JPH05165163A - Dye image forming method - Google Patents

Abstract

PURPOSE:To obtain a pigment image forming method easily obtaining a color print excellent in image sharpness and in print glossy. CONSTITUTION:In the method for forming the dye image by color developing a silver halide color photographic sensitive material provided with a photographic sensitive layer on a print paper base for photography provided with a polyolefin coated film layer on both sides of a base paper, the surface of the side having at least the photographic sensitive layer on the base is <=1.0mum in the average roughness (SRa) of the center surface calculated by the formula, the polyolefin coated film layer of the front surface side contains a titanium oxide particle of >=14wt.% in density, a gelatin contained in the photographic sensitive layer is <=7.5g/m<2> and after color development processing, bleaching processing and fixation processing are executed. In the formula, Lx is length of X axial direction in measuring surface region, Ly is length of Y axial direction in measuring surface region, SA is area of measuring surface region, SA= LxXLy, SA=25mm<2>, and Lx=Ly=5mm.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an image forming method for a silver halide color photographic light-sensitive material, and more particularly to an image forming method capable of easily providing a color print excellent in sharpness and gloss.

[0002]

BACKGROUND OF THE INVENTION Silver halide photographic light-sensitive materials (hereinafter, also simply referred to as "light-sensitive materials") have excellent image quality and high sensitivity, but further improvement in image quality is desired. Important factors related to image quality are sharpness that affects the vividness and three-dimensional effect of an image, and gloss that affects the sharpness and high quality of prints.

As a support for color paper for color printing, a reflective support having a polyolefin coating layer on both sides of a base paper is used, which greatly affects the sharpness and gloss.

As a means for improving the sharpness, there is a method of increasing the density of titanium oxide particles contained in the polyolefin coating layer on the side of the support on which the silver halide emulsion is coated.
For example, JP-A-62-275246, JP-A-3-156439, and JP-A-3-156.
No. 444, etc., this method had a drawback that coating unevenness was large.

Further, as a means for improving the gloss, it is effective to improve the smoothness of the support, and, for example, JP-A-63-234251.
No. 2, JP-A-2-83086, No. 2-93640, No. 2-97942, No. 2
No. 216139, No. 2-281251, etc., it was found that this method tends to cause coating unevenness at the beginning of coating.

As a result of various studies, it was found that the gelatin unevenness at the beginning of coating was improved by reducing the amount of gelatin, but it had a drawback that the density change was large during storage for a relatively short time after printing.

On the other hand, manufacturers are required to provide light-sensitive materials to users at a lower price, which requires improvement in the productivity of light-sensitive materials.

[0008] Manufacturers have made various efficiencies in order to increase the production of photographic materials. Among them, among them, the speed at which a photographic constituent layer such as a silver halide emulsion layer is coated on a support, the so-called Increasing the coating speed immediately leads to an improvement in productivity, and therefore a higher coating speed is desired.

However, it is difficult to apply the coating layer uniformly and at high speed without failure, and streaky failures and unevenness are likely to occur, which is an obstacle to speeding up.

In recent years, the demand for large-format prints has been increasing, and even a slight coating failure, which has not been a serious problem in the past, becomes conspicuous in large-format prints and becomes an important quality problem. It is known that such coating properties are greatly influenced by the composition of the silver halide emulsion coating solution and the quality of the support to be coated, and under such circumstances, deterioration of coating unevenness is not allowed at all. Therefore, these comprehensive improvements are required.

On the other hand, the so-called "DPE" in which color negative films are collected, developed and baked on color paper to produce a color print has been conventionally performed in a large developing laboratory (called a large laboratory). In order to improve the efficiency of the collection and delivery system, you can use "DP
I started to do "E".

In the minilab, of course, speeding up the development process
There is a strong demand for simplification, and as one of the means, rapid processing using high silver chloride color paper has already been developed until it occupies most of the market.

As a method for simplifying the remaining development processing and reducing management, it is very effective to use a common bleach-fixing step in the development processing steps of color negative films and color papers or to separate the bleaching solution and fixing solution of the color paper bleach-fixing solution. And
Various studies have been made and practical application is near. However, it has been found that these methods have a serious drawback that the stain is large after running treatment, especially after relatively short-term storage, which is an obstacle to practical use.

[0014]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a dye image forming method capable of easily obtaining a color print having excellent image sharpness and print gloss.

[0015]

The above object of the present invention is to color develop a silver halide photographic light-sensitive material comprising a photographic printing paper support having a polyolefin coating layer on both sides of a base paper and coated with a photographic light-sensitive layer. In the method of forming a dye image by means of a method, the surface of at least the photographic photosensitive layer of the support has a center plane average roughness (SRa) of 1.0 μm or less calculated by the following formula, and the surface side polyolefin Titanium oxide particles are contained in the coating layer at a density of 14% by weight or more, and the gelatin contained in the photographic photosensitive layer is 7.5 g / m ² or less, and after color development processing, bleaching processing and then fixing Achieved by the dye imaging method being processed.

[0016]

[Equation 2]

In the equation, Lx is the length of the measurement surface area in the X-axis direction,
Ly is the length of the measurement surface area in the Y-axis direction, S _A is the area of the measurement surface area, S _A = Lx × Ly, S _A = 25 mm ² , Lx = Ly
= 5 mm.

The present invention will be described in more detail below.

In the present invention, the center surface average roughness (SRa) of the support can be measured using, for example, a surface roughness analyzer SE-3AK manufactured by Kosaka Laboratory.

The base paper used for the support according to the present invention is
It is selected from commonly used materials. That is, natural pulps such as sulfite bleached softwood pulp (NBKP), sulfite bleached hardwood pulp (LBKP), alkali sulfate sulfate bleached softwood pulp (NBSP), alkali sulfate bleached hardwood pulp (LBSP) You may use it in combination of 1 type (s) or 2 or more types. When used in combination, a desirable pulp blending ratio is a hardwood pulp / softwood pulp ratio of 95/5 to 60/40. Further, straw pulp, esparto pulp, bamboo pulp, and synthetic fibers may be blended with the above natural pulp. The thickness of the base paper is
It is selected according to the application, but its basis weight is 50-250g
/ M ² is commonly used.

The following various additives are preferably added to the base paper to enhance the paper strength such as water resistance. For example, as the sizing agent, alkyl ketene dimer fatty acid salt, rosin, maleated rosin, alkenyl succinate, alkyl succinate and polysaccharide are used in an amount of 0.2 to 2% per pulp.

As a dry paper strengthening agent, cationized starch,
Cationized polyacrylamide, anionized polyacrylamide, carboxy-modified polyvinyl alcohol and the like are used.

As the wet paper strength enhancer, melamine resin, urea resin, epoxidized polyamide resin and the like are used.

Further, as the fixing agent, polyvalent metal salts such as aluminum sulfate and aluminum chloride, and cationic polymers such as cationized starch are used.

As the white pigment, various pigments such as clay, talc, calcium carbonate, titanium oxide and barium sulfate may be contained as required.

Generally, the surface of the pulp is tub-sized or size-pressed with a liquid containing various water-soluble polymer additives.

For example, as the water-soluble polymer, cationized starch, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polyacrylamide, gelatin and the like are used.

Salt, mirabilite, etc. are used as the inorganic electrolyte, glycerin, polyethylene glycol, etc. are used as the hygroscopic substance, hydrochloric acid, sodium hydroxide, sodium carbonate, etc. are used as the pH adjusting agent. Additives such as inhibitors and defoamers are used in combination.

The pulp is appropriately beaten to form a pulp slurry containing the above additives as required, and is made into paper by a paper machine such as a Fourdrinier paper machine, dried and supercalendered. Surface sizing is performed before or after this drying.

The support according to the present invention is obtained by coating both sides of the base paper obtained as described above with a polyolefin resin.

The polyolefin resin is, for example, a homopolymer of α-olefin such as polyethylene or polypropylene and a mixture of these various polymers, and a particularly preferable polyolefin is a high density polyethylene, a low density polyethylene or a mixture thereof. The molecular weight of these polyolefins is not particularly limited, but polyolefins in the range of 20,000 to 200,000 are generally used.
The thickness of the polyolefin resin coating layer is not particularly limited, and is usually about 15 to 50 μm.

The titanium oxide used in the polyolefin resin coating layer of the present invention may or may not be surface-treated with aluminum hydroxide, alcohol, a surfactant or the like. These white pigments are contained in an amount of 14% by weight or more, preferably 15 to 18% by weight, based on the polyolefin resin of the polyolefin resin coating layer on the side of the reflective support on which the photographic emulsion is coated.

The SRa of the support according to the present invention is 1.0 μm or less, preferably 0.05 to 0.09 μm. SRa is 1.0
As a method for producing a support having a thickness of μm or less, the coating resin layer is thickened, the pressing pressure at the time of resin coating is increased,
Increase the machine calender pressure to improve the flatness of the base paper, adjust the pulp fiber length, porosity, average fiber width and average fiber thickness forming the base paper, and use one side of the wet paper base paper as a heating mirror dryer. The methods such as using a piece of luster or paper obtained by adhesion are used alone or in combination.

The silver halide grains used in the present invention are
It has a silver chloride content of 90 mol% or more and a silver bromide content of 10
It is preferable that the mol iodide content is less than 0.5 mol% and the silver iodide content is less than 0.5 mol%. More preferably, the silver bromide content is 0.1-1.
It is mol% of silver chlorobromide.

The silver halide grains of the present invention may be used alone or as a mixture with other silver halide grains having different compositions. Further, it may be used as a mixture with silver halide grains having a silver chloride content of less than 90 mol%.

Further, in a silver halide emulsion layer containing silver halide grains having a silver chloride content of 90 mol% or more, the silver chloride content in all silver halide grains contained in the emulsion layer. The proportion of silver halide grains of 90 mol% or more is 60 wt% or more, preferably 80 wt% or more.

The composition of the silver halide grain may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different. Also, when the composition inside and outside the particle is different, the composition may change continuously,
It may be discontinuous.

The grain size of the silver halide grain is not particularly limited, but considering other photographic properties such as rapid processing property and sensitivity, it is preferably 0.2 to 1.6 μm, more preferably 0.25 to
It is in the range of 1.2 μm. The particle size can be measured by various methods generally used in the technical field.

The grain size distribution of the silver halide grains may be polydisperse or monodisperse. Monodisperse silver halide grains having a variation coefficient of 0.22 or less, more preferably 0.15 or less in the grain size distribution of silver halide grains are preferred. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution and is defined by the following equation.

Coefficient of variation = standard deviation of grain size distribution / average grain size The silver halide grains used in the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The particles may be grown at one time, or after the seed particles are made,
You may grow it.

The method of reacting the soluble silver salt with the soluble halogen salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but a method obtained by the simultaneous mixing method is preferable. .. Further, the pAg controlled double jet method described in JP-A-54-48521 may be used as one form of the simultaneous mixing method.

If necessary, a silver halide solvent such as thioether may be used.

The silver halide grains may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. It is also possible to prepare particles having a shape such as an octahedron, a tetrahedron, a dodecahedron, and use the particles. Further, grains having twin planes may be used.

As the silver halide grains, grains having a single shape may be used, or grains having various shapes may be mixed.

The silver halide grains are cadmium salt, zinc salt,
To add a metal ion using a lead salt, a thallium salt, an iridium salt (including a complex salt), a rhodium salt (including a complex salt), and an iron salt (including a complex salt) to be included inside and / or on the surface of the particle. Further, reduction sensitizing nuclei can be imparted to the inside of the grain and / or the grain surface by placing in a suitable reducing atmosphere.

The silver halide emulsion used in the present invention is
After completion of the growth of silver halide grains, unnecessary soluble salts may be removed or may be contained.

The silver halide grain may be a grain in which a latent image is mainly formed on the surface, or may be a grain mainly formed inside the grain. Grains whose latent image is mainly formed on the surface are preferable.

The silver halide emulsion is chemically sensitized by a conventional method. That is, a sulfur-containing compound capable of reacting with silver ions, a sulfur sensitizing method using active gelatin, a selenium sensitizing method using a selenium compound, a reduction sensitizing method using a reducing substance,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

In the present invention, a chalcogen sensitizer can be used as the chemical sensitizer. The chalcogen sensitizer is a general term for a sulfur sensitizer, a selenium sensitizer, and a tellurium sensitizer, but for photography, the sulfur sensitizer and the selenium sensitizer are preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbazide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine.

The addition amount of the sulfur sensitizer varies over a considerable range depending on various conditions such as pH, temperature and size of silver halide grains, but as a guide, it is 10 mol per mol of silver halide. ^It is preferably about ^-7 to 10 ^-1 mol.

A selenium sensitizer can be used in place of the sulfur sensitizer, and as the selenium sensitizer, aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, Selenoamides,
Selenoids such as selenocarboxylic acid salts and esters, selenophosphates, diethyl selenide, diethyl diselenide and the like can be used.

Further, reduction sensitization can be used together. The reducing agent is not particularly limited, but examples thereof include stannous chloride, thiourea dioxide, hydrazine and polyamine. or,
A noble metal compound other than gold, such as a palladium compound, can also be used in combination.

The silver halide grains used in the present invention preferably contain a gold compound. The gold compound preferably used in the present invention is + even if the oxidation number of gold is +1
It may be trivalent, and various gold compounds are used. Representative examples are chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide, gold. Examples include selenide.

The gold compound may be used to sensitize the silver halide grains, or may be used so as not to substantially contribute to the sensitization.

The amount of the gold compound added varies depending on various conditions, but as a guide, it is 10 ^-8 to 10 ^-1 per mol of silver halide.
And is preferably 10 ⁻⁷ to 10 ⁻² mol. These compounds may be added at any step of silver halide grain formation, physical ripening, chemical ripening and after chemical ripening.

The emulsion used in the present invention can be spectrally sensitized in a desired wavelength region by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. Further, a dye which does not have a spectral sensitizing effect by itself with the sensitizing dye, or a compound which does not substantially absorb visible light, and which contains a supersensitizing agent for enhancing the sensitizing effect of the sensitizing dye is contained in the emulsion. You may let me.

As gelatin used in the present invention, in addition to lime-processed gelatin, acid-processed gelatin, Bulletin of Society of Science of Photography of Japan (Bull.Soc.Sci.Phot.Japan) ) No. 1
An enzyme-treated gelatin as described on pages 6,30 (1966) may be used, or a hydrolyzed product or an enzymatically decomposed product of gelatin may be used.

The amount of gelatin coated on the light-sensitive material of the present invention is 7.5 g / m ² or less, more preferably 6.5 to 7.2.
It is g / m ² .

The following general formulas (I), (II), (III), (IV), and
It is preferable to contain at least one selected from the compounds represented by (V) and (VI).

[0060]

[Chemical 1]

In formulas (I) to (IV), R ₁ represents a hydrogen atom, an alkyl group or an aryl group, and R ₂ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a nitro group, a carboxyl group or a sulfo group. Represents a group, a sulfamoyl group, a hydroxyl group, an alkoxy group or a thiazolyl group.
Z ₁ represents a group of non-metal atoms necessary for forming a thiazoline ring. R ₃ and R ₄ are each an alkyl group, an aryl group,
It represents —COR or —SO ₂ N (R ′) (R ″) (R, R ′ and R ″ each represent an alkyl group or an aryl group). However, R ₃ and R ₄ may form a ring together with the nitrogen atom.
R ₅ , R ₆ and R ₇ each represent a halogen atom or an alkyl group. R ₈ and R ₉ each represent a hydrogen atom, an alkyl group, an aryl group or a nitrogen-containing heterocyclic group. R ₁₀ is a hydrogen atom,
It represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylsulfamoyl group or an arylsulfamoyl group. R ₁₁ and R ₁₂ each represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a cyano group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an alkylsulfonyloxy group or a heterocyclic group. However, R ₁₁ and R ₁₂ may form a ring.

R ₁₃ in the general formula (V) represents an alkylene group or an arylene group, and R ₁₄ in the general formula (VI) represents a lower alkyl group having 1 to 5 carbon atoms (preferably methyl or ethyl).

The substitutable groups represented by R _{1 to} R ₁₃ include those having further substituents.

The compounds represented by the general formulas (I) to (VI) are known compounds and are disclosed in JP-A-54-27424 and JP-A-57-157244.
No. 59, No. 84237, No. 59-226344, No. 60-263938, No. 6
The compounds described in 1-233743 and the like are included.

Hereinafter, general formulas (I) to be used in the present invention will be described.
Representative specific examples of the compound represented by (VI) are shown below, but the present invention is not limited thereto.

[0066]

[Chemical 2]

[0067]

[Chemical 3]

[0068]

[Chemical 4]

[0069]

[Chemical 5]

[0070]

[Chemical 6]

[0071]

[Chemical 7]

The compounds represented by the above general formulas (I) to (VI) can be added to any photographic constituent layer, but in view of photographic performance such as fog and sensitivity, it is preferably a non-photosensitive layer. Is. Further, the above compound is added at the time of preparing a colloidal emulsion for the photographic constituent layers, and it is possible to prevent the putrefaction and decomposition action of the emulsion due to bacteria, mold and the like after the addition.

Of the compounds of the above general formulas (I) to (VI),
The compounds of the general formulas (I), (II) and (IV) are preferred, and the compounds of the general formulas (I) and (IV) are more preferred. The amount added to the photographic constituent layers is 5 × 10 ^-7 to ² per 1 m 2.
× 10 ^-3 mol is preferable, and more preferably 5 × 10 ^{-6 to} 5 ×.
It is 10 ^-4 mol. When it is contained in the photosensitive material,
It is dissolved in a solvent such as water, methanol, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, benzyl alcohol, ethanolamine, diethanolamine, triethanolamine, or added in the form of an emulsion (as an emulsion). Is preferred.

Known acylacetanilide type couplers can be preferably used as the yellow dye-forming coupler. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous. Above all, a coupler represented by the following general formula (YI) is preferably used.

[0075]

[Chemical 8]

In the formula, R ₂₁ represents a halogen atom or an alkoxy group. R ₂₂ represents a hydrogen atom, a halogen atom or an alkoxy group which may have a substituent. R ₂₃ represents an optionally substituted acylamino group, alkoxycarbonyl group, alkylsulfamoyl group, arylsulfamoyl group, arylsulfonamide group, alkylureido group, arylureido group, succinimide group, alkoxy group or Represents an aryloxy group. Z ₂ represents a group capable of splitting off upon coupling with the oxidation product of the color developing agent.

As the magenta coupler, various magenta couplers can be used, and among them, the coupler represented by the following general formula (MI) can be preferably used.

[0078]

[Chemical 9]

In the formula, Z ₃ represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z ₃ may have a substituent.

X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. R represents a hydrogen atom or a substituent.

In the general formula (M-I), the substituent represented by R is not particularly limited, but is typically alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl. Other groups such as halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, and the like. Carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups, and spiro. A compound residue, a bridged hydrocarbon compound residue, etc. are also mentioned.

The substituent represented by R, the group capable of splitting off by the reaction with the oxidation product of the color developing agent represented by X, the nitrogen-containing heterocycle formed by Z and the ring formed by Z may have. The preferred range and specific examples of the substituents, and the preferred range of the magenta coupler represented by the general formula (M-I) are the same as those described in EP 0327272, page 5, line 23 to page 8, line 52. ..

Specific examples of the compound include European Patent Publication 02
73712 Nos. 6 to 21 Compounds M-1 to M
-61 and compounds 1-223 described in No. 0235913, pp. 36-92.

These couplers are based on the Journal of the Chemical Society.
ciety), Perkin I (1977), 2047-2052, US Pat. No. 3,725,067, JP-A-59-99437, 58-42045.
No. 59, No. 162548, No. 59-171956, No. 60-33552, No. 60-33552
60-43659, 60-172982, 60-190779, 62-20945
It can be synthesized with reference to No. 7 and No. 63-307453.

[0085] aforementioned couplers can also be used with other types of magenta couplers, usually 1 mol of silver halide per 1 × 10 ^-3 mol to 1 mol, preferably 1 × 10 ^-2 mol to 8 × 10 ^- It can be used in the range of ¹ mol.

Typical cyan dye-forming couplers are phenol-type and naphthol-type 4-equivalent or 2-equivalent cyan dye-forming couplers, among which 2-acylamino.
A -5-alkylphenol type coupler and a 2,5-diacylaminophenol type coupler are preferably used.

The color photographic material of the present invention may contain various known photographic additives. Examples thereof include UV absorbers (for example, benzophenone-based and benzotriazole-based compounds), anti-staining agents (for example, hydroquinone derivatives), surfactants (for example, sodium alkylnaphthalenesulfonate, sodium alkylbenzenesulfonate, alkyl succinate). Sodium sulfonate, polyalkylene glycol, etc.), water-soluble anti-irradiation dyes (eg azo, styryl, triphenylmethane, oxonol and anthraquinone compounds), hardeners (eg halogeno-s-triazine) , Vinyl sulfone-based, acryloyl-based, ethyleneimine-based, N-methylol-based, epoxy-based compounds and water-soluble aluminum salts, etc.), film physical property improving agents (eg glycerin, aliphatic polyhydric alcohols, polymer dispersions (latex) , Solid or liquid paraffin and colloidal silica, and the like), a fluorescent brightening agent (e.g., diaminostilbene based compounds) and can be given various oil-soluble paint or the like.

As the photographic layers constituting the light-sensitive material of the present invention, in addition to each emulsion layer, each layer such as an undercoat layer, an intermediate layer, a yellow filter layer, an ultraviolet absorbing layer, a protective layer and an antihalation layer may be used as required. Can be provided as appropriate.

The method for adding the hydrophobic photographically useful compound such as the above-mentioned dye-forming compound or image stabilizer to the light-sensitive material is as follows.
Various methods such as a solid dispersion method, a latex dispersion method and an oil-in-water emulsion dispersion method can be used, which can be appropriately selected according to the chemical structure of the hydrophobic compound.

Various methods for dispersing a hydrophobic compound can be applied to the oil-in-water type emulsion dispersion method, and the boiling point is usually about 150 ° C.
In addition to the above high boiling point organic solvents, if necessary, a low boiling point, and /
Alternatively, a water-soluble organic solvent is used in combination to dissolve, and a stirrer using a surfactant in a hydrophilic binder such as an aqueous gelatin solution, a homogenizer, a colloid mill, a flow jet mixer, and a dispersing device such as an ultrasonic device, After emulsifying and dispersing, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be added at the same time as the dispersion liquid or the dispersion.

The color developing agents used in the color developing solution in the present invention include known color developing agents widely used in various color photographic processes. These developers include aminophenol-based and p-phenylenediamine-based derivatives. Since these compounds are more stable than the free state, they are generally used in the form of salts, for example, hydrochlorides or sulfates. Also, these compounds are generally used in a concentration of about 0.1 g to about 30 g, preferably about 1 g, per liter of color developer.
Use at a concentration of g to about 15 g.

Examples of aminophenol-based developers include o-aminophenol, p-aminophenol and 5-amino.
-2-Hydroxytoluene, 2-amino-3-hydroxytoluene, 2-hydroxy-3-amino-1,4-dimethylbenzene and the like are included.

Particularly useful primary aromatic amine-based color developing agents are N, N-dialkyl-p-phenylenediamine-based compounds, and the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N, N-diethyl-p-phenylenediamine hydrochloride and N-
Methyl-p-phenylenediamine hydrochloride, N, N-dimethyl-p-
Phenylenediamine hydrochloride, 2-amino-5- (N-ethyl-N-
Dodecylamino) toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate,
N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N, N-diethylaniline, 4-amino-N- (2-
Methoxyethyl) -N-ethyl-3-methylaniline-p-toluenesulfonate and the like can be mentioned. In addition to the above-mentioned developers, known developer component compounds can be added to the developer used for processing the color light-sensitive material of the present invention. For example, an alkali agent such as sodium hydroxide or potassium carbonate, an alkali metal sulfite salt, an alkali metal bisulfite salt, an alkali metal thiocyanate salt, an alkali metal halide, benzyl alcohol, a water softener and a thickening agent may be optionally contained. You can also

The temperature of the developing solution is 15 ° C. or higher, generally 20 to
It is preferably carried out at 50 ° C, particularly 30 ° C to 45 ° C. Of developer
The pH value is usually 7 or higher, most commonly about 10 to about 13. The developing time is not particularly limited, but is preferably 3 minutes or less.
The effects of the present invention are more excellent in so-called rapid processing, which is a short processing time, and a great effect is obtained when the developing time is 90 seconds or less, particularly 30 seconds or less.

The light-sensitive material according to the present invention may contain these color developing agents in the hydrophilic colloid layer as a color developing agent itself or as a precursor thereof, and can be processed in an alkaline activating bath. The color developing agent precursor is a compound capable of forming a color developing agent under alkaline conditions. It is a Schiff base type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, a phosphoric acid amide derivative precursor, and a sugar. Examples include amine reactant precursors and urethane type precursors.

It is necessary to add these aromatic primary amine color developing agents or their precursors in such an amount that sufficient color can be obtained by the amount thereof when activated.
This amount is largely different depending on the kind of the light-sensitive material, but is generally in the range of 0.1 to 5 mol, preferably 0.5 to 3 mol per mol of silver halide. These color developing agents or their precursors can be used alone or in combination.

To be incorporated in the light-sensitive material, it can be dissolved in a suitable solvent such as water, methanol, ethanol or acetone and added, or a high boiling organic solvent such as dibutyl phthalate, dioctyl phthalate or tricresyl phosphate. Can also be added as an emulsified dispersion, or can be added after impregnating a latex polymer as described in Research Disclosure No. 14850.

The color light-sensitive material of the present invention, after color development,
Bleached and fixed.

In the present invention, a ferric complex salt of an organic acid represented by the general formula (A) or (B) is used as a bleaching agent in the bleaching solution.

[0100]

[Chemical 10]

In the general formula (A), A _{1 to} A ₄ are each
Identical or different, --CH ₂ OH, --COOM or --PO ₃ M
Represents ₁ M ₂ . M, M ₁ and M ₂ each represent a hydrogen atom, an alkali metal (eg sodium, potassium) or ammonium group. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms (for example, propylene, butylene, pentamethylene, etc.). Examples of the substituent include a hydroxyl group and an alkyl group having 1 to 3 carbon atoms (methyl, ethyl, propyl, etc.).

In the general formula (B), A _{1 to} A ₄ have the same meanings as defined in the above general formula (A), and n represents an integer of 1 to 8. B ₁ and B ₂ may be the same or different and each represents a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms (for example, ethylene, propylene, butylene, pentamethylene, etc.). As the substituent, X in the general formula (A) is used.
Are the same as those listed as the substituents of.

The preferred specific examples of the compounds represented by formula (A) or (B) are shown below.

[0104]

[Chemical 11]

[0105]

[Chemical 12]

These (A-1) to (A-12) and (B-
As the ferric complex salt of the compounds 1) to (B-7), a sodium salt, potassium salt or ammonium salt of these ferric complex salts can be optionally used. From the viewpoint of the purpose and solubility of the present invention, ammonium salts and potassium salts of these ferric complex salts are preferably used.

Of the above-mentioned compound examples, those particularly preferably used in the present invention are (A-1), (A-3),
(A-4), (A-5), (A-9), (B-1),
(B-2) and (B-7).

The ferric organic acid complex salt of an organic acid represented by the general formula (A) or (B) is contained in an amount of 0.1 mol or more, preferably 0.2 mol or more, and more preferably 0.2 to 1.5 mol / l, per liter of the bleaching solution. The range is 1.

As the bleaching agent which can be used in combination with the compound represented by the above general formula (A) or (B) in the bleaching solution, a ferric complex salt of the following compound (for example, a salt of ammonium, sodium, potassium, triethanolamine, etc.) can be used. ) Is illustrated.

A'-1 ethylenediaminetetraacetic acid A'-2 trans-1,2-cyclohexanediaminetetraacetic acid A'-3 dihydroxyethylglycinic acid A'-4 ethylenediaminetetrakismethylenephosphonic acid A'-5 nitrilotrismethylenephosphonic acid A'-6 Diethylenetriamine pentakismethylenephosphonic acid A'-7 Diethylenetriaminepentaacetic acid A'-8 Ethylenediaminedioltohydroxyphenylacetic acid A'-9 Hydroxyethylethylenediaminetriacetic acid A'-10 Ethylenediaminedipropionic acid A'-11 Ethylenediamine diamine Acetic acid A'-12 Hydroxyethyliminodiacetic acid A'-13 Nitrilotriacetic acid A'-14 Nitrilotripropionic acid A'-15 Triethylenetetramine hexaacetic acid A'-16 Ethylenediaminetetrapropionic acid Organic acid (III) complex salt may be used in the form of a complex salt,
Iron (III) salts such as ferric sulfate, ferric chloride, ferric acetate, ferric ammonium sulfate, ferric phosphate, etc. and aminopolycarboxylic acid or a salt thereof are used to prepare iron ( II
I) Ionic complex salts may be formed. When used in the form of complex salt, one kind of complex salt may be used, or 2
More than one kind of complex salt may be used. Further, when a complex salt is formed in a solution using a ferric iron salt and an aminopolycarboxylic acid, one or more ferric iron salts may be used.
Furthermore, one or more aminopolycarboxylic acids may be used. Further, in any case, the aminopolycarboxylic acid may be used in excess to form the iron (III) ion complex salt.

The bleaching solution containing the above iron (III) ion complex may contain a metal ion complex salt of cobalt, copper, nickel, zinc or the like other than iron.

The bleaching solution contains imidazole and its derivatives described in JP-A-1-295258 or the general formula described in the specification.
By containing at least one of the compounds represented by [I] to [IX] and these exemplified compounds, it is possible to exert an effect on the rapidity.

In addition to the above bleaching accelerator, JP-A-62-123459
Compounds described on pages (14) to (30) of Japanese Patent No.
-17445, Exemplified compounds described on pages 22 to 25, JP-A-53-956
The compounds described in No. 30, No. 53-28426 and the like can also be used in the same manner.

These bleaching accelerators may be used alone or in combination of two or more, and the addition amount is generally preferably in the range of about 0.01 to 100 g, and more preferably 0.05 to 50 g, per liter of the bleaching solution. And particularly preferably 0.05 to 15 g.

When a bleaching accelerator is added, it may be added and dissolved as it is, but it is generally dissolved in water, an alkali, an organic acid or the like in advance and then added. If necessary, methanol or ethanol is added. It can also be added by dissolving it using an organic solvent such as acetone.

The pH of the bleaching solution is preferably 5.5 or less, more preferably 2.5 to 5.5. The pH of the bleaching solution is the pH of the processing tank during the processing of the light-sensitive material, and can be clearly distinguished from the so-called replenisher pH.

The temperature of the bleaching solution is preferably 20 ° C to 50 ° C, preferably 25 ° C to 45 ° C.

In the case of color paper treatment, the treatment time with the bleaching solution is preferably 40 seconds or less, more preferably 30 seconds or less, most preferably 25 seconds or less, and the effect of the present invention is remarkable even in rapid processing. appear. Here, the processing time with the bleaching solution means the time from when the tip of the light-sensitive material starts to be immersed in the bleaching solution in the bleaching bath until the tip comes out of the bleaching solution.

To the bleaching solution, a halide such as ammonium bromide, potassium bromide or sodium bromide is usually added. Further, various fluorescent whitening agents, antifoaming agents or surfactants may be contained.

The replenishing amount of the bleaching solution is preferably 50 ml or less, preferably 30 ml or less per 1 m ² of the light-sensitive material for the color paper, and 180 ml or less per 1 m ² of the light-sensitive material for the color negative film. It is preferably 140 ml or less, and the lower the replenishment amount, the more remarkable the effect of the present invention becomes.

The replenisher for the bleaching solution preferably comprises a part or all of the overflowing solution of the bleaching solution prepared by processing different color light-sensitive materials. That is, bleaching baths A and B
In the case of two series treatments, the bleaching bath A overflow solution is used as a bleaching bath B replenisher. The light-sensitive materials processed in the bleaching baths A and B may be of different types, for example, color negative film and color paper; color negative film or color paper and color reversal (reversal) film or paper; silver chloride concentration, There are various combinations such as color negative films having different silver bromide concentrations or sensitivities; color papers having different silver chloride concentrations, silver bromide or sensitivities, etc., but a combination of color negative films and color papers is preferable. Particularly preferred in embodiments of the invention.

In the present invention, in order to increase the activity of the bleaching solution, air or oxygen may be blown in the treatment bath and the treatment replenisher storage tank, if desired.
Alternatively, a suitable oxidizing agent such as hydrogen peroxide, bromate, persulfate or the like may be added as appropriate.

Next, a thiosulfate and / or a thiocyanate is preferably used as the fixing agent used in the fixing solution in the fixing step performed after the bleaching step. The addition amount of thiosulfate is preferably 0.4 mol / 1 or more, and the addition amount of thiocyanate is preferably 0.5 mol / 1 or more.

In addition to these fixing agents, the fixing solution further includes boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide. A pH buffer consisting of various salts such as the above may be used alone or in combination of two or more kinds.

Further, it is desirable to add a large amount of alkali halide or ammonium halide, for example, a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride or ammonium bromide. Also, alkyl amines,
A compound known to be added to a fixing solution such as polyethylene oxides can be appropriately added.

In the fixing solution, ammonium ion is preferably 50 mol% or less of all cations, more preferably 20 mol% or less, and particularly preferably 0 to 10 mol% when the fixing treatment is carried out directly from the bleaching solution. This is a preferred embodiment because it can prevent the stain and reduce the pollution by reducing ammonium ions. Decreasing ammonium ions may affect the fixability, so it is preferable to use thiocyanate in combination with about 0.5 to 3.0 mol / l, or to use thiosulfate at a concentration of 0.4 mol / l or more, preferably Is 1.0 mol / l or more, particularly preferably 1.2 to
The preferred embodiment is 2.5 mol / l.

The replenishing amount of the fixing solution is 120 m / m ²
l or less, more preferably ² per 1 m ² of the light-sensitive material
It is 0 to 1000 ml, particularly preferably 50 to 800 ml.

The pH of the fixing solution is preferably in the range of 4-8. The compound represented by the general formula [FA] described on page (15) of JP-A-1-295258 and its exemplified compounds may be added to the fixing solution, and a small amount of a light-sensitive material is prepared by using the fixing solution. Another effect is that sludge generated during treatment over a period of time is extremely small. Good results are obtained when the amount of the compound represented by the general formula [FA] added is in the range of 0.1 to 200 g per liter of the treatment liquid.

Sulfites and sulfite-releasing compounds may be used in the fixing solution. Specific examples of these compounds include:
Examples thereof include potassium sulfite, sodium sulfite, ammonium sulfite, ammonium hydrogen sulfite, potassium hydrogen sulfite, sodium hydrogen sulfite, potassium metabisulfite, sodium metabisulfite, and ammonium metabisulfite. Further, compounds represented by the general formula [B-1] or [B-2] described on page (16) of JP-A-1-295258 are also included.

These sulphite and sulphite-releasing compounds are present as sulphite ions of at least 0.1 per liter of fixer.
It is preferable to contain 05 mol, 0.08 to 0.65 mol /
The range of 1 is more preferable, and the range of 0.10 to 0.50 mol / l is particularly preferable. The range of 0.12 to 0.40 mol / l is particularly preferable.

The processing time with the fixer is arbitrary, but 6
The time is preferably 30 minutes or less, more preferably 5 seconds to 4 minutes 20 seconds, and particularly preferably 10 seconds to 3 minutes 20 seconds. In the processing method of the present invention, it is preferable as an embodiment of the present invention to apply forced liquid agitation to the bleaching solution and the fixing solution. The reason for this is not only that the effect of the object of the present invention is better achieved, but also that rapid processing suitability is achieved. Forced liquid stirring here is not normal liquid diffusion movement,
This means that stirring means is added to force stirring.
As the forced stirring means, there are JP-A 1-206343 and 1-2.
The means described in No. 95258 can be adopted.

In the present invention, the crossover time between the color developing tank and the bleaching tank is 10 seconds or less, preferably 7 seconds or less, which is a different effect from the present invention. A method which has an effect and further reduces the processing liquid brought in by the light-sensitive material by installing a duck hill valve or the like is also a preferable mode for carrying out the present invention.

The fixing treatment employed in the present invention is followed by washing or stabilizing treatment, preferably stabilizing treatment with a stabilizing solution.

The stabilizing solution may contain a chelating agent having a chelate stability constant for iron ions of 8 or more.
Preferred for the purposes of the present invention. Here, the chelate stability constant is the value of Stability Co. by LG Sillen / AEMartell.
nstants of Metal-ion Complexes '' The Chemical Socie
ty, London (1964), S.Chaberek AEMartell "Orga
nic Sequestering Agents ”means a constant generally known by Wiley (1959).

The chelate stability constant for iron ions is 8
Examples of the chelating agent described above include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. The iron ion means ferric ion (Fe ³⁺ ).

The amount of chelating agent used is 1 liter of stabilizing solution.
A preferable result is obtained in the range of 0.01 to 50 g, and more preferably in the range of 0.05 to 20 g.

As a preferable compound added to the stabilizing solution, an ammonium compound can be mentioned. These are supplied by ammonium salts of various inorganic compounds. These may be used alone or in combination of two or more. The amount of the ammonium compound added is preferably in the range of 0.001 to 1.0 mol, more preferably 0.002 to 2.0 mol, per liter of the stabilizing solution.

Further, the stabilizing solution preferably contains sulfite. The sulfite may be any organic substance or inorganic substance as long as it releases a sulfite ion, but is preferably an inorganic salt. Preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite. These sulfites are preferably added in an amount such that at least 1 × 10 ^-3 mol / l is added to the stabilizing solution, and more preferably 5 × 10 ^-3 to 10 ^-1.
It is added so that the amount becomes mol / l, and it has a particularly anti-staining effect. As an addition method, it may be added directly to the stabilizing solution, but it is preferably added to the stabilizing replenishing solution.

Other generally known compounds that can be added to the stabilizing solution include polyvinylpyrrolidone (PVP K-
15, K-30, K-90), organic acid salts (oxalic acid, acetic acid, succinic acid,
Oxalic acid, benzoic acid, etc., pH adjusters (phosphate, borate, hydrochloric acid, sulfuric acid, etc.), fungicides (phenol derivatives, catechol derivatives, imidazole derivatives, triazole derivatives, siabendazole derivatives, organic halogen compounds, etc.) Antifungal agents, etc., which are known as slime control agents in the paper-pulp industry) or optical brighteners, surfactants, preservatives, metal salts of Bi, Mg, Zn, Ni, Al, Sn, Ti, Zr, etc. Etc. One or two or more of these compounds can be arbitrarily selected and used within a range that does not impair the effects of the present invention.

No washing treatment is required after the stabilizing treatment, but rinsing by a small amount of washing in a very short time, surface washing and the like can be optionally performed.

The soluble iron salt is preferably present in the stabilizing solution. Soluble iron salt should be at least 5 × 10 ^-3 mol / mol in stabilizing solution
It is preferably used in a concentration of 1, more preferably in the range of 8 × 10 ^-3 to 15 × 10 ^-2 mol / l, and further preferably in the range of 12 × 10 ^-3 to 10 ^-1 mol / l. is there. Further, these soluble iron salts may be added to the stabilizing solution (tank solution) by adding them to the stabilizing solution replenishing solution, or may be added to the stabilizing solution (tank solution) by eluting from the photosensitive material into the stabilizing solution. Alternatively, it may be added to the stabilizing solution (tank solution) by adhering it to the photosensitive material to be processed from the prebath and bringing it in.

Further, in the present invention, the ion exchange resin treatment is carried out to remove calcium ions and magnesium ions from
A stabilizing solution adjusted to ppm or less may be used, or a method of incorporating the antifungal agent or the halogen ion-releasing compound may be used.

The pH of the fixing solution in the present invention is preferably in the range of 5.5 to 10.0. The pH adjusting agent that can be contained in the stabilizing solution may be any of generally known alkali agents or acid agents.

The treatment temperature during the stabilization treatment is 15 to 70 ° C.
Is preferable, and more preferably in the range of 20 to 55 ° C.
The processing time is preferably 120 seconds or less, more preferably 3 to 90 seconds, and most preferably 6 to 50 seconds.

The replenishing amount of the stabilizing solution is preferably from 0.1 to 50 times, particularly preferably from 0.5 to 30 times, the carrying-in amount of the pre-bath (bleach-fixing solution) per unit area of the light-sensitive material in view of rapid processing property and storability of dye image. preferable.

The stabilizing tank is preferably composed of a plurality of tanks, preferably 2 to 6 tanks, particularly preferably 2 to 3 tanks, more preferably 2 tanks, and a counter current system. It is preferable to adopt a method of supplying to the post-bath and causing the overflow from the pre-bath.

[0147]

EXAMPLES The present invention will now be described in detail with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 Canadian Standard Freeness (JI
SP-8121-76) 20% of softwood bleached sulfate pulp (NBSP) beaten to 250 ml and 80% of hardwood bleached sulfate pulp (LBSP) beaten to the same freeness of 280 ml were mixed to prepare a papermaking raw material. ..

The papermaking additive was added to the pulp dry weight,
Used in the amounts shown below.

Cationized starch 2.0% Alkyl ketene dimer resin 0.4% Anionic polyacrylamide resin 0.1% Polyamide polyamine epichlorhydrin resin 0.7% Adjusted to pH 7.5 with sodium hydroxide Papermaking raw materials containing the above additives Paper is made with a machine, size press and machine calender are applied, and the rice basis weight is 170
A base paper having a g / m ² , a tightness of 1.0 and a water content of 8% was produced. As a size press treatment agent, a 5% size liquid prepared by dissolving carboxyl-modified PVA and sodium chloride in water at a ratio of 2: 1 was used, and this was applied to both sides of the base paper at an application amount of 2.2 g / m ^2. did.

Corona discharge was applied to both the front and back sides of the obtained base paper, and the surface was made of high density polyethylene (specific gravity 0.94, MI = 6.8) containing the anatase type titanium dioxide in the concentration shown in Table 1 by the extrusion coating method. A polyolefin resin coating layer with a thickness of 35 μm is formed, and a polyethylene resin coating layer is formed on the back surface by coextrusion coating method with polyethylene not containing titanium dioxide,
The resulting laminate was pressed against a cleaning roll having a smooth surface at 20 ° C. to produce a photographic paper support having SRa values shown in Table 1.

[0152]

[Table 1]

On each support thus produced, each layer having the constitution shown in Tables 2 and 3 was applied by the continuous simultaneous multi-layer coating method using a slide hopper to prepare multi-layer color light-sensitive material samples 1 to 1. 17 was produced. The coating liquid was prepared as follows.

First layer coating solution Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, (ST-2) 6.67 g, additive (HQ
-1) To 0.67 g and 6.67 g of a high boiling point organic solvent (DNP), 60 ml of ethyl acetate was added and dissolved, and this solution was 220 ml of 10% gelatin aqueous solution containing 7 ml of 20% surfactant (SU-1).
A yellow coupler dispersion was prepared by emulsification and dispersion using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the conditions described below to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Further, as a hardening agent, (H-1) was added to the second and fourth layers, and (H-2) was added to the seventh layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension.

[0156]

[Table 2]

[0157]

[Table 3]

The additives used for each layer are summarized below.

DBP: dibutyl phthalate DOP: dioctyl phthalate DNP: dinonyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinylpyrrolidone HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5- Di-sec-dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di (1, 1-dimethyl-4-hexyloxycarbonylbutyl) hydroquinone HBS-1: 1-methyl-4- (4-dodecylphenyl) sulfamoylbenzene SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: sulfo Succinic acid di (2-ethylhexyl) ester / sodium SU-3: sulfosuccinic acid di (2,2,3,3,4,4,5,5-octafluoropentyl) ester / sodium H 1: tetra (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy -s- triazine sodium

[0160]

[Chemical 13]

[0161]

[Chemical 14]

[0162]

[Chemical 15]

(Preparation of blue-sensitive silver halide emulsion) In 1000 ml of 2% gelatin aqueous solution kept at 40 ° C., the following (solution A) and (solution B) were taken for 30 minutes while controlling pAg = 6.5 and pH = 3.0. Are added at the same time, and the following (solution C) and (solution D) are added to pAg =
Simultaneous addition was carried out over 180 minutes while controlling 7.3 and pH = 5.5.
At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added to 600 ml (Solution D) After adding 300 g of silver nitrate and adding 600 ml of water, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with a gelatin aqueous solution to obtain an average particle size. A monodisperse cubic emulsion EMP-1 having a diameter of 0.85 μm, a coefficient of variation of 0.07 and a silver chloride content of 99.5 mol% was obtained.

The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitization Dye BS-2 1 × 10 ⁻⁴ mol / mol AgX (preparation of green-sensitive silver halide emulsion) (solution A) and solution B
The average particle size is 0.43 μm in the same manner as EMP-1 except that the addition time of (C liquid) and the addition time of (D liquid) are changed.
A monodisperse cubic emulsion EMP-2 having a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was obtained.

The following compounds were used for EMP-2:
Chemical ripening was carried out at 120 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (red Preparation of Sensitive Silver Halide Emulsion) (Solution A) and (Solution B)
Except that the addition time of (C liquid) and the addition time of (D liquid) are changed, the average particle size is 0.50 μm in the same manner as EMP-1.
A monodisperse cubic emulsion EMP-3 having a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was obtained.

The following compounds were used for EMP-3:
Chemical ripening at 90 ° C for 90 minutes to give a red-sensitive silver halide emulsion (E
m-R) was obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX STAB- 1: 1- (3-acetamidophenyl) -5-mercaptotetrazole

[0171]

[Chemical 16]

Using each of the color paper samples shown in Table 1 thus prepared, after wedge exposure, a running process was carried out under the following processing conditions. The running was accomplished by repeating the development process and replenishment for 14 days until the total amount of the color developing replenisher solution became twice as much as the color developing tank solution.

(Processing Conditions-A) Processing Process Temperature Time Replenishment Amount * (1) Color development 35.0 ± 0.3 ° C. 45 seconds 160 ml (2) Bleach fixing 35.0 ± 0.5 ° C. 60 seconds 160 ml (3) Stability 30-34 ° C. 90 240 ml / sec (3-tank cascade) (4) Drying 60-80 ° C 30 sec- * Replenishment amount is a value per 1 m ² of light-sensitive material. Color development tank solution Triethanolamine 10g Diethylene glycol 5g N, N-diethylhydroxylamine 5.0g Potassium bromide 0.02g Potassium chloride 2g Diethylenetriamine pentaacetic acid 5g Potassium sulfite 0.2g 3-Methyl-4-amino-N-ethyl-N- ( β-Methanesulfonamidoethyl) aniline sulfate 5.2g Potassium carbonate 25g Potassium hydrogen carbonate 5g Add water to make the total volume 1000ml, and adjust to pH 10.10 with potassium hydroxide or sulfuric acid.

Color developing replenisher triethanolamine 14.0 g diethylene glycol 8.0 g N, N-diethylhydroxylamine 6.0 g potassium chloride 1.3 g diethylenetriaminepentaacetic acid 7.5 g potassium sulfite 0.3 g 3-methyl-4-amino-N-ethyl-N -(β-Methanesulfonamidoethyl) aniline sulfate 7.8g Potassium carbonate 30g Potassium hydrogencarbonate 1g Add water to bring the total volume to 1000ml, and adjust to pH 10.60 with potassium hydroxide or sulfuric acid.

Bleach-fixing tank solution and replenishing solution Ethylenediaminetetraacetic acid ferric ammonium salt 100 g Ethylenediaminetetraacetic acid 3.0 g Ammonium thiosulfate (70% solution) 150 g Ammonium sulfite (40% solution) 51.0 g Ammonia water or glacial acetic acid pH 6.0 Adjust the amount to 1, and add water to make the total volume 1000 ml.

Stabilization tank solution and replenishing solution o-Phenylphenol 0.2 g Ubitex CK (manufactured by Ciba Geigy) 1.0 g Zinc sulfate 0.5 g Ammonium sulfite (40% solution) 5.0 ml 1-hydroxyethylidene-1,1-diphosphonic acid ( 60% solution) 5.0g Ethylenediaminetetraacetic acid 1.5g Benzisothiazolin-3-one 0.2g Adjust the pH to 7.8 with aqueous ammonia or sulfuric acid and make up to 1000ml with water.

(Processing condition-B) Treatment process Temperature Time Complementary amount (ml / m ² ) (1) Color development 35 ° C. 45 seconds 160 (2) Bleach 38 ° C. 20 seconds 30 (3) Fixed 38 ° C. 20 Sec 30 (4) Stabilization * 30 ℃ 90 seconds 240 (5) Drying 60 to 80 ℃ 30 seconds ― * The stabilization tank was a three tank cascade system.

Color developing tank solution Diethylene glycol 15 g Potassium bromide 0.02 g Potassium chloride 2.0 g Potassium sulfite (50% solution) 0.5 ml 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) aniline Sulfate 6g Diethylhydroxylamine (85% solution) 5g Triethanolamine 10g Potassium carbonate 30g Ethylenediaminetetraacetic acid 2g Optical brightener (PK-Conc made by Nisso Corp.) 2g Add water to make 1000ml and add potassium hydroxide Alternatively, the pH was adjusted to 10.15 with sulfuric acid. Color development replenisher Diethylene glycol 17g Potassium chloride 3g Potassium sulfite (50% solution) 1.0ml 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate 8.8g Diethylhydroxylamine ( 85% solution) 7g Triethanolamine 10g Potassium carbonate 30g Ethylenediaminetetraacetic acid 2g Optical brightener (PK-Conc manufactured by Nisso Corp.) 2.5g Water is added to make the total volume 1000 ml, and pH is adjusted to 11.0 with potassium hydroxide or sulfuric acid. Adjusted to.

Bleaching tank liquid Organic acid Ferric sodium salt (A-1) 100 g Ethylenediaminetetraacetic acid 2 g Ammonium bromide 178 g Glacial acetic acid 50 ml Water was added to make 1000 ml, and the pH was adjusted to 7.0 using aqueous ammonia or glacial acetic acid. To do.

Bleaching replenishing solution Organic acid Ferric sodium salt (A-1) 120 g Ethylenediaminetetraacetic acid 2 g Ammonium bromide 178 g Glacial acetic acid 50 ml Water was added to 1000 ml, and the pH was adjusted to 6.3 using aqueous ammonia or glacial acetic acid. To do.

Fixing tank solution and fixing replenishing solution Ammonium thiosulfate 180 g Ammonium thiocyanate 120 g Sodium metabisulfite 3 g Ethylenediaminetetraacetic acid 0.8 g Water is added to make 1000 ml, and the pH is adjusted to 6.5 with acetic acid and aqueous ammonia.

Stable tank solution and stable replenisher o-Phenylphenol 0.15g Zinc sulfate (heptahydrate) 0.2g Ammonium sulfite (40% solution) 5.0ml 1-Hydroxyethylidene-1,1-diphosphonic acid (60% solution) 2.5g Ethylenediaminetetraacetic acid 2.0g Optical brightener (Tinopearl SFP, Ciba Geigy) 2.0g Ammonia water or sulfuric acid is added to pH 7.8 and water is adjusted to 1000 ml.

The following photographic performances of the running-treated samples thus obtained were evaluated.

<Sharpness> Wedges obtained by closely baking on a resolution chart with white light and developing with each running processing solution were measured for yellow, magenta and cyan images with a microphotometer to obtain sharpness. Was evaluated.

Sharpness = (maximum density in a dense line print image of 3 lines / mm−minimum density) / (maximum density in large area−minimum density) An average of yellow, magenta and cyan is evaluated, and this value The larger the value, the better the sharpness. 50% or more is good.

<Gloss> White light was applied to the entire surface of the sample, and after development processing was performed with each running processing solution, the gloss was visually evaluated.

○… Satisfying results △… Slightly unsatisfactory but acceptable results ×… Unacceptable results <Coating unevenness> Uniform color was obtained by inserting a color separation filter into white light to obtain a gray density of about 1.0. After exposure, development processing was performed with each running processing solution, and coating unevenness was visually evaluated.

◯: Good Δ: Slightly bad, but within practically acceptable limit ×: Not possible <Short-term image storability> A color separation filter was inserted into white light and exposed through a wedge-shaped wedge, immediately after sample preparation and at 23 ° C.
・ Short-term image storability was evaluated by measuring the density after storage for 3 months under the condition of 70% RH.

(Stain) Evaluation by increase in blue light measurement density is less than 0.01. Good 0.01 or more ... No (image density) Evaluation by change in blue light measurement density of 1.0 is less than 0.05 ... Good 0.05 or more ... No Results are shown in Table 4. Show.

[0190]

[Table 4]

From the results in Table 4, it can be seen that Samples 4 to 13 of the present invention are good in all photographic performances.

Example 2 On a triacetyl cellulose film support, each layer having the composition shown below was sequentially formed from the support side to prepare a multilayer color negative photosensitive material sample.

Each numerical value shows the amount of the additive added per 1 m ² . However, silver halide and colloidal silver are equivalent to silver. The sensitizing dye is shown by the number of moles per mole of silver contained in the same layer.

First layer: antihalation layer Black colloidal silver 0.2 g UV absorber (UV-4) 0.23 g High boiling point solvent (Oil-1) 0.18 g Gelatin 1.4 g Second layer: First intermediate layer Gelatin 1.3 g 3 layers: low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.4 μm, AgI 2.0 mol%) 1.0 g Sensitizing dye (SD-1) 1.8 × 10 ^-5 mol Sensitizing dye (SD-2) 2.8 × 10 ^-4 mol Sensitizing dye (SD-3) 3.0 × 10 ^-4 mol Cyan coupler (C-3) 0.70 g Colored cyan coupler (CC-1) 0.066 g DIR compound (D-1) 0.03 g DIR compound (D-3) 0.01g High boiling point solvent (Oil-1) 0.64g Gelatin 1.2g Fourth layer: Medium-sensitive red-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.7 µm, AgI 8.0 mol%) 0.8 g increase Sensitizing dye (SD-1) 2.1 × 10 ^-5 mol Sensitizing dye (SD-2) 1.9 × 10 ^-4 mol Sensitizing dye (SD-3) 1.9 × 10 ^-4 mol Cyan coupler (C-3) 0.28 g Colored dosia Coupler (CC-1) 0.027 g DIR compound (D-1) 0.01 g high boiling solvent (Oil-1) 0.26 g gelatin 0.6 g Fifth layer: high-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.8 μm, AgI 8.0 mol%) 1.70 g Sensitizing dye (SD-1) 1.9 × 10 ^-5 mol Sensitizing dye (SD-2) 1.7 × 10 ^-4 mol Sensitizing dye (SD-3) 1.7 × 10 ^-4 Mol Cyan coupler (C-3) 0.05g Cyan coupler (C-4) 0.10g Colored cyan coupler (CC-1) 0.02g DIR compound (D-1) 0.025g High boiling solvent (Oil-1) 0.17g Gelatin 1.2 g 6th layer: 2nd intermediate layer gelatin 0.8g 7th layer: low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.4 μm, AgI 2.0 mol%) 1.1 g Sensitizing dye (SD-4) 6.8 × 10 ^-5 mol sensitizing dye (SD─5) 6.2 × 10 ^-4 mol magenta coupler (M─2) 0.54g magenta coupler (M─3) 0.19g colored magenta coupler (CM─1) 0.06g DIR compound (D-2) 0.017 g DIR compound (D-3) 0.01 g High boiling point solvent (Oil-2) 0.81 g Gelatin 1.8 g Eighth layer: Medium-speed green sensitive emulsion layer Silver iodobromide emulsion (average grain size 0 0.7 μm, AgI 8.0 mol%) 0.7 g Sensitizing dye (SD-6) 1.9 × 10 ⁻⁴ mol Sensitizing dye (SD-7) 1.2 × 10 ⁻⁴ mol Sensitizing dye (SD-8) 1.5 × 10 ^{− 5} mol Magenta coupler (M-2) 0.07g Magenta coupler (M-3) 0.03g Colored magenta coupler (CM-1) 0.04g DIR compound (D-2) 0.018g High boiling solvent (Oil-2) 0.30g Gelatin 0.8g 9th layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (average grain size 1.0 μm, AgI 8.0 mol%) 1.7 g Sensitizing dye (SD-6) 1.2 × 10 ^-4 mol Sensitizing dye (SD ─7) 1.0 × 10 ^-4 mol Sensitizing dye (SD-8) 3.4 × 10 ^-6 mol Magenta coupler (M-2) 0.09g Magenta coupler (M-4) 0.04g Colored magenta coupler (CM-1) 0.04 g high boiling point Solvent (Oil-2) 0.31g Gelatin 1.2g 10th layer: Yellow filter layer Yellow colloidal silver 0.05g Color stain inhibitor (SC-1) 0.1g High boiling point solvent (Oil-2) 0.13g Gelatin 0.7g Formalin scavenger ( HS-1) 0.09g Formalin scavenger (HS-2) 0.07g 11th layer: low-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.4 μm, AgI 2.0 mol%) and silver iodobromide emulsion (average) Particle size 0.7 μm, AgI 8.0 mol%) 0.5g Sensitizing dye (SD-9) 5.2 × 10 ^-4 mol Sensitizing dye (SD-10) 1.9 × 10 ^-5 mol Yellow coupler (Y-2) 0.65g Yellow coupler (Y-3) 0.24g DIR compound (D-1) 0.03g High boiling solvent (Oil-2) 0.18g Gelatin 1.3g 12th layer: high sensitivity blue sensitive emulsion layer Silver iodobromide emulsion (average) Particle size 1.0 μm, AgI 8.0 mol%) 1.0 g Sensitizing dye (SD-9) 1.8 × 10 ^-4 mol Sensitizing dye (SD-10) 7.9 × 10 ^-5 mol Yellow color Puller (Y-2) 0.15g Yellow coupler (Y-3) 0.05g High boiling point solvent (Oil-2) 0.074g Gelatin 1.30g Formalin scavenger (HS-1) 0.05g Formalin scavenger (HS-2) 0.12g No. 13 Layer: First protective layer Fine grain silver iodobromide emulsion (average particle size 0.08 μm, AgI 1.0 mol%) 0.4 g UV absorber (UV-4) 0.07 g UV absorber (UV-5) 0.10 g High boiling solvent ( Oil-1) 0.07g High boiling point solvent (Oil-3) 0.07g Formalin scavenger (HS-1) 0.13g Formalin scavenger (HS-2) 0.37g Gelatin 1.3g 14th layer: 2nd protective layer Alkali-soluble matting agent ( Average particle size 2 μm) 0.13 g Polymethylmethacrylate (average particle size 3 μm) 0.02 g Sliding agent (WAX-1) 0.04 g Gelatin 0.6 g In addition to the above composition, coating aid SU-4, dispersion aid S
U-1, viscosity modifier, hardener H-2, H-3, stabilizer S
T-11, antifoggant AF-1, weight average molecular weight 10,0
Two AF-2s, 00 and 1,100,000, were added.

The emulsion used in the above sample was prepared in the same manner as in Example 1. Each emulsion was optimally gold and sulfur sensitized.
The average particle size is shown as a particle size converted into a cube.

The additives used for sample preparation are as follows.

Oil-1: dioctyl phthalate Oil-2: tricresyl phosphate Oil-3: dibutyl phthalate SC-1: 2-sec-octadecyl-5-methylhydroquinone SU-4: sulfosuccinic acid dioctyl ester sodium HS- 1: 4-ureidohydantoin HS-2: hydantoin H-3: bis (vinylsulfonylmethyl) ether ST-11: 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene AF-1: 1 -Phenyl-5-mercaptotetrazole AF-2: Poly-N-vinylpyrrolidone

[0198]

[Chemical 17]

[0199]

[Chemical 18]

[0200]

[Chemical 19]

[0201]

[Chemical 20]

[0202]

[Chemical 21]

[0203]

[Chemical formula 22]

The sample thus prepared was wedge-exposed with white light and then processed under the following conditions.

(Processing condition-C) Processing step Processing time Processing temperature Complementary amount * Color development 3 minutes 15 seconds 38 ℃ 536ml Bleach 45 seconds 38 ℃ 134ml Settling 1 minute 30 seconds 38 ℃ 536ml Stability ** 90 seconds 38 ℃ 536ml Dry 1 minute 40-70 ℃ ― * Replenishment amount is the value per 1m ² of light-sensitive material.

** Stable was adopted with a counter current of three tanks, and the replenisher was added to the stable final tank.

The composition of the processing liquid used in the above processing step is as follows.

Color developer Potassium carbonate 30g Sodium hydrogen carbonate 2.5g Potassium sulfite 3.0g Sodium bromide 1.3g Potassium iodide 1.2mg Hydroxylamine sulfate 2.5g Sodium chloride 0.6g 4-Amino-3-methyl-N-ethyl- N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make 1000 ml, and adjust to pH 10.06 with potassium hydroxide or 20% sulfuric acid.

Color developing replenisher solution potassium carbonate 35 g sodium hydrogen carbonate 3 g potassium sulfite 5 g sodium bromide 0.4 g hydroxylamine sulfate 3.1 g 4-amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate Salt 5.8g Potassium hydroxide 2g Diethylenetriaminepentaacetic acid 3.0g Add water to make 1000ml, and adjust to pH 10.12 with potassium hydroxide or 20% sulfuric acid.

As the bleaching tank solution, the fixing tank solution, the stabilizing tank solution, and the replenishing solutions, the processing solutions used in the processing condition B of Example 1 were used.

In parallel with the above processing step C, after exposing the samples 1 to 13 used in Example 1 and using the overflow solution of the bleaching solution of the above processing step C as a replenisher for the bleaching solution, The treatment was performed according to the same treatment steps as the treatment condition-B of Example 1. That is, it becomes as follows.

Processing step C (color negative film) (color developing solution)-(bleaching solution)-(fixing solution)-(stabilizing solution) Processing step B (color paper) (color developing solution)-(bleaching solution)-(fixing) Solution)-(Stabilizer) A replenisher is added to each step. The overflow solution of the bleaching solution in the processing step was all run as a replenisher for the processing step B.

That is, as the bleaching replenisher for color paper, piping was run so that the overflow of the bleaching solution for the color negative film would all flow (replenish) into the bleaching solution for color paper, and a running process was carried out. The running process was continuously carried out until the amount of the bleaching solution flowing in was twice the tank capacity of the bleaching solution for color paper (this is referred to as 2R). In addition, the processing amount of color paper and the processing amount of color negative film are as follows.
Color paper E version (8.
The running treatment was performed at a ratio of treating 24 sheets of 2 cm × 11.7 cm).

The results of evaluation of Samples 1 to 13 treated under the above conditions in the same manner as in Example 1 are summarized in Table 5.

[0215]

[Table 5]

From the results shown in Table 5, the samples 4 to 13 of the present invention are also shown.
Is excellent in all photographic performances.

[0217]

According to the present invention, a color print excellent in image sharpness and print gloss can be easily obtained, and the image quality is less deteriorated even if the processing steps of the color negative film and the color paper are partially common. A forming method could be provided.

Claims (1)

[Claims] 1. A method for forming a dye image by color-developing a silver halide photographic light-sensitive material comprising a photographic printing paper support having a polyolefin coating layer on both sides of a base paper and coated with a photographic light-sensitive layer. In, the surface of at least the photographic photosensitive layer side of the support has a center plane average roughness (SRa) calculated by the following formula is 1.0 μm or less, and the surface side polyolefin coating layer has titanium oxide particles. It is contained at a density of 14% by weight or more, and the amount of gelatin contained in the photographic light-sensitive layer is 7.5 g / m ² or less, and after color development processing, bleaching processing and then fixing processing are performed. A method for forming a dye image. [Equation 1] In the formula, Lx is the length of the measurement surface area in the X-axis direction, Ly is the length of the measurement surface area in the Y-axis direction, S _A is the area of the measurement surface area, and S _A =
Lx × Ly, S _A = 25 mm ² , and Lx = Ly = 5 mm.