolidones, 1-phenyl-4,41-dimethyl-3-pyrazolidone, l-phenyl-4-methyl-4-hydroxymethyl- 3-pyrazolidone, 5.5-dimethyl-1-phenyl-3-pyrazolidone, etc.; ascorbic acids, etc. can be used alone or in combination.

Further, the developer described in JP-A-56-154116 can also be used.

Although it is preferable not to include a silver halide solubilizer in the developer, as long as the internal latent image does not substantially contribute to the completion of development by the surface development centers of the silver halide grains,
Such developers, which may include halogenated 1M solubilizers (e.g. sulfites), may be included in the alkaline processing composition (processing element) or in the appropriate layer of the photosensitive element. Good too.

The developer may contain preservatives such as sodium sulfite, potassium sulfite, ascorbic acid, and reductones (eg, piperidinohexose reductone).

The developer contains sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
The content of these agents, which may include trisodium phosphate, sodium metaborate, etc., is chosen to provide a pH of the developer between 9 and 13, preferably between 10 and 11.2.

The developer also contains, for example, benzimidazoles, such as 5-
It is advantageous to include compounds commonly used as antifoggants, such as nitrobenzimidazole; benzotriazoles, such as pensitriazo, -l, 5-methyl-benzotriazole.

For detailed examples of developers, preservatives, buffers, and development methods for black and white photosensitive materials, and how to use them, see
Research Disclosure” magazine Na17643 (1
(Published in December 1978) Section XIX-XX1 etc.

When the light-sensitive material of the present invention is a color light-sensitive material, the one-color developer used for color development processing is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, aminophenol compounds are also useful, but p-phinidine diamine compounds are preferably used, and representative examples thereof include 3
-Methyl-4-amino-N,N-diethylaniline, 3
Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or P-
Examples include toluene sulfonate. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. In addition, as mentioned above, nucleating agents and nucleating accelerators may be included, and if necessary, hydroxylamine, diethylhydroxylamine, sulfites, hydrazines, phenyl semicarbazides, triethanolamine, catechol Sulfonic acids, triethylenediamine (l,4-diazabicyclo(2,2
, 21 octane), various preservatives such as ethylene glycol, organic solvents such as diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, sodium Boron High Tri any fogging agents, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, aminopolycarboxylic acids,
Various chelating agents such as aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,
Hydroxyethyliminodiacetic acid, l-hydroxyethylidene-1゜l-diphosphonic acid, nitrilo-N,N,N-
1-rimethylenephosphonic acid, ethylenediamine-N,
,,,N.

Representative examples include N',N'-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof.

The pH of these color developing solutions is generally 9 to 12, preferably 9.5 to tt, S.

The photographic emulsion layer after color development is usually subjected to desilvering treatment.

The desilvering process may be carried out simultaneously with bleaching and fixing (bleaching and fixing), or separately (bleaching and fixing). Furthermore, in order to speed up the process, a bleaching process and a bleaching and fixing process may be used. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents include iron (■),
Compounds of polyvalent metals such as cobalt (■), chromium (V[), * (II), etc., peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include ferricyanide-dichromate. ; Iron (III) or cobalt (■)
organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,
Methyliminodiacetic acid, l.

Aminopolycarboxylic acids such as 3-diaminopropanetetraacetic acid, glycol ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; persulfates; bromates; permanganates; nitrobenzenes, etc. may be used. I can do it.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

After desilvering, it is common to undergo a water washing and/or stabilization process.

The pl+ of the washing water in the processing of the photosensitive material obtained according to the present invention is from 4 to 9, preferably from 5 to 8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 seconds at 15 to 45°C.
minutes, preferably in the range of 30 seconds to 5 minutes at 25-40'C. Furthermore, instead of washing with water, the treatment can be carried out directly with a stabilizing solution. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8,543 and 5B-14,83
All known methods described in No. 4, No. 60-220,345 can be used.

It is also possible to add various botanical agents and antifungal agents to this stabilizing bath. The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

The various processing solutions in the above-mentioned treatments are used at temperatures of 10"C to 50C. Normally, temperatures of 33C to 38C are standard.

When the light-sensitive material obtained according to the present invention is used for a film unit for diffusion transfer method, it is preferable to process it with a viscous developer. This viscous developer is a liquid composition containing processing components necessary for the development of silver halide emulsions (and the form of diffusion transfer color accumulation), and the solvent is mainly water.
Other hydrophilic solvents such as methanol and methyl cellosolve may also be included. Preferably, the treatment composition contains a hydrophilic polymer such as high molecular weight polyvinyl alcohol, hydroxyethyl cellulose, sodium carboxymethyl cellulose. These polymers are preferably used to give the treatment composition a viscosity of 1 poise or more, preferably about 500 to 1000 poise, at room temperature.

The above treatment composition is described in U.S. Pat. No. 2.543.181;
2,643.886, 2,653,732, 2,723,051, 3,056,491, 3
．． It is preferable to use it by filling it into a container that can be ruptured by pressure, such as those described in No. 056.492 and No. 3,152,515.

[Effect]

In the present invention, when at least one hydrophilic colloid layer is formed using a coating liquid with a viscosity of 50 to 200 centipoise, density unevenness is less likely to occur (although the mechanism of action is not clear). Since the image density is proportional to the thickness of the hydrophilic colloid layer, especially the photographic emulsion layer, when coating using the above-mentioned coating solution, the reflective support is coated with an approximately -like thickness regardless of its surface irregularities. This is thought to be due to the ability to form a thin layer.

JP-A No. 63-11934, which was mentioned in the section of the prior art, discloses a technique for eliminating coating unevenness during the production of film photographic materials. This technique is used to prevent uneven coating on surfaces, and even if the coated surface is made smooth using this technique, if this technique is applied to a reflective support that has an uneven surface, the unevenness will cause the coated layer to become uneven. The thickness of the image will change, and density unevenness will occur.

The present invention is different from the prior art because it forms a coating layer with a uniform thickness regardless of its unevenness.

〔Example〕

Example 1 A 1M aqueous solution of potassium bromide and a solution of silver nitrate were added to an aqueous gelatin solution to which 0.13 g of 3.4-dimethyl-1,3-thiazoline-2-thione was added per mole of Ag, while stirring vigorously. Add at the same time at 75°C for approximately 12 minutes.
A monodisperse octahedral silver bromide emulsion with an average grain size of 0.35 was obtained. To this emulsion were added 25 mg of sodium thiosulfate and 25 mg of chloroauric acid (tetrahydrate) per mole of silver, and the
Chemical sensitization treatment was performed by heating for 0 minutes. Using the thus obtained silver bromide grains as cores, they were further grown by further treatment for 40 minutes in the same precipitation environment as the first time, and finally the octahedral monodisperse core/shell silver bromide grains had an average grain size of 0.67ffi. An emulsion was obtained. After washing with water and desalting, this emulsion was mixed with 3.0 ml of silver per mole of silver. Sodium thiosulfate of Orsgfi and chloroauric acid (tetrahydrate) were added and heated at 60°C for 60 minutes to perform chemical sensitization treatment to obtain an internal latent image type silver halide emulsion.

(Production of color photographic paper A) A paper support laminated on both sides with polyethylene using a core/shell type internal latent image emulsion (the polyethylene on the first layer side contains a white pigment (TiOx, etc.) and a bluish dye (such as ultramarine). A full multilayer color photographic paper A having the layer structure shown in Table 1 was prepared on a paper (thickness: 100 μm) having a layer structure shown in Table 1. The coating solution was prepared as follows.

1st J! Preparation of coating solution Add 10 g of ethyl acetate and 4 ae of solvent (C) to 10 g of nitrogen coupler (a) and 2.3 g of color enhancing stabilizer (c) and dissolve. This solution is mixed with 10% sodium dodecylbenzenesulfonate containing 5d. It was emulsified and dispersed in an aqueous gelatin solution of 90%. Separately, 90 g of a red-sensitive emulsion was prepared by adding the following red-sensitive dye to the above-mentioned silver halide emulsion (containing 70 g/kg of Ag) in an amount of 2.0xlO-' mole per it mole of halide.

Red-sensitive dye: Mix and dissolve the emulsion dispersion, emulsion, and development accelerator (d), adjust the concentration with gelatin, add the following nucleating agent and nucleating accelerator, and further add poly(p) as a thickener. - Sodium styrene sulfonate (Mh 700,000 to 1,000,000) was used to adjust the viscosity to the predetermined viscosity shown in Table 2 to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. l-oxy-3 as gelatin hardening agent in each layer
, 5-dichloro-8-triazine sodium salt was used.

The amount of the compound in the coating solution was adjusted to achieve the coating amount shown in Table 1.

Coating was done in multiple layers simultaneously using the slide hopper method.

The following spectral enhancers were used for each emulsion.

The structural formulas of the compounds used in this example, including an irradiation-preventing dye for the red-sensitive emulsion layer and a green-sensitive dye and a blue-sensitive dye coupler, are as follows.

(a) Cyan coupler - eradication prevention dye for green-sensitive emulsion layer■) Color image stabilizer (d) Development accelerator 0■ (e) Color mixture inhibitor 11 (fl) Magenta coupler (C) is added to the carrier color image stabilizer (i ) l:5:3 mixture of ultraviolet absorber medium (mole ratio) 0) 1:2:2 mixture of color mixing inhibitor (weight ratio) (Source) Solvent (i!OCJ+qO+TP=0 Yellow coupler color image stabilizer (ZK) -1) Nucleating agent-16 Nucleating accelerator 2-(3-dimethylaminopropylthio)-2-mercapto-1,3,4-thiadiazole hydrochloride (preparation of color photographic paper B-D (comparative sample)) The viscosity of the coating liquid for color photographic paper A was adjusted using a thickener as shown in Table 2, and sample color photographic paper B-D was obtained.The viscosity was measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). Measurements were made using a rotor No. 0.1 (type BL) at 40° C1C130 rpm sliding speed 29.8 m/5ec).

The color photographic paper produced in this way has a density of approximately 1.0.
(B/W), the exposure conditions were adjusted and the following processing steps were performed to evaluate density unevenness.

Density unevenness was evaluated by the following method.

The exposed and developed sample is punched out to a size of 4C square in diameter, and the density difference in the period 1IiI1 or more is 0.01.
Evaluation was made by counting the number of density spots.

Time Temperature color development 3 minutes 30 seconds 33°C bleach fixing 1 minute 30 seconds 33°C stability ■
1 minute Stable at 33°C ■ 1 minute
Stable at 33℃ ■ 1 minute
The replenishment method for the 33°C stable bath was a so-called countercurrent replenishment method, in which the stabilizing bath ■ was replenished, the overflow liquid from the stable bath ■ was led to the stable bath ■, and the overflow liquid from the stable bath ■ was led to the stable bath ■. .

(Color developer) Diethylenetriamine Pentaacetic acid Benzyl alcohol Diethylene glycol Sodium sulfite Sodium bromide Sulfuric acid Hydroxylamine Sodium chloride 2.0 g 12.8 g 3.4 g 2.0 g 0.26 g 2.60 g 3.20 g 3-Methyl- 4-amino-N-4,25g ethyl-N
-(β-methanesulfonamidoethyl)-aniline potassium carbonate 30.0 g Stilbene 1.0 Add water 1000 mgp
H10,20 pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fix solution]

Ammonium thiosulfate Sodium bisulfite Diethylenetriamine Iron pentaacetate (I[l) Ammonium l hydrate Ethylenediaminetetraacetic acid disodium dihydrate 2-mercapto-1,3,4゛-ol Add water and 10 g 0 g 6 g g 0.5g 000Id pl+ 6
．． 5pn was adjusted with aqueous ammonia or hydrochloric acid.

[Stabilizing liquid]

Table 2 1-Hydroxyethylidene-1,6d l, 1'-diphosphonic acid (60χ) Bismuth chloride 0.35g Polyvinylpyrrolidone 0.25g Aqueous ammonia 2.5m Nitrilotriacetic acid/3Na 1. Og5-chloro-2
- Methyl-4-50 and isothiazolin-3-one 2-octyl-4-isothiazo 50 ■ Phosphorus-3-one fluorescent brightener (4,4"-diaminostyl 1.0
g Add Reuben water 1000 ydP
H7,5 91+ is prepared with potassium hydroxide or hydrochloric acid.

Example 2 Paper support laminated on both sides with polyethylene (thickness 10
A color photographic material (E) was prepared by applying the following 1st layer to 12th layer in a multilayer manner on the 0μ). First polyethylene
On the layer application side, titanium white is used as a white pigment, and v
Contains & amount of ultramarine as a bluish dye.

(Photosensitive layer composition) The components and coating amounts in g/rd are shown below.

Regarding silver halide, the coating amount is shown in terms of silver.

1st layer (gelatin N) Gelatin...-4,30
2nd layer (antilation layer) Black colloid layer °°°゛°゛0・
lO gelatin -・・−・・
0.07 Third layer (low sensitivity red sensitive layer) Chloroiobromide jlpMt (silver chloride 1 mol%, iodide 114 mol%) spectrally sensitized with red sensitizing dye (EXS4, 2.3)
, average particle size 0.3μ, size distribution 1O%, cubic, core-youma type core-shell)...0.06 Spectral sensitized device with red sensitizing dye (ExS-1, 2, 3) SIEM2 (5 mol% iodide 1, average grain size 0.45 μ, size distribution 20%, flat plate (aspect ratio =
5)) -・・・・・・0.
10 gelatin ・−・・−・1
．． 00 cyan coupler (ExC-1) --
-=0.14 cyan coupler (ExC-2)
・・・・・・・・・0.07 Anti-fading agent (Cpd-2,3
, 4,9 equivalents) ・----0.12 Force puller dispersion medium (Cpd-5) ---0,03 Coupler solvent (Solv-1, 2, 3) ---0
,06 4th layer (high sensitivity red sensitivity N) Method-formed SIEM3 spectrally sensitized with red sensitizing dye (ExS-1, 2, 3) (116 mol% iodide, average particle size 0.75μ, Size distribution 25%, flat plate (aspect ratio -8, core demon) --- 0.15 gelatin 4,00 cyan coupler (ExC-1) ---
0.20 cyan coupler (EXC-2) ・
-・・・・・・0. IO anti-fade agent (Cpd-2,3,4
+9 equivalent) ・-・-0゜15 force puller dispersion medium (Cpd
-5) ...-0,03 coupler solvent (
Solv-1, 2, 3) ----0, 10th 5th
N (middle layer) Magenta colloid silver ・−・−・0.0
2 gelatin ・－・・・－・1
．． 00 color mixing prevention agent (Cpd-6,7) ・
-・-0,08 color mixing inhibitor solvent (Solv-4,5)
----0,16 polymer latex (Cpd-
8) ・・・・・・o, i.

6th layer (low sensitivity green sensitive layer) Chloroiobromide 111 spectrally sensitized with green sensitizing dye (t!xs-4)! M4 (silver chloride 1 mol%, silver iodide 2.5 mol%
, average particle size 0.28μ, particle size distribution 12%,
Cube, core demon type core shell)) green sensitizing dye ([!
Emulsion A spectrally sensitized with xs-4)...0.0
4 Silver iodobromide EM5 spectrally sensitized with green sensitizing dye (BxS-3) (silver iodide 2.8 mol%, average grain size 0.45
#, grain size distribution 12%, flat plate (aspect ratio = 5)
) ・・・−・・・−0,06 gelatin
・---0,80 magenta coupler CI! xH-1) -----0,10
Antifading agent (Cpd-9) ・・−・−
・0.10 stain inhibitor (Cpd-10)
...-0,01 stain inhibitor (Cpd-11)
・・・・0.001 Stain inhibitor (C
pd-12) ...-0,01 force puller dispersion medium (Cpd-5) '-...-0,0
5 coupler solvent (Solv-4,6) ・---
-0,15 7th layer (high sensitivity green sensitive layer) Method I spectrally sensitized with green sensitizing dye (ExS-4)
MEMS (silver iodide 3.5 mol%, average grain size 0.9
μ, particle size distribution 23%, flat plate (aspect ratio = 9,
Uniform-youma type)) ・・・・−0,10 Gelatin ・−・・・・0.80 Magenta coupler (ExM-1) −・・・−0,
10 Anti-fading agent (Cpd-9) -・-・-0,1O Anti-fading agent (Cpd-10) ・・−・・
0. Ol stain inhibitor (Cpd-11) ・
...-0.001 stain inhibitor (Cpd-12)
・----0.01 force puller dispersion medium (C
pd-5) ---0,05 coupler solvent (Solv-4,6) ---0,15 8th
Layer (yellow filter layer) Yellow colloidal silver gelatin color mixture prevention side (Cpd-7) Color mixture prevention agent solvent (Solv-4, 5) Polymer latex (Cpd-8) 9th layer (low sensitivity blue sensitivity 11) Blue sensitizing dye Silver chloroiodobromide EM7 spectrally sensitized with (EXS-5, 6) (chloride ff 12 mol%, silver iodide 2.5 mol%, average grain size 0.35 u, grain size...
・・−・−0,20 ・・−1,00 ・・・・−・−0,06 ・−・−0,15 −−−−−−・0.10 Fabric 8%, cubic, core-shaped deformation core shell)) −・−0,
07 Silver iodobromide EM8 (silver iodobromide 2.5 mol%, average grain size 0) spectrally sensitized with blue sensitizing dye (ExS-5, 6)
．． 45μ, grain size distribution 16%, flat plate (aspect ratio = 6)) ””-・-o, i.

Gelatin ------・0.5
0 Yellow coupler (ExY-1) ---0
, 20 stain inhibitor (Cpd-11) --
0,001 Anti-fading agent (Cpd-6)
”'-・0.10 coupler dispersion medium (Cpd-5)
-0,05 coupler solvent (Solv-2)
--0,05 10th layer (high sensitivity blue sensitive layer) Processed jlEM9 spectrally sensitized with blue sensitizing dye (EMS-5,6) (silver iodide 2.5 mol%, average grain size 1
．． 2μ, particle size distribution 21%, flat plate (aspect ratio -
14)) -m--0,25 gelatin
---1.00 Yellow coupler (ExY-1) ---0,40 Stain inhibitor (Cpd-11) ---0,
002 Anti-fading agent (Cpd-6) -'
-...-0,10 coupler dispersion medium (Cpd-5)
--0,15 coupler solvent (Solv-2)
---0,10 11th layer (ultraviolet absorption layer) Gelatin ---4,5
0 Ultraviolet absorber (Cpd-1,3,13) -1---1.00 Color mixing inhibitor (Cpd-6,14)
-・--0,06 dispersion medium (Cpd-5) ultraviolet absorber solvent (Solv-1,2) -0,
15 anti-irradiation dye (Cpd-15,16) -1・-0,0
2 anti-irradiation dye (Cpd-17,18) ---0-02
12th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0.2
μ) -・----0,07 modified poval −・・−0,02 gelatin −・−・1.50 gelatin hardening agent (H-1) −・−−−0, 1
7 Furthermore, in each layer, alkanol X is added as an emulsifying and dispersing agent.
C (Dupont) and sodium alkylbenzenesulfonate, succinic acid ester and Magefac F-120 (manufactured by Dainippon Ink) were used as coating aids. In the silver halide or colloidal silver containing layer,
(Cpd-19, 20, 21) was used as a stabilizer. The compounds used in Example 2 are shown below.

ExS-6 Cpd-1 Cpd-2 0 Cpd-4 U4■Drop(tJ Shi411qLLJ Cpd 1 H Shi5Hz(L) Cpd-5 Cpd-7 11 0■ Cpd-8 Polyethyl acrylate Cpd-13 Cpd-15 Cpd -11 ExM-1 xY-1 Cpd-21 ll xC-1 Solv-1 di(2-ethylhexyl) phthalate 5o
lv-2) Linonyl phosphate 5olv-3 di(3-methylhexyl) phthalate 5o
lv-4) Recresyl phosphate 5olv-5 dibutyl phthalate Sol Sea 6 trioctyl phosphate 5olv-
71,2-Bis(vinylsulfonylacetamido)ethane (emulsion A) Preparation of a monodispersed emulsion having the (100) crystal habit. Add silver nitrate aqueous solution and XBr to gelatin aqueous solution kept at 70°C while keeping pBr at 4.5. , an aqueous solution containing K+ is added using a double jet to form a monodispersed emulsion (100) having a crystal habit (100).
This core emulsion prepared with an edge length of 0.68 μm was used to form a shell under the following conditions, and the final grain size was adjusted to 0.68 μm.
7-1881 content was set to 3 mol%.

Chemical aggravation was performed by adding sodium thiosulfate and potassium chloroaurate to the above core. Thereafter, the shell was precipitated under the same conditions as for core formation.

In addition, the viscosity of the first layer to the seventh layer is determined by the thickener (polyP
- Sodium styrene sulfonate (M-700,000 to 1,000,000) was used to adjust the viscosity to the predetermined viscosity shown in Table 3. The viscosity was measured using a B-type viscometer (manufactured by Tokyo Keiki, model BL) with rotor No.
, 1 at a temperature of 40° C. and a rotation speed of 30 rpm. (Slipping speed 29.8mm/5ec) Also, the sample (
Samples (F) to (H) were prepared in the same manner as sample (E) except that the viscosity of the coating solution in E) was changed as shown in Table 3.

The coating method was multilayer simultaneous coating using a slide hopper method.

Evaluation method These samples (E) to (H) were tested at a concentration of 1.0 (B/W
) The exposure conditions were adjusted so that the following processing steps were performed, and evaluation was made in the same manner as in Example 1 based on the number of density spots.

Processing ■ First development (black and white development) Washing with water at 38°C for 45 seconds
38℃ 45 seconds inversion exposure 5
001ux or more Color development for 15 seconds or more
38°C Wash with water for 60 seconds 38°C Bleach-fix 38°C Wash with water 38°C Drying Shokoushigo [First developer] Nitrilo-N,N,N-trimethylenephosphonic acid, pentasodium salt Diethylenetriaminepentaacetic acid, pentasodium Salt Potassium sulfite Potassium thiocyanate Potassium carbonate Hydroquinone Monosulfonate/potassium salt Diethylene glycol l-Phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone Potassium bromide Add water 15 seconds 60 seconds 60 seconds 0.6 g 4.0 30.0 1.2 35.0 25.0 g 15.0 d 2.0 g 5.0 ■ 1000 d (pH 9,7) (Color developer) Triethanolamine N, N-diethylhydroxylamine 3.6 -Cythia 1.8-octanediolethylenediaminetetraacetic acid disodium trihydrate Sodium sulfite Potassium carbonate N-ethyl-N-(β-methanesulfonamide ethyl)-3-methylaminoaniline sulfate Potassium bromide iodide Add potassium water and give 8.0 g 60 g 0.2 g 2.0 g 0.2 g 25.0 g 8.0 g 0.5 g 1.0 ■ 1000 d (pi 10.4) Disodium trihydrate ethylenediamine tetra Acetic acid/Fe(III)/ammonium hydrate Sodium sulfite Sodium thiosulfate (700g/1 solution) Add glacial acetic acid water to give Table 3 ,0) [Bleach-fix solution] 2-Mercapto-L3.4-1-Riazole 0.5g
Ethylenediaminetetraacetic acid. [Effects of the Invention] According to the present invention, it is possible to produce a positive image-forming photographic light-sensitive material using a thin reflective support with considerably less density unevenness after development.

In a positive image-forming photographic light-sensitive material using a reflective support, density unevenness is likely to be noticeable due to the need to increase the amount of exposure due to its characteristics. can be reduced.

procedural supplement Ordinary position December 120, 1999

Claims (3)

[Claims] (1) In a method for producing a positive image-forming photographic material having at least one photographic emulsion layer containing silver halide grains on a reflective support, a coating solution forming at least one hydrophilic colloid layer on the support is used. A method for producing a positive image-forming photographic material, characterized in that the viscosity is from 50 centipoise to 200 centipoise. (2) The silver halide grains are internal latent image type silver halide grains that have not been fogged in advance, and are a photosensitive material that can be developed in the presence of a nucleating agent to directly form a positive color image. The method for producing a positive image-forming photographic material according to claim (1). (3) The method for producing a positive image-forming photographic material according to claim (1), wherein the positive image-forming photographic material is a color reversal photographic material.