JPS62189466A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain stable performance free from stains by processing a silver halide color photographic sensitive material provided with at least one silver halide emulsion layer on a reflective support with a color developing solution containing substantially no benzyl alcohol but at least one of specified compounds. CONSTITUTION:The silver halide color photographic sensitive material provided with at least one silver halide emulsion layer on the reflective support is processed with the color developing solution containing substantially no benzyl alcohol but at least one of the compounds represented by the formula in which R<1> H, alkyl, hydroxyalkyl, or carboxy, and R<2> is H, alkyl, hydroxyalkyl, or aldehydo. Said compound may be added in an optional soluble amount in the color developing solution, but a practical amount is generally 0.01-20g/l, preferably, 0.1-5g/l. The color developing solution to be used contains an aromatic primary amine color developing agent, preferably, a p-phenylenediamine derivative, in an amount of 0.1-20g, preferably, 0.5-10g per l of the developing solution.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a processing method for silver halide color photographic materials, and particularly to a processing method in which the stability of a color developer is improved and the processing time is shortened. .

(Prior Art) In recent years, in the market for color photographic light-sensitive materials, there has been a desire to shorten the processing time to shorten the finishing delivery time and to reduce laboratory work. Increasing the temperature and increasing the amount of replenishment are common methods for shortening the time of various treatment steps, but many other methods have been proposed, such as strengthening stirring or adding various accelerators.

In particular, in the processing of color photographic materials having a reflective support, the processing steps themselves are shortened, and after the color development step, the processing is generally completed with a bleach-fixing step and a water washing step.

However, in the process of shortening the processing steps and each process time as described above, in particular, the bleach-fixing step as described in the present invention is 1 minute or less, and the water washing step is 2 minutes or less. It has been found that a new problem arises in that the stain of the processed light-sensitive material increases during continuous processing. Moreover, this problem was particularly noticeable when implementing water-saving treatments that significantly reduced the amount of water used for washing. Such stains are particularly easy to visually detect in reflective light-sensitive materials and inevitably pose a practical problem.

This stain will be removed by re-rinsing, or will not occur if the rinsing time is extended sufficiently, or
In addition to the fact that this problem does not occur when the color developer is replaced with a fresh one, the oxidized components of the color developer adhere to the photosensitive material.
This is thought to be caused by insufficient cleaning.

Various preservatives and chelating agents have been studied to improve the stability of color developers. For example, as a preservative, Tokukai Sho! λ-Hiro 112r, Tatar/lpO
/≠- No., j6-≠7031 and U.S. Patent No. 37≠t
Aromatic polyhydroxy compounds described in US Pat.
No. 020 and the same! 3-. rP≠α-aminocarbonyl compounds described in No. 2j, alkanoamines described in JP-A No. 17-4C Hiro/Hiro-r and metals described in JP-A No. 17-J37≠2 I can give you salt, etc. As a chelating agent, Tokuko Akihiro t-o3
o≠26 and the aminopolycarboxylic acids described in Kou-30232, JP-A-56-273≠7, JP-Ko-Ko-Shojj
-323! Organic phosphonic acids described in No. 2 and West German Patent No. 2-22763, JP-A-Sho! Coal lO core No. 26, same j
3-≠273Q issue, same j Hiro- /J/ / core issue, same 1j
-/26 ≠ No. 7 and J-j-67! Other phosphonocarboxylic acids described in
ttz, JL-20344aO and Special Public Sho J3-
Compounds described in Kou 0900 and the like can be mentioned.

However, even if these compounds are added to a color developer for reflective light-sensitive materials containing ordinary benzyl alcohol, although some effects may be obtained depending on the compound, staining in short-time processing as in the present invention may be The outbreak could not be sufficiently prevented.

(Object of the Invention) Therefore, an object of the present invention is to provide a processing method that has stable performance without occurrence of stain even in processing with shortened processing time.

(Structure of the Invention) The object of the present invention was achieved by the method described below. That is, (1) a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a reflective support, substantially free of benzyl alcohol, and having the following general formula (1
1. A method for processing a silver halide color photographic light-sensitive material, the method comprising processing a silver halide color photographic material using a color developer containing at least one compound represented by the following.

(2) The method for processing a silver halide color photographic material according to item 1, wherein the color developer contains an aromatic primary amine color developing agent.

(3) Clause 2, wherein the light-sensitive material is bleach-fixed after color development, and then washed with water, and the bleach-fixing time is 1 minute or less, and the washing time is 2 minutes or less. A method for processing the silver halide color photographic light-sensitive material described above.

(4) In the above processing method, the amount of washing water in the washing step is equal to or less than the amount of prebath brought in per unit area of the photosensitive material.
. . , 7 to 10 times.

General Formula (I) In the formula, R1 represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, or a carboxy group, and R2 represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, or a carboxy group. R
The number of carbon atoms in the alkyl group and hydroxyalkyl group of 1 and R2 is preferably /- and 2.

The compound of general formula (I) can be used in any amount that dissolves in the color developing solution, but practically it is 0.0/-20/l.
F is generally 0°7-jP.

It is known to process the compounds of the present invention by incorporating them into color developing solutions, for example as described in US Pat.
No. 3, British Patent No. 306, No. 7j. However, the increase in staining that occurs in processing that shortens the processing time after development, such as in the present invention,
Mere use of these compounds did not result in sufficient suppression.

The present inventors have found that the cause of this stain is due to the adhesion of oxidized components of the color developer, and that benzyl alcohol, which is a component of the developer, is involved in the formation or adhesion.

As described above, it can be inferred that the staining that occurs during short-time processing can be effectively suppressed only by the combination of the present invention, in which the compound of general formula (I) is contained in a developer that does not substantially contain benzyl alcohol. It can be said that it was difficult to collapse.

Specific examples of the compound of general formula (I) are shown below, but the present invention is not limited thereto.

Specific example (1) Ho-CH2-C-CH2-OH (2)
CH-CH20H The above compound is commercially available and can be easily obtained. Tautomers of these compounds, such as enol forms and dimers, are also included in the compounds of the present invention.

The color developer used in the present invention contains a known aromatic primary amine color developing agent. Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D/N, N-diethyl-p-phenylenediamine D-co-co-amino-diethylaminotoluene D-32-amino-j-(N-ethyl-N-lacrylamino)toluene D-Hiroshi ≠-[N-ethyl-N- (β-Hydroxyethyl)aminocoaniline 1)-j Komethyl-Hiro-[N-ethyl-N-(β
-hydroxyethyl)aminocoaniline D-4N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-Hiroshi-aminoaniline D-7N-(,2-amino-!-diethylaminophenylethyl)methane Sulfonamide D-f N,N-dimethyl-p-phenylenediamine D-5' Hiro-amino-3-methyl-N-ethyl-N-methoxyethyl ayu IJ 7 D-io Hiro-amino-3-methyl- N-ethyl N
-β-ethoxyethylaniline D-// Hiro-amino-3-methyl-N-ethyl-N
-β-phthoxyethylaniline These p-7 engineered nylene diamine derivatives may also be salts such as sulfates, hydrochloric acid groups, sulfites, and p-toluenesulfonates. The amount of the aromatic-grade amine developing agent used is in a concentration of about 0°Iy to about 20 F, more preferably about O1!1 to about ioy, per liter of developer solution.

As is well known, the color developer used in the present invention may contain t-hydroxylamines.

Although hydroxylamines can be used in the free aban form in color developers, it is more common to use them in the form of water-soluble acid salts. Common examples of such salts are sulfates, oxalates, chlorides, phosphates, carbonates, acetates, and the like. The hydroxylamines may be substituted or unsubstituted, and the nitrogen atom of the hydroxylamines may be substituted with an alkyl group.

The amount of hydroxylamine added is preferably O-! It is 1.

If the stability of the color developer is to be maintained, it is preferable that the amount added be small.

Also, as a preservative, sodium sulfite, potassium sulfite,
It is preferable to contain sulfites such as sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts. The amount of these additions is ay-ao1p/l, preferably 0F-19/l.
As long as the stability of the color developer is maintained, the smaller the amount, the better.

Other preservatives include JP-A No. 74-4c7031, J4-J2/IfO, and JP-A No. 74-4c7031.
Ter 1toitit, No. 2 and U.S. Pat. No. 37≠t! ≠Aromatic polyhydroxy compound described in Hiroshi issue, JP-A-Shoj Co.
μ301O and jJ-rF Hiroshi, α- described in No. 2J'
Aminocarbonyl compounds, various metals described in JP-A No. 7-≠I/L/Hiroshi and JP-A No. 17-137≠2, various sugars described in JP-A-12-102727, JP-A No. 17-137≠2, etc.
7/, hydroxamic acids described in No. 31, rY-i6o
α,α′-dicarbonyl compound described in tut4, 1Jt
Salicylic acids described in y-/1rozrr No. 13
Alkanolamines described in No. j32, poly(alkyleneimines) described in No. jA-y Ko3 Ko2, j, g
Examples include gluconic acid derivatives described in No.-7tj447. Two or more of these preservatives may be used as needed.
May be used together.

The color developer used in the present invention preferably has a pH of ~12, more preferably ~//, 0, and the color developer may contain other known developer component compounds. I can do it.

In order to maintain the above pH, it is preferable to use various buffers.

Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt, N,N dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3. ≠-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, co-amino-λ-methyl/,
3-propanediol salt, valine salt, florin salt, trishydrodiaminomethane salt, lysine salt, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates have excellent solubility, pH, and buffering ability in the high pH range of 0 or higher, and even when added to color developers, they improve photographic performance. It is particularly preferable to use these buffers because they have the advantages of not having any negative effects (fogging, etc.) and being inexpensive.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, and boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate,! Examples include -sulfo-hydroxyammonium, sodium chloride (!-sodium sulfosalicylate), and potassium j-sulfo-2-hydroxybenzoate (!-potassium sulfosalicylate). However, the present invention
It is not limited to these compounds.

The amount of the buffer added to the color developer is 0.7 mol/1
or more, particularly o, imol/l-o,
Particularly preferred is u mol/l.

In addition, various chelating agents can be used in the color developer as an agent for preventing precipitation of calcium or magnesium, or to improve the stability of the color developer.

The chelating agent is preferably an organic acid compound, for example, JP-Ko-Sho≠l-0301791. No. and same≠Hiro-JO2J2
Aminopolycarboxylic acids described in the issue, JP-A-Sho! 6-273
μ7, special public Shoj6-J? J! Organic phosphonic acids described in No. 1 and West German patent Cococoa No. 63, published by JP-A-Sho! 2-10
No. 2726, No. 2730, No. 2730, No. 2726, No. 2726, No. 2730, No. 2726, No. 2726, No.
No. 27, same! ! -/Koro2≠/issue and J-3--6!
Examples include phosphonocarboxylic acids described in JP-A No. 914, etc., and compounds described in JP-A No. 11-20341170, JP-A No. 3-0200, and the like. Specific examples are shown below, but the invention is not limited to these.

・Nitrilotriacetic acid ・Diethylenetriaminepentaacetic acid ・Triethylenetetraminehexaacetic acid ・N , N , N -trimethinephosphonic acid ・Ethylenediamine - N, N, N' , N' -tetramethylenephosphonic acid ・ /, 3-diamino -Pronotoru≠acetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, l,-2-diaminopronoR7tetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediamineforthohydroxyphenylacetic acid・Cophosphonobutane-/, co-tricarboxylic acid ・/-hydroxyethylidene-/,/-diphosphonic acid ・N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid Chelates of these Two or more types of agents may be used in combination as necessary. These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example, 0.0 per liter. /f-10f.

Any development accelerator can be added to the color developer if necessary. However, it does not substantially contain benzyl alcohol, and the amount added is 0 per liter of color developer. rnl/l or less, preferably not at all. Other development accelerators include Tokko Sho J7-/AO♂♂ and Sho J7-4? lr7
No., Jf-7. JDT issue, same! ! -/JJIrO issue,
PT-YOIY and U.S. Pat.
♂ Kota and the same jO-7! ! ! p expressed in No. II
-Phenylenediamine compound, JP-A-Sho, 3-0-1
No. 37744, Special Publication Showa Guhiro-JOO74A, Japanese Patent Publication No. 7
Grade ammonium salts represented by No. 4-/1612 and J2-Ko3 Hirolamb, etc., p-7 minophenol described in U.S. Patent No. 2410/ko2 and No. 4'/15'≠4λ, etc. U.S. Patent No. 21 ≠ 203, U.S. Patent No. 31 Cor.
No. 2, No. ≠λjQ7P4, No. 3, No. 3, No. 31, U.S. Patent No. RXZAT, No. 2191. Amine compounds described in No. P26 and No. Jj12J4At, etc., Japanese Patent Publication No. 57-itort, No. 4!
2-212O1, U.S. Pat.
7, t k"i"oid, other/-phenyl-j-
Hyrazolidones, hydrazines, menion type compounds,
Thione type compounds, imidazoles, etc. can be added as necessary.

In the present invention, any antifoggant can be added to the color developer as necessary. As antifoggants, alkali metal halides such as potassium bromide, sodium bromide, potassium iodide, and organic antifoggants can be used.

Examples of organic antifoggants include benzotriazole, t-nitro(nitroimidazole, j-nitroinindazole, !-methylbenzotriazole, j-nitrobenzotriazole, !-chlorobenzotriazole, coachazolyl benzene). Nitrogen-containing heterozygos compounds such as mitasol, λ-thiazolylmethyl-benzimidazole, hydroxyazaindolizine and l-phenyl-
Mercapto-substituted hetero compounds such as mercapto-tetrazole, comel-cabutobenzimidazole, comel-cabutobenzothiazole, as well as mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. Particularly preferred are nitrogen-containing heteroterminal compounds. These antifoggants may be eluted from the color photosensitive material during processing and may accumulate in the color developer.

The color developer of the present invention preferably contains a fluorescent brightener. As a fluorescent brightener, Hiroshi, μ'-diamino-λ
, 2'-disulfostilbene type compounds are preferred. The amount added is 0-1y/l, preferably 0. /f−λP/l.

Further, various surfactants such as alkylphosphonic acid, arylphosphonic acid, aliphatic carmenic acid, and aromatic carboxylic acid may be added as necessary.

The processing temperature of the color developer of the present invention is 20-J.

'cFF is preferably 30 to 4t00 (:).The processing time is 0 seconds to j minutes, preferably 30 seconds to λ minutes.

It is preferable that the amount of replenishment is small, but preferably 2Q to 600ml of photosensitive material/rrL2! 0 to JOOynl. More preferably, it is 100m1-λ00rttl.

In the present invention, a bleach-fixing process is performed after color development.

The process time of the bleach-fixing process in the present invention is 1 minute or less, which is significantly shorter than the process time of a normal bleach-fixing process (about 7 minutes and 30 seconds). The bleach-fix process time (hereinafter simply referred to as "bleach-fix time") is the time from when the photosensitive material comes into contact with the bleach-fix solution until it comes into contact with the washing water of the next bath. In addition to the time during which the photosensitive material is immersed in the bleach-fixing bath, the time for moving between towers, that is, the time for residence in the air, is added. In the present invention, the preferable bleach-fixing time is 30 seconds to 60 seconds.

The bleach-fix solution of the present invention may contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfite, etc. as preservatives. Contains sulfite ion releasing compounds such as sulfites (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are approximately 0.0λ to 0.30 mol/converted to sulfite ion.
It is preferable to contain 1, more preferably o, 1o.
No1. zomol/l.

Other preservatives that can be used in the present invention include hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds (e.g. acetaldehyde sodium bisulfite).
etc. can be mentioned.

Bleaching agents used in the bleach-fixing bath of the present invention include organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aminopolycarboxylic acids, aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acids. ) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates: hydrogen peroxide, and the like. Among these, organic complex salts of iron(t) are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids useful for forming organic complexes of iron(t),
Aminopolyphosphonic acids, organic phosphonic acids, or their salts are listed as follows: ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β-oxyethyl)-N,N
', N'-triacetic acid, 7.2-diaminopropanetetraacetic acid, triethylenetetraminehexaacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, cyclohexanediaminetetraacetic acid, /+J-diamino-λ-propartur tetraacetic acid acetic acid tyliminodiacetic acid, iminodiacetic acid, hydroxyl iminodiacetic acid, dihydroxyethylglycine ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediaminetetrapropionic acid, ethylenediamine nipropionic acid, phenylenediaminetetraacetic acid, cophosphonobutane/, 2. ≠-Triacetic acid, /, 3-diaminopropanol-N, N, N'.

N'-tetramethylene phosphonic acid, ethylenediamine-N, N, N', N'-tetramethylene phosphonic acid, /, J-propylene diamine-N, N, N', N'
Examples include -tetramethylenephosphonic acid, /-hydroxyethylidene-/, /'-diphosphonic acid, and the like.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, iron-faced complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because they have a high bleaching edge.

The amount of these bleaches per liter of bleach-fix solution is set to 0. /Jr~O,S mol is preferable, and 0.2~O, p mol is more preferable.

The fixing agent used in the bleach-fix solution of the present invention is a known fixing agent, namely, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid. , 3°t-dithia-7,! -Water-soluble silver halide solubilizers such as thioether compounds such as octanediol and thioureas, and these can be used alone or in combination. Also,
It is also possible to use a special bleach-fixing solution consisting of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A No. 1999/1999, ttJjμ. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred.

The amount of fixing agent per liter of bleach-fix solution is preferably 0.3 to λ mol, more preferably o, r to liter.

It is in the range of 0 mol.

The pH range of the bleach-fix solution in the present invention is preferably from Hiroto to t, and more preferably from j to 7.3.

If the pH is lower than this, the desilvering performance will be improved, but the deterioration of the solution and the formation of cyan dye will be promoted. On the other hand, if the pH is higher than this, desilvering is delayed and staining is likely to occur.

In order to adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added as necessary.

Further, the bleach-fix solution may contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

Further, a bleach accelerator can be used in the bleach-fixing solution, if necessary. Specific examples of useful bleach accelerators are described in U.S. Pat.
No. 71, West German Patent No. 1. λriQ.

1/, No. 2, J, Oj9, WIlr, JP-A-53-JJ7j&, No. 13-5713/, No. 37
≠Iir No. j3-477j2, No. 3-7262
No. 3, No. 13-Yr630, No. 13-9'jt, JI
No. z3-io Hiroshi No. 232, same! 3-/2 Hirohiro 2-Hiro No., same j3-/μ1623, same j3-λr Hiro, No. 26,
Ri-chi Disclosure A/7i2y issue (/97
Compounds containing a mercapto group or disulfide group, such as those described in JP-A No. 1, July 1999; Thiazolidine derivatives, such as those described in JP-A No. 0/2; JP-A No. 4T-
rt.

No., Tokukai Shoj Co. 20♂32, same! 3-3273!
No. 3,706. Thiourea derivatives described in No. J-6/: West German Patent No. 1. /27,7/! No., Tokukai Shoj
′? -/12.3j; West German Patent No. 76
6, Koil O, same, 7≠t.

Polyethylene oxides described in Japanese Patent Publication No. 30; polyamine compounds described in Japanese Patent Publication No. Akihiro t-rrJa; and others in Japanese Patent Publication No. 2≠3hiro, Japanese Patent Publication Akihiro t-rrJa. y1. up issue, same j
3-ta μ227, same! Hiro-3j727, same evening-1
trot issue and the same! ? -/43 The compounds described in No. 0 and iodine and bromine ions can also be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred in US Pat.
J rrzr, West German Patent No. 1,290,112,
Tokukai Akira! The compounds described in No. 3-2j430 are preferred.

Additionally, the bleach-fix solution of the present invention may contain bromides (e.g. potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride) or iodides (e.g. ammonium iodide).
rehalogenating agents. Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, as required
Inorganic acids and organic acids having pH buffering ability such as sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc., organic acids and their alkali metal or ammonium salts, or
Corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The processing temperature in this bleach-fixing step is 70° to 100°C, preferably 200 to 100°C. The amount of replenishment is preferably 20vtl-400ml, preferably JOml to 00rnl.

After the desilvering step (bleach-fixing or fixing), treatments such as water washing and/or stabilization are performed. Various compounds can be used in the water washing and stabilization steps for various purposes. For example, it is known to add bactericidal agents and anti-inflammatory agents to prevent the growth of various types of bacteria, mold, and algae. For example, the Journal of Antibacterial
and Antifungal Agents (J, Ant
ibact.

Antifung, Agents) vol, / /
IAJ' 1p207~. 2Jj (/913)
and the compounds described in "Chemistry of Antibacterial and Antifungal" by Hiroshi Horiguchi), or JP-A-77-1! Hiro 3, JP-A-77-! r/4A! , Japanese Patent Publication No. Shoj7-971.30. JP-A Show jr-IO, t/4cJ, JP-A Show j1-/J Hiro63
6. Tokukai Akira! Tar 5' / Hirosan〇, Tokukai Sho! Tar/261
33, Tokukai Sho 1? -/llj$#, JP-A Sho ty-1r 33t, JP-A Sho tO-23 7JO1 JP-A 1. o-2
397! /, Japanese Patent Application Publication No. 1973- 72 Hiro /, Japanese Patent Application Publication No. 1973-
2&0rij2, Japanese Patent Publication No. 4/1988/-Kol≠2, Japanese Patent Publication No. 47-1999.
2♂9 Hiroshi 7, Tokukai Sho Otsu l-215'4' j, Tokukai Sho j'? -/jll17j, special application Show 1, o-1or<su7
The compounds and methods for their use described in the specification can be applied. In particular, inthiazolone derivatives (-1-octyl-hiro-inthiazolin-3-one, !-chloro-2-methyl-≠-
Sulfanilamide derivatives (such as inthiazolin-3-one), sulfanilamide derivatives (such as sulfanilamide), and benzotriazole derivatives (such as benzotriazole, j-methyl-benzotriazole, !-chlorobenzothiazole) are useful. It is known to add various chelating agents for the purpose of improving image stability after processing. For example, inorganic phosphoric acid, organic carzenic acid, aminopolycarboxylic acid, and organic phosphonic acid are useful; JP-A-77-tj≠3, JP-A-37-7-73, No. 0, JP-A-Sho! I-/≠t3
Hiro issue, Tokukai Sho issue-/34! -1,34, JP-A No. 3?
-/2tJ-33, Tokukai Sho! Tar/l≠3μ3, Tokukai Sho! ? -/r'131111-, JP-A-ShojP-/1
≠3≠T issue, Tokukaisho! Day 1rrsst issue, ° Tokukai Showt
o-i3zytttko issue, JP-A-4 O-2Jrr 32, JP-A-10-2397≠, JP-A-60-23-7
μ2, JP-A No. 9710, JP-A No. 60-
Ko3ri 73/No., JP-A-I, O-, ZA, ZP, RR, JP-A-4O-2T2/L/, JP-A-61-≠011
No. 7, JP-A No. 61-da 0-0, JP-A-47-uOJ'
/ issue, JP-A-Shoti-4c.

No. 32, JP-A No. 6/-Hiro 1jJ, JP-A 67-Hiro!
The compounds and methods of use described in JP-A-4/-219-2 and JP-A-4/-λ♂≠J can be applied. Particularly useful are ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, l-hydroxyethylidene/,/'-diphosphonic acid, and ethylenediaminetetramethylphosphonic acid.

Metal compounds can also be used in combination with these clearing agents. For example, bismuth compounds (% Kaisho! I-/J Hiroj
J4), Ba, Ca, Ce, Go.

In, La, Mn5Ni, Pb, Ti, Sn%Zn.

Zr compound (JP-A-Shoj9-/+r4'j4'4'),
Among the compounds such as Mg, AI, and S (Japanese Unexamined Patent Publication No. 11-11-334), Bi, ca, and Mg1Al are particularly useful.

In addition, surfactants are used to effectively promote water washing (JP-A-Sho, r7-/97j4cO specification), and methods of contacting with ion exchange resins to remove components that have an adverse effect (JP-A (Shoto-22034#), reverse osmosis treatment method (Japanese Patent Application Publication No. Shoto-22034#)
, activated carbon, clay material, polyamide-based polymer compound, polyurethane-based polymer compound, phenol resin, epoxy resin, polymer compound having a hydrazide group, polymer compound containing polytetrafluoroethylene, heptahydric or polyhydric alcohol Methods such as contacting with methacrylic acid monoester-polyhydric alcohol methacrylic acid polyester copolymer (JP-A No. 60-2431!/), electrodialysis treatment method (JP-A No. 6/-219 Hiroshi), etc. are applicable. can.

Furthermore, methods such as ultraviolet irradiation and passing through a magnetic field can also be applied to prevent the growth of bacteria and mold. Furthermore, in case of continuous processing,
Ko JJ-/No. 33, Ko JJ-2635' Hiro No. 1, Ko JJ-/No. 4/
-4 Aoa No. 1, same Otsu/-san〇≠ri No. 6/-Hiroshi 01
The methods of No. 1, ti-4Lozt, 61-Hiro 017, 6l-vQjI, and j/-14060 can be applied.

In addition to the above-mentioned additives, a fluorescent brightener, a hardening agent, etc. may be added to the water washing and stabilizing bath.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate in order to improve image storage stability.

Depending on the purpose, two or more of the same or different desired compounds may be used in combination as various additives. It is preferable that the amount added be the minimum amount necessary to achieve the purpose, from the viewpoint of the physical properties of the emulsion film (stickiness, etc.) of the photographic material after processing.

It is preferable that the water washing or stabilization step be carried out in multi-stage countercurrent flow in a tank or more to reduce the amount of replenisher. The amount of replenisher is o, 1-t relative to the amount of pre-bath brought in per unit area of the photosensitive material.
It is preferably o times, more preferably 3 to 30 times.

The water washing or stabilization processing time of the present invention varies depending on the type of sensitive material and processing conditions, but is from 20 seconds to -minutes, and more preferably from 20 seconds to 1 minute and 30 seconds.

The water washing or stabilization treatment temperature of the present invention is 0~μs'
c and dust, preferably 2J0C-μ0°C, more preferably 30 to 3!0C.

In order to increase the effect of washing out components in the membrane during water washing or stabilization treatment, it is preferable to circulate and stir the liquid.
In particular, methods in which the liquid stream strongly hits the surface of the emulsion film of the light-sensitive material (
For example, gas stirring, liquid spraying, etc.) are recommended.

Each treatment bath may be provided with a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, nitrogen stirring, air stirring, etc., as necessary.

The silver halide emulsion used in the present invention substantially contains silver iodide, silver bromide, silver chlorobromide, or silver chloride, and the silver halide preferably used contains 2 to 10 moles of silver chloride. It contains silver chlorobromide.

The silver halide grains used in the present invention may have different phases in the interior and the four surface layers, may have a multiphase structure such as a bonded structure, or may have a uniform phase throughout the grain. Moreover, they may be mixed.

Average grain size of silver halide grains used in the present invention (
In the case of spherical or nearly spherical particles, the particle diameter is the particle size, and in the case of cubic particles, the particle size is the particle size, and the particle size is the average particle size based on the projected area) is preferably λμ or less and 0.7μ or more, but it is particularly preferable. is/μ or lessQ,/! μ
That's all. The grain size distribution may be narrow or wide, but the value (variation rate) obtained by dividing the standard deviation value of the grain size distribution curve of the silver halide emulsion by the average grain size is -2.
It is preferable to use a so-called monodispersed silver halide emulsion within 0%, particularly preferably within tri, in the present invention.

In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are used in an emulsion layer having substantially the same color sensitivity (monodispersity is defined as the above-mentioned type). (preferably one with a variable rate) can be mixed in the same layer or coated in separate layers. Furthermore, a polydisperse silver halide emulsion of -21gI or higher or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, dodecahedral, dodecahedral, etc.).
), may have an irregular crystal shape such as a spherical shape, or may have a composite shape of these crystal shapes. Tabular grains may also be used, and in particular, tabular grains with a length/thickness ratio of 5 or more, particularly 5 or more, have a total projected area of ! An emulsion occupying Q or more may also be used. An emulsion consisting of a mixture of these various crystal forms may also be used. These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the grains.

The photographic emulsion used in the present invention is described in "The Chemistry and Physics of Photography JCP" by Glafkides.
ie et Physique Photogra
phique (published by Paul Monte1, /ri6
7th year)], “Photographic Emulsion Chemistry J [”G, F,
Photographic Emulsi by Duffin
on Chemistry (Focal Pres.
Zelikman et al., "Production and Coating of Photographic Emulsions J [V, L.

Making a by Zelikman et al.
ndCoating Potographic Em
ulsin (Focal Press, 19617
It can be prepared using the method described in [2013]. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good.

It is also possible to use a method in which particles are formed in an excess of scissor ions (so-called back-mixing method). As a form of simultaneous mixing method, pAg in the liquid phase in which silver halide is produced is
The method of keeping constant is the so-called chondral
A double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Furthermore, emulsions prepared by the so-called conversion method, which involves a process of converting silver halide that has already been formed before the silver halide grain formation process is completed, into silver halide with a smaller solubility product, and Emulsions which have undergone similar halogen conversion after the completion of the silver grain formation process can also be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

After grain formation, silver halide emulsions are usually subjected to physical ripening, desalting and chemical ripening before being used for coating.

Known silver halide solvents (e.g. ammonia, Rodankali or U.S. Pat. No. 3.27/, 117, JP-A-Sho,
tl-/ko34 (No. 12, JP-A-13-,!'2 HiroOf
No., Tokukai Akira! 3-/F Ko 31 No., Tokukai Shoj≠-/0
The thioethers and thione compounds described in JP-A No. 07/7 or Japanese Patent Application Laid-Open No. Sho J'≠-/jjfJr) can be used in precipitation, physical ripening, and chemical ripening. In order to remove soluble silver salts from the emulsion after physical ripening, Nudel water washing, flocculation sedimentation method, ultrafiltration method, etc. are used.

The silver halide emulsion used in the present invention contains sulfur-containing compounds (such as thiosulfate,
Sulfur sensitization using reducing substances (such as stannous salts, amines, dorazine derivatives, formamidine sulfinic acid, and silane compounds): A noble metal sensitization method using a metal compound (for example, a total complex salt or a complex salt of a metal in Group 1 of the periodic table such as Pt, Ir5Pd, Rh, Fe, etc.) can be used alone or in combination.

Among the above chemical sensitizations, sulfur sensitization alone is more preferred.

The blue-sensitive, green-sensitive and red-sensitive emulsions of the present invention are spectrally sensitized with methine dyes and others so that they have color sensitivity. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

For these pigments, any of the nuclei commonly used for cyanine pigments can be used as basic heteronuclear nuclei. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.: A nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei: and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes contain pyrazoline-! as a core having a ketomethylene structure. -one nucleus, thiohydantoin nucleus, λ-theoxazolidine-co, ≠-dione nucleus, thiazolidine-2,4t-dione nucleus,
J-A membered heteroartic ring nuclei such as rhodanine nuclei and thiobarbital acid radicals can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Representative examples include U.S. Patent No. λ, trr, rttr;

77, 2.2t, J, 3y7,060, 3,
72.30/, same 3. ! 27,1. tA/issue, same! ,6
i7, 2tyJ No., 3,421, 91.14, 3,66 Otsu, Hiro 1o, 3,672. tyr issue, same j
, 1,79, No. ll-21, same! , 703
.

No. 377, No. 3,762, 30/No. 3, No. 3. xi Hiroshi, 1
．． No. 09, same! , 137. ItJ issue, same≠.

No. 024.707, British Patent/, J Guru, No. 21/,
Same/, j07, JrOj, special public service No. 11J-41
'36 issue, same! 3-/ko37J', Tokukai Sho! λ-1i
The otir number and the same r J -i o y ya are written in the number.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. Compared to a four-equivalent color coupler in which the coupling active position is a hydrogen atom, a two-equivalent color coupler substituted with a leaving group can reduce the amount of coated silver. Couplers in which the color-forming dye has adequate diffusivity, non-chromatic couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 2,1t
07. ．． No. 210, Ko, 1r7j, Oj7 and No. 3,216,101. It is written in the number etc.

The use of two-equivalent yellow couplers is preferred for the present invention, as described in U.S. Pat. ≠Or, / 5FF issue, same issue j,
! 4t7, ri No. 27, ri No. 3. Ri3! ,,901
No. and Hiroshi No. 022.

1a20, etc., or Japanese Patent Publication No. Sho J'♂-10732, U.S. Patent No. Ko, ≠0/, 73-2, U.S. Pat. /10j3 (/10j3), British patent number 1
, Il, 2j, No. 020, West German Application No. 2. Ko/
Ri, Ri No. 17, Ri, Ri No. 2. JA/, JG No. 1, JG No. 2, 3
Kota, No. 517 and λ.

A typical example thereof is a nitrogen atom separation type yellow coupler described in Kou 33.112. The .alpha.-piparoylacetanilide coupler has excellent color fastness, particularly light fastness, while the .alpha.-benzoylacetanilide coupler provides a high color density.

The magenta coupler that can be used in the present invention is preferably an oil-protected indacylon or cyanoacetyl coupler! - Pyrazoloazole couplers such as pyrazolone and pyrazolotriazoles are mentioned. The j-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye. j//, No. 012, No.-93
≠No. 3,703, same No. 2. l, No. 00.771, No. 1
．． Of, No. 73, No. 3,042. l.

! No. 3, same No. 3. /j co, t26 and 3゜ys
t, ois issue, etc. As a leaving group for two-equivalent pyrazolone couplers, U.S. Pat.
10. Preferred are the nitrogen atom leaving groups described in US Pat. It also has a ballast group as described in European Patent No. 73.4jj! - Pyrazolone couplers provide high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
Pyrazolobenzimidazoles described in No. 36, t7, preferably pyrazolo(t,/-c]C1r2.p]triazoles described in U.S. Pat. No. 3,7,047, Research Disclosure; 2≠220 (
Examples include the pyrazolotetrazoles described in Research Disclosure 2≠2JO (June 1991).

Imidazo (:/
, 2-b) pyrazoles are preferred, as described in European Patent No. iii
, pyrazolo [/.

z-b)[/+λ,≠]triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers. Gua Hong.

Naphthol couplers described in λ-ri No. 3, preferably US Pat.

/≠6, 3rd issue, same No. ≠, 22g, 233 and same No. μ, 2'? A typical example is the oxygen atom dissociating type 2-equivalent 7-toll coupler described in JP, No. 200. Specific examples of phenolic couplers are given in U.S. Pat.
No. 2.772,742, No. 2', r5Ft
, r, No. 24, etc. Humidity and temperature robust cyan couplers are preferably used in the present invention and are typically described in U.S. Pat. No. 3,772,0.
A phenolic cyan coupler having an alkyl group greater than or equal to an ethyl group at the meta-position of the phenol nucleus described in US Pat. No. 2,772. /lpλ No. j, 7 I, 301, No. Hiroshi, /2t, No. 6 J, No. Hiroshi,
33 Hiroshi, No. 0//, No. μ, No. 327°/7J, West German Patent Publication No. 3,322,7 Kota and Tokugaku Akira! t-4A
267/ issue, etc. - Diacylamino-substituted phenolic couplers and U.S. Patent No. J,! ! j,
4th λ, 1st Hiroshi, 3JJ, Tatata, 4th L, ≠j
It has a phenylureido group at the co-position as described in i, tr, and ≠, Hiroshi 27.717, etc., and! −
These include phenolic couplers having an acylamino group in the position.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such dye-diffusive couplers are described in US Pat. Specific examples of magenta couplers are given in European Patent No. 170 and West German Application No. 3.170. Ko3hiro.

! No. 33 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are described in U.S. Patent No. 3. μj/, ta
O-go and Dodai-hiro, oiro.

It is described in No. 277. Specific examples of polymerized maze/ta couplers are described in British Patent No. 2,102,173 and US Patent No. ψ, 347. ．． It is described in No. 212.

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

The coupler used in the present invention can be introduced into the light-sensitive material by an oil-in-water dispersion method. In the oil-in-water dispersion method, the boiling point is /
After dissolving in either a high boiling point organic solvent of 7j'C or higher and a low boiling point so-called auxiliary solvent, or a mixture of both, finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. do. Examples of high boiling point organic solvents are described in, for example, US Pat. No. 2,322.027. Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

Specific examples of high boiling point organic solvents include phthalate esters (dibutyl phthalate, dicyclohexyl phthalate),
(di, 2-ethylhexyl 7-talate, decyl phthalate, etc.), phosphoric acid or phosphonic acid noesters ()
! j phenyl phosphate, tricresyl phosphate, co-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-λ-ethylhexyl phosphate, ) IJ dodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-coethylhexyl phenyl phosphonate etc.), benzoic acid esters (2-ethylhexylbenzoate, 1.dodecylbenzoate, λ-ethylhexyl-p-hydroxybenzonate, etc.), amides (
(diethyldodecaneamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (stearyl alcohol, 2. tert-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, etc.) , instearyl 2-ctate, trioctyl citrate, etc.), aniline derivatives (N,N-dibutyl-2-butoxy-j-t
ert-octylaniline, etc.), hydrocarbons (halafine, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. Further, as an auxiliary solvent, those having a boiling point of about JO"C or more, preferably about JO"C or more, and about ito
Organic solvents of 0c or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, λ-ethoxyethyl acetate, dimethylformamide, and the like.

Examples of latex dispersion process steps, effects, and latex for impregnation are disclosed in U.S. Pat.

No. 363, West German Patent Application (OLS) No. 2. ! Hiroshi.

Core number and the same number 2. tQ/, No. 230, etc.

Typical usage amounts for color couplers range from 0.00 to 1 mole per mole of photosensitive silver halide, preferably from 0.0 to 0 for yellow couplers.
．． 5 mole, and 0.5 mole for the magenta coupler. OOJ or 0.
3 mol, and for cyan couplers 0.002 to 0.
It is 3 moles.

The light-sensitive materials produced using the present invention may contain hydroquinone derivatives, amine phenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamide phenols as color antifogging agents or color mixing inhibitors. It may also contain derivatives and the like.

Known anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include no-idofquinones, 6-hydroxychroman q, j-hydroxycoumarans, spirochromans, p-alkoxyphenols,
Typical examples include bisphenol [-centered hindered phenols, gallic acid derivatives, methylene dioxybenzenes, amine phenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Can be mentioned. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

In preventing deterioration of yellow dye images due to heat, humidity, and light, compounds having a hindered amine and hindered phenol fractional structure in the same molecule, as described in U.S. Pat. No. 2TR+323, have shown good results. give. In addition, in order to prevent deterioration of the agenta dye image, especially deterioration caused by light, spiroindanes described in JP-A No. 1999-1992-11 J4tF, and hydroquinone diethers or monomers described in JP-A No. 2003-111103 Ether substituted chromans give favorable results.

In order to improve the storage stability of cyan images, especially the light fastness, it is preferable to use a benzotriazole ultraviolet absorber in combination. This ultraviolet absorber may be co-emulsified with Cyankabu 2-.

The amount of ultraviolet absorber applied may be sufficient to impart photostability to the cyan dye image, but if too much is used in Atb, it may cause silkworms to change in the unexposed areas (white areas) of the color photographic material. Since there is
'mol/77!2~/.

It is set in the range of jxlo-3 mol/m2.

In the conventional light-sensitive material layer structure of color paper, an ultraviolet absorber is contained in one layer on both sides adjacent to the cyan coupler-containing red-sensitive emulsion layer, preferably in both layers. When an ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with a color mixing inhibitor. When a UV absorber is added to the protective layer, another protective layer may be applied as the outermost layer. This protective layer can contain a matting agent of any particle size.

In the photosensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer.

The light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation or halation.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the invention may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener.

Water-soluble brighteners may be used, and water-insoluble brighteners may be used in the form of dispersions.

The present invention, as described above, is applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. Further, each of the above-mentioned emulsion layers may be made up of two or more emulsion layers having different sensitivities, or a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity.

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation layer,
It is preferable to provide an auxiliary layer such as a back layer as appropriate.

Gelatin is advantageously used as a binder or protective colloid that can be used in the emulsion layer or intermediate layer of the photosensitive material of Kinen Rij, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, albumin, casei/etc.
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose ester sulfates, etc., sugar derivatives such as sodium alginate, starch derivatives:
Various synthetic hydrophilic polymeric substances such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, Sci, and Phot.

Enzyme-treated gelatin as described in Japan, A/lr, page 30 (/44) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

In addition to the above-mentioned additives, the photosensitive material of the present invention further contains various stabilizers, anti-staining agents, developers or their precursors,
Development accelerators or precursors thereof, lubricants, mordants, matting agents, antistatic agents, plasticizers, and other various additives useful for photographic materials may be added. Representative examples of these additives are Research Disclosure/76≠
J (/F7J' year/J month) and /17/l (15
7F/July).

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

[Example 1] Table A was placed on a paper support laminated on both sides with polyethylene.
A multilayer color photographic paper with the layer structure shown below was created. The coating solution was prepared as follows.

Preparation of first layer coating solution Add ethyl acetate λ7..2td and solvent (c
) was added and dissolved, and this solution was emulsified and dispersed in an IO% gelatin aqueous solution lrj'Kt containing 1ml of 70% sodium dodecylbenzenesulfonate. On the other hand, a blue-sensitive sensitizing dye shown below was added to a silver chlorobromide emulsion (silver bromide 1rOmo 1%, Ag7 (containing 7P/Kf) in an amount of y, ox/Omol per silver chlorobromide/mol to form a blue-sensitive emulsion. The emulsified dispersion and emulsion were mixed and dissolved, the gelatin concentration was adjusted to have the composition shown in Table 1, and the first
An If4 coating solution was prepared. The coating liquids for the λth layer to the seventh layer were also prepared in the same manner as the first layer coating liquid. The gelatin hardening agent for each layer is /-oxy-J,j-dichloro-5-
Triazine sodium salt was used.

The following spectral sensitizers were used in each emulsion.

Blue-sensitive emulsion layer (silver halide/per mol 7.0×10'mo
l addition) Green-sensitive emulsion layer (C silver f7ide/mol u, 0x10'm
ol addition)5O3I(N(C2I]5)3 (per silver halide/mol 7.0X10 mo
l addition) blue-sensitive emulsion layer (silver halide/per mol 1.Ox10-'mo!
Addition) The following dyes were used as irradiation prevention dyes in each emulsion layer.

Green-sensitive emulsion M: Red-sensitive emulsion layer: The structural formulas of the compounds used in this example, such as couplers, are as follows.

(a) Yellow coupler (b) Color image stabilizer (c) Solvent (d) (e) Magenta coupler (f) Color image stabilizer (g) Solvent (h) Ultraviolet absorber (i) Color mixing inhibitor (j) Solvent (i so CoHxaO%P=0 (k) Cyan coupler α (k□) (1) Color image stabilizer (m) Solvent The multilayer color photographic paper obtained as above was exposed imagewise, and the following In each of processing steps A and B, continuous processing was performed until three times the amount of the color developing tank was replenished.

Processing step A〉 Color development (336C) J minutes 30 seconds Bleach fixing (33°C) Water washing for 7 minutes 30 seconds (
2 hiro~30℃)/min I ■ (l)
7 minutes ■ (#) 1 minute drying (, rO'C) 7 minutes Processing step B> Color development (JA 0C) μ! Second bleach fixing (J4'C) ≠J seconds water washing (2
(See ~ JO0C) 30 seconds l ■ (#)
30 seconds I ■ (#) 30 seconds drying (, rO'C) The i minute direction water washing process was a countercurrent water washing from water washing (■) to water washing (2).

The compositions of the color developer and bleach-fix solution used in the above processing steps A and B are as follows.

water f 00rnl
r 00ml diethylenetriamine lOy
J, Oy Benzyl pentaacetate Alcohol listed in Table 2 Diethylene glycol listed in Table 2 Sodium sulfite listed in Table 2 Co, oy λ
, Jy potassium bromide /, Of
-Potassium Carbonate JO,Of 30
．． Of Chemicals Used in the Present Invention Table - Table -
Compounds listed in 2 (listed in Table-/) N-ethyl-N-(β!, jp 7.j
)-methanesulfonamidoethyl)-3-methyl-hiro-amine aniline sulfate hydroxylamine sulfate 10 fl 3. j
P-salt fluorescent whitening agent (Nutilbe/, OP/, jp1 series) Add water to toooyd 1oo
pH adjustment (pH) with KOH to,io
io, 3゜ (bleach-fix solution) Tank solution Replenisher water a o
onlt vo oIILl ammonium thiosulfate /! 01ll JOOrdj(
70ch) Sodium sulfite III 36
7 Ethylenediaminetetravinegar '61 /1
0f acid (III) ammonium ethylenediaminetetraacetic acid jfl 10
f Add acid water to 10100O1000tnl
pH 6.7j 6.30 Color development The replenishment amounts of the coloring solution, bleach-fixing solution and washing water were 1.0 IRI, 100 ml, and 10 f/1/2 doors of photographic paper.

In processing steps A and B, changes in yellow and magenta stain density of the unexposed areas of the photographic paper from the start to the end of processing were measured.

Table 2 shows the amount of change in each stain concentration after the end of the continuous treatment with respect to the start of the treatment.

Table 1 As is clear from Table 2, by shortening the color development time in processing step A, (sample 4.2) yellow and magenta post-processing stains worsened, which is not included in the present invention. By adding the compound, the sample and
It is not as good as /.

Also, in treatment step B, when there is no benzyl alcohol (sample plate 6), the stain of the sample in the same treatment step is improved, but by further adding the compound described in the present invention, the stain is significantly reduced. It can be seen that the results are improved (Samples 17-1).

(Example 1) The amount of washing water in Example 1 was changed to
The same procedure as in Example 1 was carried out, except that a solution containing 03y/l of DEDTA-2Na per water/l was used as the water washing replenisher. The results are shown in Table 3.

As is clear from Table 3, by shortening the color development time in processing step C (sample 16J), the yellow and magenta post-processing stains worsened, and by adding the compound described in the present invention, , Sample A improves somewhat, but
It's not even close to /.

Also, in the treatment process, when there is no benzyl alcohol (sample plate 6), the stain is improved compared to sample A2 in the same treatment process, but by further adding the compound described in the present invention, the stain is significantly improved. (Sample shop 7-ri).

(Example 3) The formulation of the washing replenisher in Example 1 is as follows: A-E! Compound I of the present invention was subjected to continuous processing in the same manner as in Example 1 and λ, and changes in stain were measured. As far as possible, a remarkable stain improvement effect was observed even in rapid processing.

Washing recipe A Nurphanilamide 0.2y/1Washing recipe B Benzotriazole 0. Jy/1Water washing prescription C ethylene siaban-N, 0. jy/IN, N
', N'-tetramethylenephosphonic acid pH 7.0 with KOH Water washing recipe 1) /-Hydroxyethyl i#rnlden-/,/-diphosphonate Bismuth chloride 0.3! Taporivinylpyrrolidone O1λ! 1 Ammonia water (26%) 0, Jrl nitrilotriacetic acid/jNa/, Of! -Kuroro Komechi jOdal-≠-Inchiazolin-3-one 11 Octiludai! Osg Sothiazoline-3-one fluorescent brightener (μ, Hiro'i, op-diaminostilbene type) Add water / 000ytl Add KOH l) H7,j Water washing formula E l-Hydroxyethyl J, owlden ／、／
-Diphosphonic acid (60%) Ammonium light pan o, zy Sulfanilamide 700 Da 7/% Nia water (26%) 1. Add rml water and add 1ooovtl KOH p)l 7. j Patent Applicant: Fuji Photo Film Co., Ltd. Date of March 1987: Mr. Commissioner of the Patent Office ~Te゛・'・2, Title of the invention: Processing method for silver halide color photographic light-sensitive materials 3, Relationship with the amended person's case Patent Applicant Address: 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Date of Amendment Order: Voluntary 5. We will submit a revised version of Specification 6, the subject of amendment (with no changes to the content).

Claims (4)

[Claims] (1) A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a reflective support, substantially free of benzyl alcohol, and having the following general formula (
A method for processing a silver halide color photographic light-sensitive material, which comprises processing with a color developer containing at least one compound represented by I). (2) The method for processing a silver halide color photographic material according to claim 1, wherein the color developer contains an aromatic primary amine color developing agent. (3) The photosensitive material is bleach-fixed after color development, and then washed with water, and the bleach-fixing time is 1 minute or less, and the washing time is 2 minutes or less. A method for processing a silver halide color photographic light-sensitive material according to Item 2. (4) In the above processing method, the amount of washing water in the washing step is equal to or less than the amount of prebath brought in per unit area of the photosensitive material.
．． 4. The method for processing a silver halide color photographic light-sensitive material according to claim 3, wherein the processing ratio is 1 to 50 times. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. , represents an aldehyde group.)