JPH01307746A - Manufacture of color print - Google Patents

Abstract

PURPOSE:To make possible the rapid processing of the color print with simplicity by image-wisely exposing a photosensitive material having a wt.ratio of oil/coupler of <=1/5, and subjecting the obtd. material to color development and desilverization, and washing the obtd. material with a water or a water contg. alcohol, followed by heating the obtd. material and printing it to a photosensitive material for the color print in an undried state. CONSTITUTION:The silver halide color photographic sensitive material for photography, comprises at least one layer of photosensitive emulsion layers mounted on a supporting body, and a photosensitive emulsion has the wt.ratio of oil/coupler of <=1/5, preferably <=1/10, further preferably 0 (not contg. an oil). The photosensitive material is image-wisely exposed and then subjected to the color development and the desilverization, and washed with the water or the water contg. alcohol, followed by heating the obtd. material and printing it to the photosensitive material for the color print in the undried state. Thus, the simple and rapid processing of the photosensitive material makes possible, and the color print capable of sufficiently satisfying quality requirements in the field of a news photograph, etc., is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for easily and quickly producing color prints.

[Conventional technology]

Traditionally, in the field of news photography, photosensitive materials (hereinafter also referred to as photosensitive materials) taken at crime scenes are simply developed, washed with water, dried, and then left undried using an enlarger to create a print-ready image. This is printed on a material and used as is, or it is sent by reflection by facsimile or the like.

In these conventional news photographs, black and white film/paper systems have generally been used. However, with the recent advances in colorization of printed matter and even newspaper articles, there is a growing demand for similar simple and rapid processing to be performed on color film/paper systems as well.

By the way, in color sensitive materials for photography, in order to disperse the coupler in gelatin, the coupler is mixed with a relatively large amount of oil, that is, at least 3 parts by weight per layer per 1 part by weight of the coupler, generally 1 part by weight. The method used is to dissolve it in oil and disperse it in gelatin.

For this reason, even if you try to print a photosensitive material for color printing in an undried state after color development, desilvering treatment, and washing with water, a large amount of oil and water contained in the photosensitive material will be removed. There was a problem in that the light was scattered due to this, making it impossible to obtain prints with sufficient image quality to be used as press photographs. For this reason, prior to printing, the moisture content is generally
8g/n? It was extremely difficult to easily and quickly produce color prints.

[Problem to be solved by the invention]

Therefore, an object of the present invention is to provide a method for easily and quickly producing color prints from already photographed color photosensitive materials with image quality that fully satisfies the requirements in fields such as news photography.

(Means for Solving the Problems) An object of the present invention is to provide a halogenated emulsion having at least one photosensitive emulsion layer on a support, and having an oil/coupler weight ratio of 175 or less in the photosensitive emulsion. This is achieved by exposing a color photographic material for silver photography, subjecting it to color development and desilvering, washing it with water or alcohol-containing water, and then printing it into a light-sensitive material for color printing in an undried state. .

The color photographic material used in the present invention has an oil/coupler weight ratio of 115 or less, preferably 1/10 or less,
More preferably, it is O (does not contain oil). It is described in No. 581.

Any known silver halide emulsion for light-sensitive materials can be used. In the case of light-sensitive materials for color printing, use silver chloride bromide emulsion (silver chloride is 90% for rapid processing).
In the case of a color photographic material, a silver iodobromide emulsion (the content of silver iodide is preferably 2 to 15 mol %) is preferable. Further, the shape of the silver halide grains may be spherical, cubic, octahedral, rhombic dodecahedral, tetradecahedral, etc., and tabular grains (preferably aspect ratio 5 to 20) are preferable for high-sensitivity photosensitive materials. The particles may have a uniform phase or a multilayer structure. Further, the particles may be surface latent image type particles or internal latent image type particles.

The particle size distribution may be polydisperse or monodisperse (preferably standard deviation/average particle size<15%), but the latter is preferred. These silver halide grains may be used alone or in combination depending on the purpose.

The photographic emulsion used in the present invention is as follows: Research Disclosure (RD) Vol. 176, No. 17643 (■, ■,
It can be prepared using the method described in Section 2) (December 1978).

The emulsion used in the present invention is usually subjected to physical ripening and chemical ripening.
Use the one that has been synthesized and spectrally sensitized.

Additives used in such processes are described in Research Disclosure Vol. 176, No. 17643 (January 1978).
(February) and Volume 187, No. 18716 (November 1979), and the relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below.

Attachment 1 type RD17643 RD1871
6■ Chemical sensitizers page 23, page 648, right column 2
Sensitivity enhancer Same as above 5 Increase whitening
Agent page 24 7 Coupler page 25 8 Organic solvent page 25 10 Ultraviolet absorber 11 Anti-stain agent Page 25 right column Page 650 left ~
Right column 12 Dye image stabilizer page 25 13 Hardener page 26 page 651 left column 14 Binder page 26 Same as above 15
Plasticizer, lubricant Page 27 Page 650 Right column 17
Static prevention page 27 Same as above agent Various color couplers can be used in the present invention, and specific examples thereof are given in the above-mentioned Research Disclosure (
RD) N117643, ■-C-G. As dye-forming couplers, the three subtractive primary colors (i.e. yellow, magenta and cyan)
It is important to have a coupler that gives a 4-equivalent or 2-equivalent coupler during color development, and a specific example of a diffusion-resistant 4-equivalent or 2-equivalent coupler is the above-mentioned RD17.
In addition to the couplers described in the patents described in Sections 643, 1-C and D, the following can be preferably used in the present invention.

Typical examples of yellow couplers that can be used include known oxygen atom elimination type yellow couplers and nitrogen atom elimination type yellow couplers. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include hydrophobic 5-pyrazolone and pyrazoloazole couplers that have a ballast group.

As the 5-pyrazolone coupler, a coupler in which the 3-position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of the hue and coloring density of the coloring dye.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol couplers and phenol couplers, and representative examples include preferably oxygen atom-eliminating two-equivalent naphthol couplers. Couplers that can also form cyan dyes that are stable against humidity and temperature are
Typical examples of preferred examples include phenolic cyan couplers having an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus, 2,5-diacylamino-substituted as described in U.S. Pat. No. 3.772.002. These include phenolic couplers, phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, and 5-amidenaphthol cyan couplers described in European Patent No. 161,626A.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
Specific examples of magenta couplers are described in US Pat. No. 4,366.237, and specific examples of yellow, magenta or cyan couplers are described in European Patent No. 96.570.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye-forming couplers are described in U.S. Patent No. 3.
No. 451,820 and No. 4.080.211. Specific examples of polymerized magenta couplers are described in British Patent No. 2.102.173 and U.S. Pat.
．． 367, 282.

The various couplers used in the present invention can be used in combination in two or more layers in the same photosensitive layer, or in two or more different layers using the same compound, in order to satisfy the characteristics required for the photosensitive material. It can also be introduced into

The standard usage amount of color couplers is in the range of 0.001 to 1 mole per mole of photosensitive Sm halide, preferably 0.01 to 0 for yellow couplers.
．． 5 moles, 0 for magenta couplers, OO3 to 0
．． 3 moles, and 0.002 to 0 for cyan couplers.
．． It is 3 moles.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. An example of an oil, i.e., a high boiling point organic solvent, used in the oil-in-water dispersion method is given in U.S. Pat.
．． 322.027, etc. Further, the process and effects of latex dispersion method as one of the polymer dispersion methods, and specific examples of latex for impregnation are described in U.S. Patent No. 4.1.
No. 99,363, West German Patent Application (OLS) No. 2,541
, 274 and 2,541.230, and the dispersion method using a solvent-soluble polymer is described in PCT Application No. JP87100492.

Examples of organic solvents used in the above-mentioned oil-in-water dispersion method include phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, etc.). phate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesine. In addition to acid esters (e.g. tributyl trimesate), the above oil and organic solvents having a boiling point of about 30°C to 150°C, such as lower alkyl acetates such as ethyl acetate and butyl acetate,
Ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc. may be used in combination.

The photosensitive material used in the present invention is a commonly used transparent plastic film (cellulose nitrate, cellulose acetate,
The photosensitive emulsion described above is coated on a flexible support such as polyethylene terephthalate (polyethylene terephthalate, etc.) or paper. For details on supports and coating methods, see Research Disclosure, Vol. 176, No. 17643, Section XV (p. 2).
7) Described in Section X (p. 28) (December 1978 issue).

The color sensitive material for TI shadows used in the present invention comprises a blue-sensitive silver halide emulsion layer containing a yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a red-sensitive halogen emulsion layer containing a cyan coupler. It is preferable to contain a silver halide emulsion layer, of which at least a blue-sensitive silver halide emulsion has an oil/coupler weight ratio of 115.
The oil/coupler weight ratio of these three types of silver halide emulsions is preferably 175 or less, and most preferably.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phinidine diamine compounds are preferably used, and a typical example is 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-meth+-xyethylaniline and their sulfates,
Examples include hydrochloride and p-toluenesulfonate. 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,
It is common to include development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercap 1-compounds. In addition, as necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo(2,2゜2〕octane)), etc. Various preservatives, organic compounds such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, and sodium boron hydride. fogging agents, auxiliary developing agents 4 such as l-phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids; for example,
Ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, ■-hydroxyethylidene-1. 1-diphosphonic acid, nitrilo-N,N,N-
) rimethylenephosphonic acid, ethylenediamine-N, N,
N'.

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

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents, such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol, alone or Can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but in general it is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 or less.
It can also be less than 1I11. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. 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 (■), Kobal l-(I[[
), compounds of polyvalent metals such as chromium (Vl), 1iiJ (n), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (1) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, I,3-diamino Aminopolycarboxylic acids such as propanetetraacetic acid, glycol ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; persulfates; bromates; permanganates; nitrobenzenes, etc. can be used. Among these, aminopolycarboxylic acid iron(III) complex salts including ethylenediaminetetraacetic acid iron(III) complex salts and O persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Complex salts are particularly useful in both bleach and bleach-fix solutions.

The pH of the bleach or bleach-fix solution using these aminopolycarboxylic acid iron(I[I) complex salts is usually 5.5 to 8, but in order to speed up the processing, the pH may be lowered. You can also.

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

Specific examples of useful bleach accelerators are described in the following specification. Namely, U.S. Patent No. 3,893,858, West German Patent No. 1,290.812, and Japanese Unexamined Patent Publication No. 1986-95.6.
No. 30, Research Disclosure Fish 17.129
issue (July 1978) etc.)! or a compound having a disulfide bond; JP-A-50-140
．． Thiazolidine derivatives described in No. 129; U.S. Pat.
．． Thiourea derivatives described in No. 706.561; JP-A-5
8-16.235; West German Patent No. 2.
Polyoxyethylene compounds described in Japanese Patent Publication No. 748.430; polyamine compounds described in Japanese Patent Publication No. 45-8836; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide bond are preferred from the viewpoint of a large promoting effect, and are particularly preferred, as described in US Pat.
．． Preferred are the compounds described in US Pat. No. 630, and also preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the photosensitive material.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for Preservatives for the bleach-fix solution are preferably sulfites, bisulfites, sulfinic acids, or carbonyl bisulfite adducts.

The silver halide color photographic light-sensitive material of the present invention is subjected to a water washing treatment after desilvering treatment. The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used, such as couplers), the use
Furthermore, it can be set over a wide range depending on the temperature of the washing water, the number of washing tanks (the number of stages), the replenishment method such as counterflow or forward flow, and various other conditions. The relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the 5o
Society of MotionPicture an
d Te1evision Engineers No. 64
Volume, P.

24B-253 (May 1955 issue),
You can ask for it.

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. As a solution to such problems in processing the color brightening material of the present invention,
The method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 61-131.632 can be used very effectively. Also, JP-A-57-8.542
Chlorinated disinfectants such as isothiazolone compounds and cyabendazoles, chlorinated isocyanurate, and other benzotriazoles listed in the issue, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, and "Microorganisms" edited by Sanitation Technology Association. Sterilization and sterilization 1. Anti-mildew technology" and "Encyclopedia of anti-bacterial and anti-mildew agents" edited by the Japanese Society of Anti-bacterial and Anti-fungal agents can also be used.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-
9, preferably 5-8. 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 minutes at 15-45°C, preferably 20 minutes.
A range of 30 seconds to 5 minutes at 5 to 40°C is selected. Furthermore,
The light-sensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-open No. 57-8.543, 5B-14,83
All known methods described in No. 4, No. 60-220,345 can be used.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing.

In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,
Indoaniline compounds described in No. 597, No. 3.34 of the same
2.599, Research Disclosure 14,8
Schiff base-type compounds described in No. 50 and No. 15.159, aldol compounds described in No. 13.924, metal salt complexes described in U.S. Pat.
Examples include urethane compounds described in No.-135.628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated. Typical compounds are disclosed in JP-A-56-64,339 and JP-A-57-144,547.
No. 5B-115,438, etc.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to. In addition, for saving silver in photosensitive materials, West German Patent No. 2,226.770 or U.S. Patent No. 3
．． A treatment using cobalt intensification or hydrogen peroxide intensification as described in No. 674.499 may also be carried out.

In the method of the present invention, the image-exposed photosensitive material is washed with water or alcohol-containing water after color development and desilvering treatment. Alcohol is added to promote drying, and methyl alcohol, ethyl alcohol, etc. can be used. The alcohol content is suitably 0 to 30% by weight. The washing liquid may contain formalin, a surfactant, an antifungal agent, or a chelating agent. The washing may be carried out by immersing the material, or by pouring a washing liquid onto the sensitive material.

The washed photosensitive material for shadows is dried to remove the washing liquid adhering to its surface, or dried for a short time if necessary, and then printed into a photosensitive material for color printing using an enlarger in an undried state. Here, undried state means 10 g/d or more, preferably 15 g/d.
/g or more of washing liquid (mainly water).

Incidentally, when necessary drying is performed prior to printing as in the conventional method, the water content is generally about 1 to 8 g/rd.

〔Effect of the invention〕

According to the method of the present invention, since a photosensitive material with a specific oil/coupler ratio or no oil is used, the photosensitive material is subjected to image exposure, color development, and desilvering treatment, followed by simple water washing and Color prints can be produced from the photosensitive material for printing by simply drying it if necessary and applying it to an enlarger in an undried state. Therefore, the production time for color prints can be significantly shortened. Furthermore, the image quality of color prints obtained through such simple and rapid processing fully satisfies the quality requirements in fields such as news photography, and the method of the present invention is particularly useful in such fields. be.

<Example 1> A color photosensitive material 101 for multilayer photography was prepared, which consisted of each layer having the following composition on an undercoated cellulose triacetate film support.

1st layer: antihalation layer black carp VGf1 0.25g/
m Ultraviolet absorber U-10,1g/% Ultraviolet absorber U-20,1glrrrHigh boiling point organic solvent O41130mg/ggelatin
1.9g/m 2nd layer; Intermediate FJ-1 Cpd A 10o+g
/ryf High boiling point organic solvent Of! 3 1
2 mg/ rrr gelatin
0.4 g/rrr Third layer; Intermediate layer-2 Surface-covered fine grain silver iodobromide emulsion (average grain size 0.06 μAgI content 1 mol%) Silver@
0.05g/d Gelatin 0.4g/rd 4th
Layer: 1st red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (monodisperse cubic with average grain size 0.2μ/Igl content 4 mol%) Silver 1 0 .4 g/rrl coupler C-10,2g/nf coupler C-20,05g/rrr high boiling point organic solvent O4l -140mg/nl gelatin 0.8g/rrf 5th layer;
Second red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (monodisperse cubic emulsion with average grain size 0.3 μAgr content 4 mol %) Silver amount 0.4 g/ r4 Coupler C-10,2g1rd Coupler C-30,2g/rrf Coupler C-20,05g/rrrHigh boiling point organic solvent O4l -140mg/m Gelatin
0.8 g/rrf 6th layer; 3rd red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes s-i and S-2 (average grain size 0.4 μAgl containing f!t2 mol%) Monodisperse cube) Silver amount 0.4 g/m Coupler C-30, 1 g/rd Gelatin 1.1 g/m 7th layer: Intermediate layer-3 Dye D-10, 02 g/rrl Gelatin 0.6 g/rrr 8th layer Intermediate layer-4 Surface-covered fine-grain silver iodobromide emulsion (average grain size: 0.06 μAgl content: 1 mol %) Silver amount: 0.
05 g/rd Compound Cpd A O, 2g/r
d Gelatin 1.0g/n? 9th layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion spectrally enhanced with sensitizing dyes S-3 and S-4 (monodisperse cubic with average grain size 0.2 μAgI content 4 mol %) S reversal amount 0 .5 g/rd Coupler C-40,3g1rd Compound Cpd B 0.03g/
rrr gelatin 0.5g1r
d 10th layer; 2nd glaucoma emulsion layer Silver iodobromide emulsion containing enhancing dyes S-3 and S-4 (monodisperse cubic with average grain size 0.4 μAgl content 4 mol %) Silver amount 0.4 g 1 rl Coupler C-40,3g/rd Compound Cpd,8 0.03g/
m gelatin 0.6g/rrr
11th layer: 3rd green-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-3 and S-4 (Agl-containing N2 emulsion with an average grain size of 0.5μ and an average aspect ratio of 5)
Mol% tabular emulsion) Silver amount 0.5g/nf Coupler C-40.8g/A compound Cpd B 0.08g
/rd gelatin 1. Og/
m 12th layer: Intermediate layer-5 Dye D-20.05g/m Gelatin 0.6g/rd 1st
3N: Yellow filter layer Yellow colloidal silver 0.1g/m Compound Cpd A 0.01g/n?
Gelatin 1.1 g/rrr
141st! li First blue emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-5 and S-6 (monodisperse cubic emulsion with average grain size 0.2 μAgI content 3 mol %) Silver amount 0.6 g/rd Coupler C-50, 6g/rd Gelatin 0.8g/m No. 15
Layer: Second blue-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-5 and S-6 (average grain size 0.5μ aspect ratio 7 Agl content 2
Mol% tabular emulsion) Silver amount 0.4 g/rt (Coupler C-50.3 g/rrl Coupler C-60.3 g/rrr Gelatin 0.9 g/% No. 16
Layer: Third blue-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-5 and S-6.

(A tabular emulsion with an average grain size of 1.0 μm and an Agl content of 2 mol % and an aspect ratio of 7) S reaction amount 0.4 g/m Coupler C-60, 7 g/gelatin resistance L 2 g/m 17th layer: 1st protective layer UV rays Absorbent U-10,04g/m 〃U-30,03g/nf ” U 4 0.03g/m〃U-
50,05g/rrr" U-60,05g/ffl Compound Cpd CO,8g/n? D-30,05g/n (gelatin 0.1g/rrr18th layer; Silver bromide emulsion (average grain size 0.06 μAgI content 1 mol%) Silver amount 0.
1g/nf polymethyl methacrylate particles (average particle size 1.5μ) 0
．． 1g/nf 4:6 copolymer of methyl methacrylate and acrylic acid (average particle size 1.5μ) 0.1 g/rd Silicone oil 0.03 g/
rrl Fluorine-containing surfactant W-I Lmg/
rrr gelatin 0.8g/r
rr In addition to the above composition, gelatin hardener H-1 and a surfactant were added to each layer.

The compounds used in each layer are as follows.

H (t) CsH++ C-20il N 0111 Diptyl phthalate Cpd A i1 Cpd B Cpd C U-3 RI Shi4■9(t) (CHt) aSO3Call+ 1 D-3 CIl□=CH5O□CHzCONllCllzC1l
Using □=CH5O□CHzCONllCII□W- as a conventional photosensitive material, the oil amount (g
/ m') was increased as follows (sample N).

102) was prepared.

1st layer High boiling point organic solvent 0i11 0.10 2nd layer 〃'' 0i13 0.02 3rd layer 4th layer 〃〃01110.22 5th layer '' 0ill O,42 6th layer
〃〃0I110,65 8th layer 〃” 0i13 0.10 9th layer
” olz O, 35 10th layer
〃〃01110.30 11th layer 〃〃0ill O,60 13th layer
〃” Oil 3 0.02 14th layer
〃〃0ill 0.50 15th layer 〃〃01
110.55 16th layer 〃” 0ill O, 45 1st
7 layers 〃〃0ill 0.6 After exposing these samples to practical photography using a camera, they were processed according to the following processing steps.

(First developer) ■-Hydroxyethylidene-1,1-diphosphonic acid (40%) 5.8 m t
iKtSO-+ (45%) 44
mffKBr 2.
5gKSCN 1.2g
K1 4.5mgKO
H (45%) 6.5 mjl!
D IMEZONE-3” 1.4 g
KtCOz 14 gN
aHCOs 12 gD
A-1” Add 22g water II!N1) Koda
Company K's developing chemical name (color developing solution) Diethylenetriaminepentaacetic acid (40%) 51111 Phosphoric acid (85%) 8.7 Soybean 1 NaBr 0.65
gKl 30mgK
OH (45%) 37ffj!
NazS O34.5g Citrazic acid 1.3gCD-
3” l1gH3-104
” Add 1g water
11m1) Kodak developing chemicals (bleach-fix solution) EDTA-Fe-NH4-2) 1zo 120g
EDTA・4H10g Ammonium thiosulfate (70%) 150m! Ammonium sulfite 20g geltaraldehyde (50%) 15m62-amino-
5-Mercapto-1,3,4-2g Thiodiazole Kl Add 2g water 11EDTA: Abbreviation for ethylenediaminetetraacetic acid (simple water washing solution) Formalin (37%) 10+j!
Methyl alcohol 60o+j! Immediately after the 11 treatment, the window material was dried at 40 to 50°C for 10 seconds, and then enlarged to 4.5 times on Fujichrome Paper RCP Type 34 using an enlarger and baked. When 303 standard processing was performed, sample 101 produced a color print at a level that could be transmitted, but sample 102 produced only a print with a blurred image and poor color reproducibility, and the color image after transmission was poor. It was completely unusable.

The time required for sufficient drying was approximately 31 minutes and 33 minutes at 40 to 50°C for samples 101 and 102, respectively. That is, although the drying time required to obtain a satisfactory print was not significantly different in either case, there was a large difference in print quality when drying was performed using the simple drying method.

<Example 2> Sample 201, which is a color photosensitive material for multilayer photography, was prepared on a subbed cellulose triacetate film support, consisting of each layer having the composition shown below.

(Composition of photosensitive layer) The coating amount is expressed in g/d of silver for silver halide and colloidal silver, and the amount expressed in g/rrr for couplers, additives and gelatin. Regarding dye-sensitive dyes, the number of moles is expressed per mole of halogenated vA in the same layer.

1st layer (antihalation layer) Black colloidal silver...0.2 Gelatin...1.3ExM-9
-...0.06 UV-1...0.03 UV-2...-0,06 UV-3...0.06 Solv -2...0.05 Solv -3= 0.05 2 layers (middle 11i) Gelatin... 1.0UV-
1...-0,03 ExC-4...-0,02 ExF-1...0.004 Solv -1...-0,OL 3rd layer (low sensitivity red-sensitive emulsion N) Silver iodobromide emulsion (AgI 4 mol%, uniform Agl type, equivalent sphere diameter 0.5μ, coefficient of variation of equivalent sphere diameter 20%, plate-shaped particles, diameter/thickness ratio 3.0) Coated silver amount... 1.2 Iodor Silveride emulsion (Agl 3 mol%, uniform Agl type, equivalent sphere diameter 0.3μ, coefficient of variation of equivalent sphere diameter 15%, spherical particles, diameter/thickness ratio 1.0) Coating 5fflffi...0. 6 Gelatin... 1.0ExS -
1--・4 xlo-' ExS -2-4xto-' ExC-1--・0.05 ExC-2・-0,50 ExC-3--0,03 ExC-4・-・0.12 ExC-5...0.01 4th layer (high sensitivity red emulsion N) Silver iodobromide emulsion (AgT 6 mol%, core shell ratio 1:
1 internal high Agl type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 15%, plate-shaped particles, diameter/thickness ratio 5.0) Application vA amount...0.7 Gelatin...1. 0BxS
-1= 3 Xl0-' ExS -2・,・2,3X10-' ExC-6...0.11 ExC-7...0.05 C-4...0.05 Solv -1 ...0.02 Solv -3...-0,02 No. 57i (intermediate N) Gelatin ...0゜5Cpd-
1...0. l 5olv -1・-0,05 6th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Agl 4 mol%, core shell ratio 1:
1 surface height Agl type, equivalent sphere diameter 0.5μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter/thickness ratio 4.0) Coated silver amount...0.35 Silver iodobromide emulsion ( Agl 3 mol%, uniform Agl type, equivalent sphere diameter 0.3 μ, coefficient of variation of equivalent sphere diameter 25%, spherical particles, diameter/thickness ratio 1.0) Coated nail withdrawal amount ・・・ 0.20 Gelatin
... 1.0ExS-3・,, 5
xto-' ExS -4・-3xlo-' ExS -5・-I -・0.03 Solv -1"-0,02 Solv -4=-0,04 7th layer (highly sensitive green-sensitive emulsion layer) Silver iodobromide emulsion (All 4 mol%, core shell ratio 3
internal high Agl type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter/thickness ratio 5.0) Coated silver amount...0.8 Gelatin...0.5ExS
-3...5 Xl0-' 1Exs -4...3 Xl0-' ExS -5= 1 xto-' [xM-8...0. I HxM-9...-0,02 ExY -11=-0.03 EXC-2--0.03 ExM-14---0, Ol 5olv-1=-0.05 Solv-4... 0.01 8th Ji (middle layer) Gelatin...0.5Cpd-
1...0.05 Solv -1...0.01 9th layer (donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (Agl 2 mol%, internal high Agl with core-shell ratio 2:1) Type, equivalent sphere diameter 1.0 μ, coefficient of variation of equivalent sphere diameter 1
5%, plate-like grains, diameter/thickness ratio 6.0) Coated silver amount , 0.35 Silver iodobromide emulsion (^gj 2 mol%, core shell ratio 1:
1 internal high Agl type, equivalent sphere diameter 0.4μ, coefficient of variation of equivalent sphere diameter 20%, plate-shaped particles, diameter/thickness ratio 6.0) Coated silver amount...0.20 Gelatin...0. 5ExS
-3=8Xl0-'t! xY -13...0.11 ExM -12-0,03 ExM -14=-0,10 Solv -1=-0,05 1st O layer (yellow filter layer) Yellow colloidal silver...0.05 Gelatin...0.5Cpd-2
...0.13 Solv-1=-0.03 Cpd-1...0.10 11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform Type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter/thickness ratio 7.0) Coated silver amount...0.3 Silver iodobromide emulsion (Ag1 3 mol%, Uniform Agl type, equivalent sphere diameter 0.3 μ, coefficient of variation of equivalent sphere diameter 25%, plate-like particles,
Diameter/thickness ratio 7.0) Coating! l! Amount...0.15 Gelatin...1.6ExS
-6--2xlo-' ExC-16...0.05 ExC-2--0,10 ExC-3...0.02 ExY -13-...1.07 Solv -1... 0.0 8 No. 1211 (high sensitivity blue-sensitive emulsion 115) Silver iodobromide emulsion (gllO mol%, internal high Agl type, equivalent sphere diameter 1.0 μ, coefficient of variation of equivalent sphere diameter 25%, multiple twin plate shape Particles, diameter/thickness ratio 2.0) Coating amount...0.5 Gelatin...0.5ExS
-6= I
...0. l UV-5...0.15 Solv-1=0. Ol 5olv -2-0,01 14th layer (second protective layer) Fine-grain silver bromide emulsion (Agl 2 mo) Iy9A, uniform Agl type, equivalent sphere diameter 0.07p)...0.5 Gelatin ...0.45 Polymethylmethacrylate particle diameter 1.5μ ...0.2 ■4-1 ...0.4Cpd
-510,0,5 Cpd-6--00,5 In addition to the above components, each layer contains emulsion stabilizer Cpd-3 (
0.04g/bo), surfactant Cpd-4 (0.02g
/rrr) was added as a coating aid.

uv-t: Same as U-3 in Example 1 UV-2: Same as U-4 in Example 1 UV-3 JV-4 UV-5: Same as U-6 in Example 1 5olv-1 phosphoric acid Tricresyl 5olv 2 Dibutyl phthalate olv-3 Cpd-2 Cpd-3 xC-2 il xC-3 n+1 [! xC-4 H I! xC-, 5 ■ CI+□ C(C1ls)s ExC-7 xM-8 ″ u I!xM-10 ns > 8 ExY -16 E!xs-1 xS-2 xS-3 [!xs-4 ExS-5 ExS-6 o-t: XF-1 same as H-1 of Example 1 Oil amount (g/r
A sensitive material (sample 202) in which rr) was increased as follows was prepared.

1st layer High boiling point organic solvent 5olv2 0.103
0.05 2nd layer ” 〃5olvl O, 25 3rd
Layer 〃〃5o1v20.25 Solv3 0.10 4th layer 〃〃5O1v10.05 Solv3 0.10 5th layer 〃〃5olvl O,15 6th layer
〃〃5olv10.35 〃〃5olv40.15 7th layer 〃〃5olv10.15 〃〃5o1v40.05 8th layer // tt 5olvl O,
0BBO2〃〃5olvl 0.25 1st QJI〃〃5olvl O,20〃”
5olv4 0.10 11th layer ” 〃5olvl O,80〃
〃 5olv3 0.30 12th layer
〃” 5olvl O, 20 13th layer
〃〃5O1v10.10〃” 5olv
2 0.15 These samples were placed in a camera and a photograph of a person was taken.

These samples were then processed through the following processing steps.

Next, the composition of the treatment liquid will be described.

(Color developer) (Unit g) Diethylenetriaminepentaacetic acid 1.01-hydroxyethylidene-3,0 1,1-diphosphonic acid sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide
1.5 mg hydroxylamine sulfate 2.44-(N-ethyl-N-β-4
, 5 hydroxyethylamino) -2-methylaniline sulfate solution was added to 1.01pH1
0.05 (Bleach solution) (Unit g) Ethylenediaminetetraacetic acid di-100.0 Sodium iron trihydrate Ethylenediaminetetraacetic acid di-10.0 Sodium salt Aminoalkyl disulfide (C#6) 0.6 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27
%) Add 6.5mJ water
1.01p)l
6.0 (bleach-fix solution)
(Unit g) Ethylenediaminetetraacetic acid di
〇, 5 Sodium salt Sodium sulfite 7.0 Sodium bisulfite 5.0 Ammonium thiosulfate aqueous solution (70χ) 170.0mβ Add water
1.01p)I
6.7 (Simple washing liquid)
(Unit: g) Formalin (37%)
2. Oal polyoxyethylene-p-0
,3 Monononylphenyl ethyl (average degree of polymerization 10) Ethylenediaminetetraacetic acid di 0,05 Sodium salt Methyl alcohol 50 pots Add 1.0 ipl+ water
Immediately after the 5.0-8.0 processing, both of the photosensitive materials were not yet dry, but they were enlarged to 3.5 times using an enlarger and printed on Fuji Color Super HR Paper Type 02A, using Fuji Color Paper Processing Chemicals CP-20.
Standard processing was performed using

In sample 201, a color print at a transmittable level was obtained. On the other hand, with sample 202, only prints with unclear images and poor color reproducibility were obtained.

The color print obtained from sample 201 was transmitted by facsimile and used as a color printing manuscript for a newspaper, and good color printing was obtained. However, when the color print obtained from sample 202 was transmitted, a color print of sufficient image quality could not be obtained.

When samples 201 and 202 were dried at 45 to 55° C. until completely dry, it took 26 minutes and 28 minutes, respectively. Under this condition, good quality prints were obtained from any sample on Fuji Color paper.

In other words, there was no significant difference within the range of normal processing, but when printing was performed without drying using simple drying, there was a large difference in image quality.

Claims (1)

[Claims] After image exposure of a color photographic light-sensitive material for silver halide photography, which has at least one light-sensitive emulsion layer on a support and in which the oil/coupler weight ratio of the light-sensitive emulsion is 1/5 or less, color development is performed. and a method for producing color prints, which comprises desilvering, then washing with water or alcohol-containing water, and then printing on a photosensitive material for color prints in an undried state.