JPH04134450A - Processing composition for silver halide color photographic sensitive material and processing method - Google Patents

Abstract

PURPOSE:To obtain the processing compsn. which has a good operability and has not an environmental problem of waste liquid, as well ha an excellent desilvering property, lessens bleach fogging and has the bleachability to decrease the stains with lapse of time by incorporating a specific metal chelate compd. into the above compsn. CONSTITUTION:This compsn. contains the metal chelate compd. formed of the compd. or salt expressed by formula and the metal salts selected from Fe((III), Mn(III), Co(III), Rh(II), Rh(III), Au(III), Au(II), and Ce(IV).

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a processing assembly for silver halide color photographic light-sensitive materials.
Regarding the product, for more details, please refer to the bleaching process after color development.
A treatment composition containing a novel bleaching agent and a treatment composition using the same.
Regarding processing methods for silver halide color photographic materials.
It is. (Prior art) Silver halide color photographic light-sensitive materials (hereinafter referred to as color light-sensitive materials)
It is called a fee. ) is basically the process of imagewise exposure, color development process and
and desilvering steps. In the color development process, exposed silver halide particles undergo color development.
It is reduced by the image agent to become silver, and the generated
Oxidized color developing agents react with couplers to form image dyes.
Form. In the subsequent desilvering process, the developed image produced during the development process is removed.
Silver is oxidized to silver salt by a bleaching agent that has an oxidizing effect (bleaching).
white), along with unused silver chloride, soluble
Silver is removed from the photosensitive layer by the fixing agent (fixed).
arrival). Bleaching and fixing are independent bleaching processes, fixing
When it is carried out as a process, and when it is carried out simultaneously as a bleach-fixing process.
There are cases where this is done. For details of these processing steps,
“The Theory on Photography” by James
James, “The Th Process” 4th Edition
eory of Photographic Process
ss 4°th edition) (1977)
It is described in. In addition to the basic processing steps mentioned above, the photographic and physical processing of dye images
To maintain physical quality or process stability
Various auxiliary steps or additions are added for such purposes. example
For example, washing process, stabilization process, hardening process, stopping process, etc.
can give. The above processing steps are generally performed using automatic processing machines.
It is true. Particularly in recent years, small automatic devices called minilabs
Developing machines are installed in stores to provide customers with quick processing services.
bis is widespread. Against this background, there has been a strong need in recent years to speed up the processing process.
It is hoped that the bleaching process will be greatly speeded up.
It is. However, the conventionally used ethylenediamine tetra
Ferric acetate complex salts have a fundamental defect of weak oxidizing power.
or the use of bleach accelerators (e.g., U.S. Pat. No. 1.138)
．． Improvements such as addition of mercapto compound described in No. 842)
The goal of rapid bleaching despite the
has not yet been achieved. In addition, these bleaching
If a bleaching agent is used, the bleaching ability may decrease due to deterioration of the bleaching accelerator.
Due to large deterioration over time, the amount of replenishment cannot be reduced, resulting in
However, the goal of significantly reducing the amount of waste liquid could not be achieved.
. Bleaching agents to achieve rapid bleaching include red blood salt, iron chloride
, bromate, etc. are known, but in red blood salt,
Due to environmental conservation issues, iron chloride may cause metal corrosion, etc.
Due to the inconvenience of handling bromate, liquid
cannot be widely used due to instability issues
. Therefore, it is easy to handle, and there is no problem in discharging waste liquid.
A bleaching agent that achieves rapid bleaching was desired. Recently, 1,3-diamide
A bleaching agent of ferric complex salt of nopropane tetraacetic acid is disclosed.
. (The problem that the invention seeks to solve). However, this bleach has a number of problems.
. One of them is the performance-related problem of bleach fog that accompanies bleaching.
That's a problem. Bleaching is a way to reduce this bleach fog.
Adding agent viii to the solution is disclosed (e.g.
, Japanese Unexamined Patent Publication No. 1-213.657), but the level of improvement is
is not fully satisfactory, especially when color development is done for less than 3 minutes.
Highly active developers are used for rapid processing that takes about
This may cause a large amount of bleaching fog.
It will strain. Another problem is that this 1,3-diaminopropane
Using a treatment solution that removes bleaching ability from four vinegars and ferric complex salts.
Increased staining during storage after processing in photos processed with
There were also additional issues. Another problem is 1,3-diaminopropane tetraacetic acid.
Processing solution with bleaching ability consisting of ferric acid complex salt, especially bleaching
In the bleach-fixing process where the process and fixing process are performed simultaneously, the liquid
The stability of
As a result, the desilvering performance decreases significantly compared to the initial stage of continuous processing.
There are also problems such as the formation of precipitates.
Treatment composition and treatment method with novel bleaching ability
It was desired. Therefore, the first object of the present invention is to provide an easy-to-handle waste liquid.
A treatment composition that does not cause environmental problems and a treatment method using the same
It is about providing. The second object of the present invention is to have bleaching ability with excellent desilvering properties.
To provide a treatment composition and a treatment method using the same.
Ru. The third object of the present invention is to have bleaching ability with less bleaching fog.
To provide a treatment composition and a treatment method using the same.
It is in. The fourth object of the present invention is to improve the bleaching ability with less staining over time.
To provide a treatment composition for growing and a treatment method using the same.
It's there. The fifth object of the present invention is to have bleaching ability with excellent stability over time.
To provide a treatment composition and a treatment method using the same.
It is in. The sixth object of the present invention is to stably achieve the above properties even during continuous processing.
We propose a treatment composition that can maintain the performance and a treatment method using the same.
It is about providing. (Means to Solve the Problem) The above purpose is to obtain a compound represented by the following general formula (1) or
The salt, Fe(II[), Mn(III),
Co(I[[), Rh(II), Rh(II
I), Au (III), Au (II) and Ce (
IV) A metal salt formed from a metal salt selected from
For silver halide color photographic light-sensitive materials containing compounds such as
achieved by the treatment composition and treatment method using the same.
Ta. General formula (I) (5R11sR1!5R11sR14sRIsxR
I@ and Rat represent a hydrogen atom, an aliphatic group or an aromatic group.
vinegar. R11 and R1 are hydrogen atoms, aliphatic groups, aromatic groups, halo
Gen atom, cyano group, nitro group, acyl group, sulfamo group
yl group, carbamoyl group, alkoxycarbonyl group,
Ryloxycarbonyl group, sulfonyl group or sulfinyl group
Represents a nyl group. However, R+s and R+s are connected to form a ring.
will not form. L is an aliphatic group, an aromatic group, or a combination thereof
represents a divalent linking group containing a group. A, is carboxyl
represents a group, a phosphono group, or a hydroxy group. and U represents 0 or l. According to the invention, an imagewise exposed silver halide color photographic
After color-developing the true light-sensitive material, at least the method of the present invention is applied.
Bleaching of developed silver by treatment with a processing composition containing a chemical compound
is carried out extremely quickly, and according to the present invention, halogenation
After imagewise exposure and color development of silver color photosensitive materials, a small amount of
At least, treatment with a treatment composition containing a compound of the present invention.
The bleaching of developed silver is extremely rapid and is faster than conventional methods.
There is also significant bleaching blade burr on the bleaching side, which allows for faster bleaching.
No, this is especially true for rapid color development with a processing time of less than 3 minutes.
When the image is subsequently treated with the treatment composition of the present invention
, appears as a large effect. In addition, the image storage stability after processing is good, and it is easy to handle.
is also preferable. The compound represented by general formula (1) will be explained in detail below.
I will clarify. General formula (R11% R11%R1S%R14
, R3-R3-R1ff, Ls and RI, expressed as
Aliphatic groups include straight chain, branched or cyclic alkyl groups,
Nyl group or alkynyl group, having 1 to 10 carbon atoms
The aliphatic group is more preferably an aliphatic group.
Kyl group, particularly preferably an alkyl group having 1 to 4 carbon atoms.
Delicious. RllxRlt%R1! , RI4, R11%R1
, , RIM and Rlg are monocyclic or
or bicyclic aryl group, such as phenyl group, naphyl group, etc.
Examples include thyl group, and phenyl group is more preferred. Acyl group represented by R1 and R7, sulfamo
yl group, carbamoyl group, sulfonyl group and sulfinyl group
The group is a group bonded to an aliphatic group and an aromatic group, respectively.
be. The aliphatic group and aromatic group are R11"" R1q
It is the same as the definition given below. Acyl group represented by R1 and Raw, sulfamo
yl group, carbamoyl group, alkoxycarbonyl group,
Ryloxycarbonyl group, sulfonyl group and sulfonyl group
The vinyl group preferably has 10 or less carbon atoms. Hydrogen atoms are preferred as R11, R12, and Re4.
Furthermore, R11 and Ro are preferably in the cis position.
stomach. In addition, R11, R eyes, RIa, Re4, R18%R4,
R19, R11 and R11 may have a substituent.
(As a substituent, for example, an alkyl group, an aralkyl group,
Alkenyl group, alkynyl group, alkokene group, aryl
group, amino group, acylamino group, sulfonylamino group,
Ureido group, urethane group, aryloxy group, sulfur group
Moyl group, carbamoyl group, alkylthio group, aryl
Thio group, sulfonyl group, sulfinyl group, hydroxy group
, halogen atom, cyano group, sulfo group, carboxy group,
Phosphono group, aryloxycarbonyl group, acyl group,
Alkoxycarbonyl group, acyloxy group, carbonyl group
Mido group, sulfonamide group, nitro group, hydroxamic acid
Examples include groups. Preferred substituents for R3, R14 and R1ff are
is a carboxy group, phosphono group, sulfo group or hydroxy group.
It is a group. More preferably carboxy group, hydroxy group
A carboxy group is particularly preferred. Also, Ro, Ray, Re3, RIa, RISNR16
,R+,,R11,R1,,L,are mutually exclusive if possible.
may be linked to form a ring, provided that RIM and Rt
q does not connect to form a ring. L is an aliphatic group, an aromatic group, or a combination thereof
Represents a divalent linking group containing a group consisting of. The divalent linking group is alkylene having 1 to 10 carbon atoms.
Group: C to C10 arylene group: C7 or less
Aralkylene group of 10; -0-ORe group group, aromatic group or hydroxy group), -3O,- and aralkylene group;
A group consisting of a combination of alkylene groups or arylene groups
is preferred, and if possible a combination of these
Also, these divalent linking groups may have a substituent.
For example, as a substituent for Ro,
things can be applied. Preferably, it can be expressed by the following formula (L,):
Ru. General formula (L,) -1-(A+T-+Lb +s * In the formula, L, and are respectively an alkylene group and an aralkyl group.
Represents a ren group or an arylene group, and A is 10”-S
CN (RIM represents a hydrogen atom, an aliphatic group, an aromatic group or a hydroxyl group)
, ) -So, - and a group consisting of a combination of these groups
represent. m and n are each independently 0 or 1. * is A, and
means a combination. Preferred specific examples of Ll include the following:
The following can be mentioned. -CHx-11-(CHt + zll(CHx +
-ShiNto4 R++ R+*R+J+CHzCHzOCH□CL---CHtCHzSC)I
xCl(z-umbrella-CH□CHzNHCHtC)It-child
. More preferably, as L, n in -a formula (L,)
=0, m=o, more preferably a methylene group and an ethyl group.
It is a tyrene group. A1 is a carboxy group, a phosphono group, a sulfo group, or a hydride group.
AI, which represents a roxy group, includes a carboxyl group, a hydrogen
A droxy group is preferred, and a carboxy group is particularly preferred.
Some sA+ are alkali metal (e.g. Na, K) salts.
You can. t and U each represent 0 or 1, t and U
At least one of them is preferably 1, and both t and u are 1.
It is particularly preferable that In the present invention, preferably represented by the following general 2(n)
It is a compound that General formula (n) Rlz RIM In the formula, R13, RIM, R13, R3 Ro, R1ff
, R11, R1? , A, , L, , t, and u are general formula (1)
are synonymous with each of R2 is Ll in general formula (1)
are synonymous, and A is synonymous with A1 in general 2 (+>). Among the compounds represented by general formula (1), more preferably
This is a compound represented by the following linear formula (III). General formula (I[1) RIx R14 where R,1% R,! , RIM, R14, RIM, R
IM, A, , L, , t, and U are those of general formula (1).
- Lx, Ls and R4 are synonymous with each other - Lx, Ls and R4 are synonymous with each other.
Ax, Ax and
and A4 are each synonymous with A in general formula (1). Specific examples of compounds represented by the general formula (]) are shown below.
However, it is not limited to these. 1゜tυυshishi I'l wealth I'I!しυυれ■υυuLtl.し rI rich υυn H 10゜16゜17゜18゜19゜NH-CHz CHl-NH HOOC-CH CH-CooIi 1 2゜OJa 15゜IIuυshishi l'l 1 year old υUI'1 20゜21°NH-CHI CB, -NO)1. C-CH CH-CH. ooH Coo)l 23°H 24°25°29°30°31°32°+1ULILL, I'1g 27, 28°33°34°35°36°HULIL and tl. Shi 11! SIUUI'l 37°38°39°40°CH C00H C)1. cOOH 4] 43゜44゜45゜OO / / / / / / 46゜50゜47゜48゜For the compound represented by general formula (1), Keihei Ueno
"Chelate Chemistry" Volume 5, Chapter 1 (Nankodo, 1975)
It can be synthesized based on the description in the annual publication). Specific synthesis examples of representative compounds are shown below. Synthesis example 1. Synthesis of compound 3 49° (J-CH2CH, -Cj! ・2HC1 Synthesis example 1-+11 Synthesis of compound 3a cis-1,4
-dichloro-2-butene 100g (0,80mo
1) and 350 g of phthalimide potassium salt (1,8
Dissolve 9 moj in dimethylformamide 1.51
After heating and stirring at 80°C for 2 hours, water 21 was added.
The mixture was further stirred for 20 minutes. Filter the precipitated solid and wash with water.
After cleaning, the object 3a is dried by air blowing.
8 g (0,775 mo 1) was obtained. Yield 97%. Synthesis Example 1-(2) Synthesis of Compound 3b 258g of 3b synthesized in Synthesis Example 1-+11 (0,
745 moj) and 93.1 g of hydrazine 1 permanent (1,
86mo f) to meta/-)Ltll, 3 o'clock
The mixture was heated to reflux for a while. The precipitated solid was separated by filtration, and the filtrate was concentrated under reduced pressure.
After shrinking, salt production #200R1 (2.33 mol)
added. At room temperature, add acetonate to the stirring area.
Ril 500- was added, and the precipitated solid was collected by filtration. Aceto
After washing with nitrile and drying, the target Th
113g (0°711mof) of 3b was obtained. Yield 95%
. Synthesis Example 1-+31 Synthesis of Compound 3 45.5g (0
Dissolve ゜286mo 1) in water 100-, hydroxylate
Added 22.9g (0,573mo#) of sodium
140 g (1°20
m o L j ○Aqueous solution 2001 and hydroxide
48. Og(1,2Ornol)○Water=e] 00 companies
was added gradually. During this time, the reaction temperature was 50-55℃.
Phenolphthalein as p11 indicator
Add a small amount of heat to maintain a light red color.
After stirring for 1 hour, let it cool and add 122 g of f4 acid.
(1,20rr+a L) of 6 anti-Z solution for about 3 minutes.
The solution was concentrated under reduced pressure to a concentration of 1, and the precipitated salt was filtered off. filter
Cool the liquid overnight (approximately 5℃) and filter out the broth and precipitated solid.
, the second target compound was obtained by recrystallizing from water-methanol.
Obtained 42.0g (0°132rr+o 7!') of item 3
1 piece. Yield ↓ 46% Melting point] 79-180°C (decomposition) The metal salt constituting the metal chelate compound of the present invention is F
e (I(1) , Mr+ (m) , Co (Il
l), Rh(II), Rh(II'), Au
(n), Au (I[l), and Ce (TV)
To be elected. More preferably Fe(III), Mn
(I[l), Ce (IV), especially Fe(nl
) is preferred. The metal chelate compound of the present invention is represented by the -line formula 〇) in Table 8.
Compounds and the metal salts, such as ferrous sulfate, ferric chloride
salt, ferric nitrate salt, ammonium ammonium ferrous sulfate, ferric phosphate
It may be used by reacting with salt etc. in solution.
Compounds that react with formula (1) in Table 7-): For metal ions
It is used at a molar ratio of 1°0 or more. This ratio is
Larger values are preferred when the rate compound is less stable.
It is usually used in the range of 1 to 30. In addition, the uninvented metal chelate compound is a metal chelate compound.
A separated compound may also be used. Examples of compounds as C: metal chelate compounds are shown below.
, but is not limited to these muni. C 1C C 9C Specific synthesis examples of typical metal chelate compounds are shown below.
vinegar. Synthesis Example 2 Synthesis of compound 3C! 31.8g of 713 (0.10mol) water 50
After dissolving it in water and adjusting the pH to 5 with aqueous ammonia, diluted with nitric acid.
Iron nonahydrate 40.4g (0.10mof) of water r=i
1o o N1 was added. Add more ammonia water,
After adjusting the pH to 5, k until the capacity reaches about 100-
N and added methanol 100-100 ml/room temperature for 1 week.
After standing, the precipitated solid was collected by filtration and mixed with water/2'tanol.
22.0g of yellow solid 3C was obtained by recrystallizing at
Composition of compound 3C obtained (0.54 mof).O ratio: 54%: Identified using a two-element analyzer. ／ ／ Uninvented metal chelate compounds: Useful in fixers and color developers.
Adding a small amount of I to the intermediate bath during the desilvering process (is it okay?
There is a bleaching solution that contains 0.05 to 1 mole per 1f of solution.
It is still effective as a bleaching agent in bleach-fix solutions. The following is a treatment solution (bleaching solution) with a desirable bleaching ability.
(general term for bleach-fix solution)
. The metal chelate compound of the present invention has bleaching ability as described above.
Contains 0.05 to 1 mole per 1f of processing solution.
However, it is still effective as a bleaching agent, with a dosage of 0.00% per liter of processing solution.
It is more preferable to contain 1 to 0.5 mol. The metal dry rate compound of the present invention is treated with a processing solution having bleaching ability.
When used as a bleaching agent, the range within which the effects of the present invention can be achieved
It may be used in combination with other known bleaching agents. the
Such bleaching agents include Fe (
I[I), Co(III) or Mn(I[I)
bleach, or Beroxonisulfate, peroxide
Examples include salts, bromates, etc. The compounds that form the above chelate bleach include ethyl alcohol.
Diaminetetraacetic acid, ethylenediaminetetraacetic acid
Disodium salt, ethylenediaminetetraacetic acid diammo
salt, ethylenediaminetetraacetic acid tetra(trimethane)
tylammonium) salt, ethylenediaminetetraacetate
Trapotassium salt, ethylenediaminetetraacetic acid tetrana
Thorium salt, trisodium ethylenediaminetetraacetate
salt, diethylenetriaminepentaacetic acid, diethylenetriamine
Liamine pentaacetic acid pentasodium salt, ethylenedia
Min-N-(β-oxydiethyl)-N,N'. N-) diacetic acid, ethylenediamine-N-(β-oxydiene)
chill')-N,N',N-triacetic acid trisodium salt,
Ethylenediamine-N-(β-oxydiethyl)-N,N
o. -N-triacetic acid triammonium salt, 1,2-diamino
Propane tetraacetic acid, 1,2-diaminopropane tetra
Acetic acid disodium salt, 1,3-diaminopropane tetra
Acetic acid, 1,3-diaminopropanetetraacetic acid diammonium
um salt, nitrilotriacetic acid, nitrilotriacetic acid trinate
Lium salt, cyclohexanediaminetetraacetic acid, cyclo
Hexanediaminetetraacetic acid disodium salt, iminodi
Acetic acid, dihydroxyethylglycine, ethyl ether di
Aminetetraacetic acid, glycolnythyldiaminetetra
Acetic acid, ethylenediaminetetraworopionic acid, phenyl
diaminetetraacetic acid, 1,3-diaminopropanol
-N,N,N',N-tetramethylenephosphonic acid, ethyl
Diamine-N, N, N', N-tetramethy
Renphosphonic acid, 1,3-propylenediamine-N,
N, N', N-tetramethylenephosphonic acid, etc.
Can you list any of these exemplified compounds?
Not limited. The bleaching ability containing the metal chelate compound according to the present invention
The treatment solution contains the metal chelate compound as a bleaching agent.
In addition, it can be used as a rehalogenating agent to promote silver meltification.
, adding halides such as chloride, bromide, and iodide.
Is it preferable? Also, instead of halides, socially soluble
Organic ligands that form silver salts may also be added. halogen
The compound is an alkali metal salt or ammonium salt, or
is added as a salt with guanidine and amine t. specifically
are sodium bromide, ammonium bromide, potassium chloride,
Examples include guanidine hydrochloride, preferably ammonium bromide.
It is mu. The amount of rehalogenating agent in the bleach solution is 0.1
~20 mol/l, preferably 03-1.5 mol/f
Ru. Bleach-fix solution containing metal chelate compound according to the present invention
In addition to containing the metal chelate compound as a bleaching agent,
Contains an adhesive (described later), and if necessary, the re-halogen
Generators may also be included. Rehaul in bleach-fix solution.
When using a chlorogenating agent, the amount is 0001 to 2.0 mole.
mol/l, preferably 0.01 to 1.0 mol/f
. The bleaching solution or bleach-fixing solution according to the present invention also includes
Bleach accelerator, corrosion inhibitor to prevent corrosion of processing bath rails, liquid p
Requires buffering agent, optical brightener, antifoaming agent, etc. to maintain H.
Added accordingly. Bleach accelerators include, for example, U.S. Pat. No. 3,893.8.
No. 58, German Patent No. 1,290,812, U.S. Patent
No. 1,138,842, JP-A-53-95630,
Research Disclosure i-No. 17129 (197
Having a mercapto group or nosulfide group as described in 8)
The compound described in JP-A No. 50-140129
Aplidine derivatives in U.S. Patent No. 3,706,561
Numeral thiourea derivatives, German Patent No. 2,748゜43
Polyethylene oxides described in No. 0, Japanese Patent Publication No. 45-8
Polyamine compound described in No. 836, JP-A-49-40
It is possible to use the imidazole compound t described in No. 493.
I can do it. Among others, U.S. Patent No. I, 138.842
The mercapto compounds described are preferred. Also, as a corrosion inhibitor, it is preferable to use nitrates.
However, ammonium nitrate and potassium nitrate are not used.
. The amount added is 0.05 to 0.05 mol/f, preferably
0.01-2.0 mol/f, more preferably 0.05-2.0 mol/f
It is 0.5 mol/l. The pH of the bleaching solution or bleach-fixing solution of the present invention is 2.0 to 8.
．． 0, preferably 3.0 to 7.5. Immediately after color development
If bleaching or bleach-fixing is to be carried out immediately, use the bleach blade bridle.
In order to suppress this, the pH of the liquid should be 6.0 or less, preferably 5.
It is best to use it at 5 or less. Also, at pH 2.0 or below, the main
The metal chelate of the invention becomes unstable and therefore has a pH of 2.
, 0 to 5.5 are preferred. For this purpose, the pH 7L buffer is oxidized by bleach.
We regret to accept any substances that have a buffering effect within the above pH range.
You can use just about anything. for example,
Acetic acid, glycolic acid, lactic acid, propionic acid, butyric acid, phosphorus
Golic acid, chloroacetic acid, levulinic acid, ureidopropionic acid
organic acids such as pyridine, dimethylpyrazole, 2-methyl
Chil-〇-oxacillin, aminoacetonitrile, etc.
Examples include breeding bases. In the present invention, pKa is 2
．． Organic acids of 0 to 5.5 are preferred. Use of these buffers
The amount is 0 to 3.0 mol/11 preferably 0.5 to 2.0 mol.
Le/I! It is. Also, these buffers can be used in combination
It's okay. To bring the pH of the processing solution with bleaching ability to y4g in the above range
is the above-mentioned acid and alkaline agent (e.g. aqueous ammonia, K
OH, NaOH, imidazole, monoethanolamine
, jetanolamine) may be used in combination. Among them,
Aqueous ammonia is preferred. During processing, aeration is applied to the processing solution that increases bleaching ability.
It is preferable to oxidize the iron(II) complex salt produced by
Delicious. This regenerates the bleach and improves photographic performance.
It is maintained stably. The bleaching or bleach-fixing process is carried out at a temperature range of 30 to 50°C.
The temperature is preferably 35 to 45°C. bleaching and
and/or bleach-fixing process time for photographic materials.
, is used for a period of 10 seconds to 5 minutes, preferably 1
0 to 60 seconds, more preferably 10 to 40 seconds
, most preferably 10 to 30 seconds. Also the print feeling
For materials, it can be done in 5 to 70 seconds, but it is preferable
preferably 5 to 50 seconds, more preferably 5 to 30 seconds, most preferably
Preferably, it is 5 to 15 seconds. For these short processing conditions
In this case, the effect of the present invention becomes apparent to Seki. A known fixing agent is used for the fixing solution or bleach-fixing solution.
Ru. These are thiosulfate, thiocyanate, and thionethi
mercapto, amines, 1,000 ions, thioureas,
iodide salts, such as ammonium thiosulfate
, sodium thiosulfate, potassium thiosulfate, thiosulfate
Anidine, potassium thiocyanate, dihydroxynityl
-thioether, 3,6-cythia 1,8-octanedi
Examples include all, imidazole and the like. Among them, thiosulfur
Acid salts, especially ammonium thiosulfate, are useful for rapid fixation.
It is preferable. Furthermore, it is possible to use two or more types of fixing agents together.
This also allows for more rapid fixation. For example, Thio
In addition to ammonium sulfate, the aforementioned ammonium thiocyanate
Concomitant use with imidazole, thiourea, thioether, etc.
It is also preferred that the second fixing agent is thiosulfate.
Added in a range of 0.01 to 100 mol% relative to ammonium.
It is preferable to add The amount of fixer is 0.1 per fixer or bleach-fixer If.
-3.0 mol, preferably 0.5-2.0 mol. The pH of the fixer depends on the type of fixer, but it is 3.0
~9.0, especially when using thiosulfate, 6
．． 5 to 80 is preferable in order to obtain stable fixing performance. To the fixing solution and/or bleach-fixing solution,
It is also possible to improve the stability of the liquid over time. In the case of fixer or bleach constant M solution containing thiosulfate,
, subdued salt and/or hydrodylamine as a fencing agent
, hydrazine, bisulfite adducts of aldehydes (e.g.
, a bisulfite adduct of acetaldehyde, particularly preferably
, aromatic aldehyde described in JP-A-1-298935
bisulfite adduct) or effective. Also, JP-A-62-
! Using the sulfinic acid compound described in No. 43048
is also preferable. In addition, the pH of the fixing solution and/or bleach-fixing solution should be adjusted.
It is also preferable to add a buffer to keep it constant. example
For example, phosphate, or imidazole, 1-methyl-
imidazole, 2-methylimidazole, l-ethyl-
Imidazoles such as imidazole, triethanol
Amine, N-orylmorpholine, N-benzoylpipera
I can give you something like gin. In addition, various types of beef meat are used in the fixing solution.
Adding a bleaching agent removes iron ions brought in from the bleach solution.
It is also possible to improve the stability of the liquid by hiding the liquid. this
Preferred chelating agents include 1-hydroxyethyl
Lyden-1,1-diphosphonic acid, ethylenediamine-N
, N, N', N'-tetramethylenephosphonic acid
, nitriloto, rimethylenephosphonic acid, ethylenediamine
cyclotetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexane
1,2-propanediaminetetraacetic acid, 1,2-propanediaminetetraacetic acid
I can list many things. The fixing step can be carried out at a temperature in the range of 30°C to 50°C, but is preferably
Specifically, the temperature is 35°C to 45°C. The fixing process time is
, for photographic materials, 35 seconds to 2 minutes, preferably 40
seconds to 1 minute and 40 seconds, and for printed photosensitive materials, 10 seconds to 1 minute and 40 seconds.
The time is from 10 seconds to 30 seconds, preferably from 10 seconds to 30 seconds. The desilvering process includes a bleaching process, a fixing process and/or a bleach-fixing process.
It is carried out by a combination of processes, typical examples of which are shown below.
Ru. ■ Bleach-fixing ■ Bleach-bleach-fixing ■ Bleach-bleach-fixing ■ Bleach-washing constant-fixing ■ Bleach-fixing ■ For photosensitive materials for fixing-bleach-fixing, ■, ■, ■, and ■ are preferred.
■, ■ or ■ are preferred. In printed sensitive materials, ■
preferable. In the present invention, after the color development process, for example, a stop bath, a water washing bath, etc.
It can also be applied to desilvering treatment. In desilvering processes such as bleaching, bleach-fixing, and fixing treatments,
The effectiveness of the present invention is that the stirring is as strong as possible.
This is preferable in terms of achieving more effective results. A specific method for strengthening stirring is disclosed in Japanese Patent Application Laid-Open No. 62-18346.
No. 0, emulsion of the photosensitive material described in No. 62-183461
A method of impinging a jet of processing liquid on a surface, and a method of
Method for increasing stirring effect using rotating means of No. 83461
Furthermore, the wiper blade installed in the liquid and the emulsion surface are connected.
The emulsion surface is made turbulent by moving the photosensitive material while touching it.
Second, there is a method to improve the stirring effect, and
One possible method is to increase the circulation flow rate. Such agitation
The agitation improvement means can be used for bleach solution, bleach-fix solution, or fixer solution.
It is also effective even if Improving stirring is achieved by adding bleach into the emulsion film.
, which speeds up the supply of fixing agent and, as a result, increases the desilvering rate.
it is considered as. In addition, the above-mentioned agitation improvement means can be used when a bleach accelerator is used.
more effective, significantly increasing the bleaching effect and bleaching
It is possible to eliminate the fixation inhibiting effect caused by whitening accelerators.
. The above strength and stirring should be done with color developing solution, washing with water, or stabilizing solution.
It is preferable to use it for anything. The color developer used in the color development process contains known aromatic compounds.
Contains primary amine color developing agent. Preferred active ingredients are p-phenylenediamine derivatives,
Typical examples are shown below, but are not limited to these.
do not have. D-IN, N-diethyl-p-phenylenediamine D-24-amino-N, N-diethyl-3-methylani
Phosphorus 4-amino-N-(β-human quinonithyl)-N-methane
Tylaniline 4-amino-N-ethyl-N-(β-hydroxyethyl
) Aniline 4-amino-N-ethyl-N-(β-hydroxyethyl
)-3-methylaniline 4-amino-N-ethyl-N-
(3-HiF'Oquinpropyl)-3-methylaniline 4-amino-N-ethyl-N-(4-hydroxybutyl
)-3-methylaniline 4-amino-N-ethyl-N-
(β-methanesulfonamidoethyl)-3-methylani
Phosphorus 4-amino-N,N-diethyl-3-((β-hydroxy
ethyl)aniline 4-amino-N-ethyl-N-(β-methoxyethyl
)-3-methylaniline 4-amino-N-(β-ethoxy
ethyl) = 3-N-dithylmethylaniline D-12 4-amino-N-(3-carbamoylpropylene)
Pyl-N-n-propyl-3-methylaniline D-13 4-amino-N-(4-carbamoylbutyl
Le-N-n-propyl-3-methylaniline D-14 N-(4-amino-3-methylphenyl)
-3-hydroxypyrrolidine D-15 N-(4-amino-3-methylphenyl)
-3-(hydroxymethyl)pyrrolidine D-16 N
-(4-amino-3-methylphenyl)-3-pyrrolidi
Carboxamide D-17 4-Amino-N-ethyl-N-(β-hydro
[oxyethyl]-3-methoxyaniline Exemplary compound D of the above p-phnynylene diamine derivatives
-5, D-6, D-7, D-8, D-12, D-17
Preferably used. In addition, these p-phenylenediamine derivatives are sulfate
, hydrochloride, sulfite, p-)luenesulfonate, etc.
It is preferable to use it as a salt. Aromatic primary amine color
-The amount of developing agent used is color developer II! Preferably
0. 0002 to 0.2 mol, more preferably about 0.0
The concentration is between 0.01 and 0.1 molar. In addition, sodium sulfite is added to the color developer as a preservative.
, Potassium sulfite, Sodium bisulfite, Potassium R acid
um, sodium metasulfite, potassium metasulfite, etc.
Add sulfites and carbonyl sulfite adducts as necessary.
can be added. Alternatively, the aromatic primary amine color developing agent may be directly applied.
JP-A-63-5341 and JP-A No. 63-63
Various hydroxylamines described in No. 3-106655
(Among them, compounds with sulfo or carboxy groups are preferred.
Yes. ), JP-A-63-43138 No. Hydroxa
Muic acids, hydrazines described in No. 63-146041, and
Hydrazides, No. 63-44657 and No. 63-58
Phenols described in No. 443, No. 63-44656
α-hydroxyketones, α-aminoketone stones and
/or 63-362 <No. 4 Ha Add various sugars
Or preferable. In addition, when used in combination with the above compounds, JP-A-6
No. 3-4235, No. 63-24254, No. 63-21
No. 647, No. 63-146040, No. 63-2784
] and monoamines described in No. 63-25654, etc.
, No. 63-30845, No. 63-i4640, No. 6
Diamines described in No. 3-43139, etc., No. 63-21
No. 647, No. 63-26655 and No. 63-4465
Polyamines described in No. 5, No. 63-53551
Nitroquine radicals, No. 63-43140 and No. 6
Alcohols described in No. 3-53549, No. 63-566
Dried snails described in No. 54 and No. 63-239447
Preferably, the tertiary amines listed above are used. Other preservatives include JP-A No. 57-44148 and the same.
Various metals described in No. 57-53749, No. 59-18
Salicylic acids described in No. 0588, No. 54-3582
Alkanolamines described in No. 56-94349
Polyethyleneimines of U.S. Pat. No. 3,746,54
The aromatic polyhydroquine compound described in No. 4, etc.
may be included. Especially aromatic polyhydromono-compounds
Addition of substances is preferable. The amount of C added to these
0.005 to 0.2 mol per developer jf, preferably 0
01~0. C'5 moles. The color developing solution used in the great invention includes other known developing solutions.
It is also possible to include liquid component compounds. The color developing solution used in the great invention has a pH of 9.0 to 12.0.
Used in WHA, preferably 95-1
It is 1.5. Are various buffers used to maintain the above pH?
preferable. Specific examples of buffering agents include sodium carbonate,
Potassium carbonate, sodium bicarbonate, potassium bicarbonate, lye
Trisodium phosphate, tripotassium phosphate, disodium phosphate
um, dipotassium phosphate, sodium borate, potassium borate
Sodium tetraborate (borax), Potassium borate
um, sodium O-hydroxybenzoate (salicylic acid)
sodium), potassium o-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (5-sulfo-2-hydroxybenzoate)
sodium phosalicylate), 5-sulfo-2-hydroxy
Potassium cybenzoate (potassium 5-sulfosalicylate)
゛ etc. can be mentioned. However, the present invention
It is not limited to these compounds. The amount of buffer added to the color developer is 0.1 mol/1 or more.
It is preferable that it is, especially 0.1 to 0.4 mol/I.
It is particularly preferable that there be. In addition, the color developer contains calcium and magnesium.
Used as an anti-settling agent or to improve the stability of color developing solutions.
Various cattle rate agents can be used for this purpose. The chelating agent is preferably an organic acid compound, such as a
Minopolycarboxylic acids, organic phosphonic acids, phosphonoca
Examples include rubonic acids. Specific examples include nitrilotriacetic acid, diethylenetriamine
N.pentaacetic acid, ethylenediaminetetraacetic acid, N. N,N-trimethylenephosphonic acid, ethylenediamine-
N, N, N', N'-tetramethylenephosphonic acid,
trans cyclohexanediaminetetraacetic acid, 1,2-dia
Minopropane tetraacetic acid, hydroxyethyliminodiacetic acid,
Glycol ether diamine tetraacetic acid, ethylene diamine
Orthohydroquine phenylacetic acid, 2-phosphonobutane-
1,2,4-tricarboxylic acid, l-hydroxyethylide
N-1゜1-diphosphonic acid, N,N'-bis(2-hydro
(roxybenzyl)ethylenediamine-N,N'-diacetic acid
etc. can be mentioned. These chelating agents are necessary
Two or more types may be used in combination depending on the situation. The amount of these chelating agents added depends on the metal ion in the color developer.
For example, the amount is sufficient to block the
from 0.001 mol to 0.005 mol, preferably 0.00 mol
It is 3 to 0.02 mol. As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, No. 38-7826, No. 44-123
No. 80, No. 45-9019, U.S. Patent No. 3,818,
Thioether compounds described in No. 247, etc., JP-A-52
-49829 and p- described in 50-15554
Phenylenediamine compounds, JP-A-50-13772
No. 6, Special Publication No. 1973-30074, Japanese Patent Publication No. 156-1973
Quaternary ammonia described in No. 826, No. 52-43429, etc.
Nium salts, U.S. Pat. No. 2.494 903, No. 3
, No. 128,182, No. 4.230.796, No. 4.230.796, No. 4.230.796, No.
No. 3,253,919, Special Publication No. 41-11431, U.S.
National Patent No. 2,482゜546, National Patent No. 2,596.92
No. 6, amine conversion described in No. 3゜582.346, etc.
Compound, Special Publication No. 37-16088, No. 42-25201
No., U.S. Patent No. 3,128.183, Special Publication No. 1977-1
No. 1431, No. 42-23883, U.S. Patent No. 3.5
Polyalkylene oxide described in No. 32,501 etc.
Also, imitations such as 2-methylimidazole and imidazole
Dazoles can be given. In addition, l-phenyl-3-virapritone is used as an auxiliary developer.
It is also preferable to add compounds such as
stomach. For example, the following compounds can be mentioned. AD 8p-2 Door, D Su AD-4 AD-5 AD-The amount of auxiliary developer added is color developer II! Hit o, o
oos mole to 0.03 mole, preferably 0.001 to 0
．． 01 mole. The color developing solution used in the present invention may further include, if necessary,
Any antifoggant can be added. Antifoggants include sodium chloride and potassium bromide.
, alkali metal halides such as potassium iodide and
Anti-capri agents can be used. As a breeding fog prevention agent
For example, benzotriazole, 6-nidropenzimine
dazole, 5-nitroisoindazole, 5-methylbase
Benzotriazole, 5-nitrobenzotriazole, 5
-Tarolow benzotriazole, 2-thiazolyl-ben
Zimidazole, 2-thiazolylmethyl-benzimida
zole, indazole, hydroxyazaindolizine,
A typical example is a nitrogen-containing heterocyclic compound such as adenine.
I can give it to you. The color developing solution used in the present invention contains an optical brightener.
You may. As an optical brightener, 4゜4'-diamino
-2,2'-disulfostilbene compounds are preferred. Addition amount is 0 to 5 g/i, preferably 0.1 g to 4 g/r
It is. In addition, alkyl sulfonic acid, aryl sulfonic acid, and
Various types such as phonic acid, aliphatic carboxylic acid, aromatic carboxylic acid, etc.
Surfactants may also be added. The processing temperature in the color developing solution in the present invention is 20 to 55°
C1 is preferably 30 to 55°C. Processing time is 20
The time is from seconds to 5 minutes, preferably from 30 seconds to 3 minutes and 20 seconds. Furthermore
Preferably it is 1 minute to 2 minutes and 30 seconds. The processing method of the present invention can also be used for color reversal processing. this
The black and white developer sometimes used is a commonly known colorant.
A black and white first developer used for reversal processing of color-sensitive materials;
It is called. Processing of black and white silver halide photosensitive materials
It is added to the black and white developer used in the liquid.
The first black-and-white development of color reversal photosensitive materials using various well-known additives.
It can be included in the image solution. A typical additive is 1-phenyl-3-birapuri.
developing agents like ton, metol and hydroquinone
, preservatives such as sulfites, sodium hydroxide, and sodium carbonate.
Accelerators consisting of alkalis such as thorium and potassium carbonate;
Potassium bromide, 2-methylbenzimidazole, methyl
inorganic or organic inhibitors such as benzthiazole;
Water softeners such as polyphosphates, trace amounts of iodide and
Development inhibitors consisting of lucapto compounds can be mentioned.
Ru. The processing method of the present invention basically includes the color development step and
It consists of kneading followed by a desilvering process. Further following this
It is preferable to carry out a washing and/or stabilization step.
stomach. The washing water used in the washing process is used to dry the photosensitive material after processing.
Contains various surfactants to prevent uneven water droplets during drying.
I can have it. These surfactants include:
Polyethylene glycol non-ionic surfactant, polyvalent
Alcohol nonionic surfactant, alkylbenzene
Sulfonate anionic surfactant, higher alcohol
Sulfate ester salt anionic surfactant, alkyl naph
Talen sulfonate amount Anionic surfactant, quaternary anion
Monium salt type cationic surfactant, amine salt type cationic surfactant
surfactant, amino acid” JF4 surfactant, base
Tine■ Is there an amphoteric surfactant side or an ionic surfactant?
is combined with various ions mixed in with the processing.
Nonionic surfactants may generate insoluble substances.
It is preferable to use sex thorns, especially alkyrufunioles.
A tyrene oxide adduct is preferred. Alkylphenol
In particular, octyl, nonyl, dodecyl, dinonyl
Phenol is preferred, and also an addition moiety of ethylene peroxide.
The number of moles is particularly preferably 8 to 14 moles. Roughly defoaming
It is preferable to use highly effective silicone surfactants.
stomach. In addition, water stains may form in the washing water and may damage the photosensitive material after processing.
To prevent mold from forming, various antibacterial agents and antibacterial agents are used.
It can also contain a fungicide. Examples of these antibacterial and antifungal agents include
Described in No. 57-157244 and No. 58-105145.
Thiazolylbenzimidazole compounds listed in JP-A-1978
4-27424 and Japanese Patent Application Laid-open No. 57-8542.
Sothiazolone compounds, represented by trichlorophenol
Talolophenol compounds and bromophenols, such as
organic compounds, organotin and organozinc compounds, thiocyanic acid
, isothiocyanate compounds, acid amide compounds,
Iazine, triazine compounds, thiourea compounds, base
Zotriazole alkylguanidine compound, benzua
Quaternary ammonia such as ruconium chloride
Antibiotics such as salts, penicillin, etc.
Journal Antibacteria and Antifa
Antibact, Ant
i-fung, Agents) Vol. General purpose as described in Arashi 5, p. 207-223 (1983)
Anti-pissing agents and the like can be mentioned. In addition, various fungicides described in JP-A No. 48-83820 can also be used.
I can be there. Moreover, it is preferable to contain various chelating agents. sharp
A preferred compound for the coating agent is ethylene diamine tetra
Aminopolycarbonate such as acetic acid, diethylenetriaminepentaacetic acid
Rubonic acid and l-hydroxyethylidene-1,1-diphos
Phonic acid, ethylenediamine-N, N, N', N'-te
an organic phosphonic acid such as tramethylenephosphonic acid, or
Maleic anhydride polyamide as described in European Patent 345172A1
Examples include hydrolysates of mer. It can also be included in the fixer or bleach-fixer mentioned above.
It is preferable to include a preservative in the subsequent washing water. The stabilizer used in the stabilization process stabilizes the dye image.
A processing solution is used. For example, organic acids and pH 3~
6 buffering capacity, aldehydes (e.g. formalin),
glutaraldehyde), JP-A-2-153348
and hexamethylenete described in U.S. Pat. No. 4,859,574.
Tolamin compound, hexahydrotriazine compound, N-
Liquids containing methylol compounds can be used.
Ru. The stabilizer contains all the compounds that can be added to the wash water.
In addition, ammonium chloride or
Ammonium compounds such as ammonium sulfite, Bi, A
Metal compounds such as 7, optical brighteners, hardeners, U.S. Patent 4
Using the alkanolamine t described in No. 786583
You can do that. In addition, a multistage countercurrent method is preferable for the water washing process and stabilization process.
The number of stages is preferably 2 to 4 stages. The replenishment amount is 1 to 5 of the amount brought in from the previous bath per unit area.
0 times, preferably 2 to 30 times, more preferably 2 to 15 times
It's double. The water used in the water washing process or stabilization process of two spatulas.
In addition to tap water, Ca
, water that has been deionized to a Mg concentration of 5■/f or less, halo
Do you use water that has been sterilized using UV germicidal lamps?
preferable. Also, tap water can be used to correct evaporation.
Is it suitable for the above-mentioned washing process or settlement process?
The water used should be deionized and sterilized.
Good. In the present invention, not only bleach solution and bleach-fix solution but also other
In order to correct the concentration due to evaporation even in the treated liquid, add an appropriate amount.
It is preferable to replenish water or correction fluid or processing replenishment fluid.
Delicious. In addition, the overflow liquid from the washing process or stabilization process should be
, using a method of flowing into a pre-bath having fixing ability.
This is preferable because it can also reduce the amount of waste liquid.
Delicious. Is it preferable to carry out the processing method of the present invention using an automatic processor?
Delicious. About the transport method in these automatic developing machines
JP-A No. 6O-19i257, No. 60-19125
No. 8, No. 60-191259. Also
In order to perform rapid processing, in automatic processing machines, there are
It is preferable to shorten the crossover. crossover
For automatic developing machines with a processing time of 10 seconds or less, see Japanese Patent Application Laid-Open No. 1999-1
319038. Continuous processing using an automatic processing machine using a processing method of a great invention.
When processing the photosensitive material, consumption of processing liquid components is required.
and also removes undesirable components eluted from photosensitive materials.
The amount of photosensitive material processed to reduce accumulation in the processing solution.
It is preferable to add a replenisher depending on the situation. In addition, each processing
Two or more treatment baths may be installed in the process, in which case supplementary
Does it use a counter-current method where the liquid is poured from the rear bath to the front bath?
preferable. Especially in the water washing process and stabilization process, 2 to 4 steps are required.
Preferably, it is a skade. The amount of replenisher should be determined based on the change in composition of each processing solution.
As long as there are no problems with true performance or other liquid contamination.
It is preferable to reduce it. For color photographic materials, the amount of color developer replenisher depends on the exposure.
100m/m/m of material ~15001rLI, preferred
Specifically, it is 100rPL1~10100O, and the color
In the case of print materials, 20 to 5 per 1 of photosensitive material.
00, preferably from 30 to 200. In the case of color photographic materials, the amount of bleach replenisher is
10-500-1 preferably 10-16 per rd
It is 0-. For printing materials, photosensitive materials 1rI!
20 to 300 rR1, preferably 50 to 15 per
It is 0i. In the case of photographic materials, the amount of bleach-fixing replenisher is as follows:
100-~3000n/, preferably 200m1
~1300-, and in the case of print materials, photosensitive materials
20-300 kura per d, preferably 50-20
It is 0-. Bleach-fix solution can be refilled as a single solution.
It's good and you can also refill the bleaching composition and fixing composition separately.
Also, overflow from bleach and/or fixing baths
It can also be used as a bleach-fix replenisher by mixing the flow liquid.
. In the case of photographic materials, the amount of replenishment liquid should be
Or 300r! L1~3000i, preferably 3001
J ~ 1000-, and in the case of printing materials, photosensitive materials
20-300, preferably 50-2
It is 00i. The amount of replenishment of washing water or stabilizing solution is from the bath per unit area.
1 to 50 times, preferably 2 to 30 times, the amount brought in.
It is preferably 2 to 15 times. To further reduce the amount of replenisher for environmental protection
It is also preferable to use a combination of various regeneration methods. Regeneration can be carried out by circulating the processing solution in the automatic processor.
It's fine, and once removed from the treatment tank, it's best to use it properly.
After the regeneration treatment, it is returned to the treatment tank as a replenisher.
The regeneration of the zero developer, which may be
Removal of accumulated materials by on-exchange treatment, electrodialysis treatment, etc.
This is done by adding chemicals called regeneration and/or regeneration side.
That's what I mean. The reproduction rate is preferably 50% or more, preferably 70%.
% or more is more preferable. Anion exchange resin is commercially available
It is possible to use JP-A No. 63-11005.
It is also preferred to use highly selective ion exchangers. Metal chelate bleaches in bleach and/or bleach-fix solutions are
, becomes reduced due to bleaching treatment. gold in this reduced state
Accumulation of genus chelates will only reduce bleaching performance.
In some cases, the image dye may become a leuco dye.
This causes a decrease in image density. For this reason, bleach and
/Or the bleach-fix solution should be continuously regenerated in conjunction with processing.
It is preferable to take Specifically, by air pump
Blow air into the bleach and/or bleach-fix solution to create oxygen.
Re-oxidation of metal chelates in a more reduced state, so-called air ray
It is preferable to do a tion. Hydrogen oxide, persulfuric acid
It can also be regenerated by adding an oxidizing agent such as salt or bromate.
I'll come. Regeneration of the fixer and bleach-fixer removes accumulated silver ions.
This is done by giving back. Other halogen that accumulates
It is also possible to remove anion ions using an anion exchange resin.
This is preferable in terms of maintaining wearability. In order to reduce the use of washing water, ion exchange or
Whether to use ultrafiltration or not, especially whether to use ultrafiltration or not
Delicious. A color light-sensitive material suitable for the processing of the present invention has a blue color on a support.
Silver halide emulsion for color-sensitive layer, green-sensitive layer, and red-sensitive layer
It is sufficient that at least 1 fan of the layer is provided, and the halogen
There are no particular restrictions on the number or order of silver oxide emulsion layers or non-photosensitive layers.
stomach. Typically, a substantially color-sensitive
Multiple silver halide emulsions with the same but different sensitivities
It is a color photosensitive material having a photosensitive layer consisting of layers.
The photosensitive layer is sensitive to blue, green, or red light.
It is a unit photosensitive layer with color properties, and is a multilayer color photosensitive material.
In general, the arrangement of unit photosensitive layers is on the support side.
A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are installed in this order.
be done. However, depending on the purpose, the above installation order may be reversed.
Also, different color-sensitive layers are sandwiched within the same color-sensitive layer.
The installation order can also be determined. Above, the silver halide photosensitive layer
Non-photosensitive layer between each layer, top layer, bottom layer, etc.
Layers may be provided. In the middle layer, Japanese Patent Application Laid-Open No. 61-437
No. 48, No. 59-113438, No. 59-11344
No. 0, No. 61-20037, No. 61-20038
Contains couplers, DIR compounds, etc. as described in the specifications.
Color mixing inhibitors, which are commonly used, may also be added.
It may also contain an ultraviolet absorbing agent, an anti-staining agent, and the like. The plurality of silver halide emulsion layers constituting each unit photosensitive layer are
West German Patent No. 1.121,470 or British Patent No. 9
23,045, a high-speed emulsion layer, a low-speed emulsion layer, and a low-speed emulsion layer as described in No.
A two-layer structure with multiple emulsion layers can be preferably used. General
Usually, they are arranged so that the sensitivity gradually decreases toward the support.
It is preferable that the halogen emulsion layers
A photosensitive layer may also be provided. Also, JP-A-57-
No. 112751, No. 62-200350, No. 62-2
Described in No. 06541, No. 62-206543, etc.
There is a low-speed emulsion layer on the side far from the support, and the support
A high-sensitivity emulsion layer may be provided on the side closer to. As a specific example, from the side farthest from the support, low sensitivity blue light
Color layer (BL) / High-sensitivity blue-sensitive layer (BH) / High-sensitivity green sensitivity
Photosensitive Jii (GH)/Low sensitivity green photosensitive layer (GL)/High
High-speed red-sensitive layer (RH)/low-sensitivity red-sensitive layer (RL)
order, or GH/BL/GL/GH/RH/RL order,
Or set in BH/BL/GH/GL/RL/RHO order, etc.
can be placed. It is also stated in Japanese Patent Publication No. 55-34932.
From the side farthest from the support, the blue-sensitive layer/GH
/' They can also be arranged in the order of RH/GL/RL. Ma
JP-A-56-25738 and JP-A-62-63936
on the side farthest from the support, as specified in the specification.
Blue photosensitive! Arranged in the order of /GL/RL/GH/RH.
You can also It is also stated in Japanese Patent Publication No. 49-15495.
The top layer is the most sensitive silver halide emulsion layer, and the middle layer is the most sensitive silver halide emulsion layer.
A silver halide emulsion layer with a higher sensitivity than that of the lower layer.
A silver halide emulsion layer with rougher photosensitivity than the middle layer is arranged.
The photosensitivity is gradually decreased toward the support.
Mention may be made of an arrangement consisting of three different layers. like this
Even if it is composed of 3M with different sensitivities,
As described in specification No. 59-202464,
Medium sensitivity from the side away from the support in the same color-sensitive layer
Emulsion rMZ high-sensitivity emulsion layer/low-sensitivity emulsion layer are arranged in this order.
You can. As mentioned above, various layers are used depending on the purpose of each photosensitive material.
You can choose the configuration and arrangement. Any of these layer arrangements can be applied to the color photosensitive material of the present invention.
can be used. In the present invention, the support of color photosensitive material and
Dry film thickness of all constituent layers excluding layer and back layer is 200μ or more
In order to achieve the purpose of the invention, the following is preferable. More preferably, it is 18.0μ or less. These film thickness regulations apply to color photosensitive materials during and after processing.
Due to color developing agents incorporated into these layers of
Depending on the amount of color developing agent remaining, bleach fog and processing may occur.
This has a major impact on staining that occurs while saving images after processing.
By getting. Especially for these bleached blades and stains.
The magenta color appears to be caused by the green-sensitive color layer.
It is a color increase or it is large compared to other cyan and yellow color increases. Note that the lower limit value in the film thickness regulations is based on the above regulations for photosensitive materials.
It can be reduced to the extent that performance is not significantly impaired.
desirable. Structure excluding the support of the photosensitive material and the twisted layer of the support
The lower limit of the total dry layer thickness is 12.0μ, which is the most
Provided between the photosensitive layer near the support and the undercoat layer of the support.
The lower limit of the total dry film thickness of the constituent layers is 1.0μ. Also, the film thickness can be reduced in both the photosensitive layer and the non-photosensitive layer.
You can. The film thickness of the multilayer color photosensitive material in the present invention is determined by the following method.
Measure with. The color photosensitive material to be measured is kept at 25°C and 50% I? H
Store under the following conditions for 7 days. First of all, this color feeling
Measure the total thickness of the optical material and then remove the tube cloth layer on the support.
After that, measure the thickness again and use the difference as above.
The thickness of the entire cloth layer excluding the support of color photosensitive material.
. This thickness can be measured using, for example, a contact-type piezoelectric transducer.
Anritus Electric C
o, Ltd., using -402B 5tand,)
can be measured. Note that the removal of the casing layer on the support
Removal can be done using an aqueous solution of sodium subzinc chlorate.
can. Next, using a scanning f-type electron microscope, the color photosensitive material was
Take a cross-sectional photograph of the material (magnification is preferably 3.000x or higher)
b) Measure the total thickness and the thickness of each layer on the support,
The total thickness measured by the film thickness measuring device mentioned above (actual thickness
The thickness of each layer can be calculated by comparing the absolute value)
. Swelling rate of the color photosensitive material of the present invention [(25°C,
Teno equilibrium swelling film thickness in HtO -25°C 155%RH
Dry total film thickness / Dry total film thickness at 25°C and 55% RH)
100) is preferably 50 to 200%, and 70 to 150%
is more preferable. If the swelling rate deviates from the above value, it will be dry.
- The amount of remaining developing agent increases, and photographic performance and desilvering properties
This may have a negative impact on film properties such as image quality and film strength.
Become. In addition, each swelling rate T (development rate) of the color photosensitive material of the present invention is
Maximum swelling in color developer (30'C 13 minutes 15 seconds)
90% of the film thickness is the saturated swelling film thickness, and the thickness is reduced to 1/2 of this.
It is preferable that the time taken to reach the target is 15 seconds or less.
, more preferably 9 seconds or less. contained in the photographic emulsion layer of the color light-sensitive material suitable for the processing of the present invention.
The silver halide contained can be of any silver halide composition.
good. i.e. silver chloride, silver bromide, silver chlorobromide, silver iodobromide, iodine
It is silver oxide or silver iodochlorobromide. Color photosensitive materials for photography and color reversal photosensitive materials (e.g.
Color negative film, reversal film, color reversal
In the case of paper), it contains 0.1 to 30 mol% of silver iodide.
Silver iodobromide, silver iodochloride or silver iodochlorobromide are preferred,
In the case of direct positive color photosensitive materials, silver bromide or chlorobromide
Silver is preferred, and in the case of paper photosensitive materials, silver chloride
Or silver chlorobromide is preferred. Silver halide grains in photographic emulsions are cubic, octahedral, and decahedral.
Those with regular crystals such as tetrahedrons, spherical, plate-shaped
crystals with irregular crystal shapes, such as crystals with twin planes,
It may be one with crystal defects or a composite form thereof.
. The grain size of silver halide is fine particles of approximately 0.2 microns or less.
However, the projection surface 8F has a large diameter of about 10 microns.
It may be grains, polydisperse emulsion or monodisperse emulsion.
. Silver halide photographic emulsions that can be used in the present invention include, for example,
Search Disclosure (RD), Nα17643
(December 1978), pp. 22-23, Arashi 3071
05 (November 1989), pp. 863-865-1,
Emulsion pre-parati
on and types)', and Nc1871
6 (November 1979), 648 pages, graphic [photograph]
True Physics and Chemistry J, published by Ballmontel (P. Glafkicles, Chemic et Ph1s
ique Photographique. Paul Montel, 1967), Duff
"Photographic Emulsion Chemistry" by Yin, CG, published by Fusucal Press,
F. Duffin. Photographic Emulsion Che
Mistry (Focal Press. 1966)), Zelikman et al.
"Cloth", published by Focal Press (V, L, Zelik
Manet al, Making and Coat
ing Photographic Emulsion,
Focal Press, 1964) etc.
Y4 can be manufactured using the method described above. U.S. Patent Nos. 3,574.628 and 3,655.39
No. 4 and British Patent No. 1.413,748, etc.
Also preferred are monodispersed emulsions. Also, tabular grains with an aspect ratio of about 5 or more
can also be used in the present invention. Tabular grains are
graphic science and engineering
Gutoff, Photographic Science
nce and Engineering), Volume 14
, pp. 248-257 (1970), U.S. Patent No. 4.4.
34.226°, 4.414.310, 4.4
No. 33.048, No. 4.439゜520 and British Patent No.
Easy by the method described in Patent No. 2.112.157 etc.
It can be prepared as follows. Even if the crystal structure is -like, it is a halo whose inside and outside are different.
It may be composed of a gen composition or a phase structure.
In addition, epitaxial bonding allows halos with different compositions to be formed.
Even if silver
Even when bonded with compounds other than silver halide such as lead oxide
good. Also, mixtures of particles of various crystal forms may be used. Silver halide emulsions are typically subjected to physical ripening, chemical ripening and
Use one that has been spectrally sensitized. used in such processes.
The additive used is Research Disclosure Demon 17.
643 (December 1978), Nα18715 (19
November 1979) and Nα307105 (January 1989)
(January), and the relevant parts are listed in the table below.
I stopped it. The known photographic additives that can be used in the present invention are also listed above.
As stated in the three research disclosures of
The relevant entries are shown in the table below. Additive type RD17643 RD18716
RD3071051 Chemical sensitizer page 23 64
Page 8 right 6t Page 866 2 Sensitivity enhancer
Page 648 Right shelf 4 Brightener page 24 Page 647
Right 6t page 868 Hardener binder page 26 page 651 left column page 874-875 page 26
651 pages; l! E i! 873~B? 4 pages 14
7. Agent 878
~Page 879 Various color couplers are used in the present invention.
A specific example is the above-mentioned RD Nu 1764.
3, ■-C-G, same fire 307105, ■-C-G
It is described in the listed patent. As a yellow coupler, for example, U.S. Pat.
No. 3,501, No. 4,022,620, No. 4,326
, No. 024, No. 4,401.752, No. 4,248,
No. 961, No. 3,973.968, No. 4,314,0
No. 23, No. 4.511649, Special Publication No. 58-1073
No. 9, British Patent Ring No. 1,425,020, No. 1,476
．． No. 760, European Patent No. 249.473A, etc.
Preferably. As magenta couplers, 5-pyrazolone and pyrazo
Roazole compounds are preferred, and European Patent No. 73,6
No. 36, US special:! f ¥4.310619, same 4.3
No. 51,897, No. 3.061.432, No. 3.72
No. 5,064, No. 4500.630, No. 4,540,
No. 654, No. 4.556, 630, Research Diss.
Closure (RD) Nα24220 (June 1984
month), RD floor 24230 (June 1984), Tokukai Sho
No. 60-33552, No. 60-43659, No. 61-
No. 72238, No. 60-35730, No. 55-118
No. 034, No. 60-185951, W○ (PCT)
Particularly preferred are those described in No. 88104795. Book
The effect related to the bleaching fog and stain of the invention is Pyrazoloa.
This is particularly noticeable for sol couplers. As cyan couplers, phenolic and naphthol
U.S. Pat. No. 4,052,212
No. 4,146,396, No. 4.228,233
, No. 4,296.200, No. 2,369.929,
No. 2,801,171, No. 2,772.162, No. 2,772.162, No. 2,772.162, No.
No. 2,895.826, No. 3,772.002, No. 3
, 758°308, 4,334.011, 4,
327.173, West German Patent Publication No. 3.329.729
European Patent No. 121.365A, European Patent No. 249°453
No. A, U.S. Patent No. 3.446.622, U.S. Pat.
, No. 999, No. 4,753.871, No. 4.451.
No. 559, No. 4,427.767, No. 4,690.8
No. 89, No. 4,254゜212, No. 4,296.19
No. 9, JP-A No. 61-42658, etc. are preferred.
Yes. Colored coupler to correct unnecessary absorption of color pigments
- Research Disclosure (RD) Arashi 176
Section 43 ■-G, U.S. Pat.
Publication No. 57-39413, U.S. Patent No. 4.004.92
No. 9, No. 4,138°258, British Patent Ring No. 1.146
．． The one described in No. 368 is preferred. Also, under U.S. patent
4,774.181 released upon coupling as described in No. 4,774.181.
A cap that corrects unnecessary absorption of coloring dyes using fluorescent dyes.
The developer described in U.S. Pat. No. 2,777,120
Contains a dye precursor group that can react with the main drug to form a dye.
It is also preferred to use couplers which have as a leaving group. As a coupler whose coloring dye has an appropriate diffusivity, American
National Patent No. 4.366.237, British Patent Ring No. 2゜125
, 570, European Patent No. 96.570, West German Patent (Public Patent)
3,234.533 is preferred. A typical example of a polymerized dye-forming coupler is
Permission No. 3.451,820, No. 4,080゜211,
4,367.282, 4,409.320, 4,409.320,
No. 4,576.910, British Patent No. 2,102.173
It is described in et al. A force that releases photographically useful residues upon coupling.
Pullers can also be preferably used in the present invention. development inhibitor
DIR couplers that emit
Closure (RD) 17643, described in sections ■ to F
patent, JP-A No. 57-151944, No. 57-154
No. 234, No. 60-184248, No. 63-3734
No. 6/U.S. Patent No. 4.248.962, U.S. Patent No. 4.7820
The one described in No. 12 is preferable. Releases nucleating side or development promoting side in image form during development
As a coupler, British Patent No. 2,097.140,
No. 2,131,188, JP-A-59-157638
, No. 59-170840 is preferred. Other couplers that can be used in uninvented photosensitive materials
- as described in U.S. Patent No. 4,130,427 etc.
Competitive coupler, U.S. Pat. No. 4,283,472;
No. 4,338,393, No. 4.310,618, etc.
Multi-equivalent coupler described in JP-A-60-185950, JP-A-60-185950;
DIR redox compound described in No. 62-24252 etc.
substance releasing coupler DIR coupler releasing coupler DIR
Coupler-releasing redox compound or DIR redox
S-releasing redox compound, European Patent No. 173.302A
A coupler that releases a dye that leaves behind color after separation is described in the issue.
Search Disclosure (RD) No. 11449, same
Bleaching described in 2424L JP-A-6]-201247, etc.
Accelerator Pressure Release Coupler, U.S. Pat. No. 4,553,477
Ligand-releasing coupler described in JP-A-63-757
Leuco dye-releasing coupler described in US Patent No. 47
No. 4,774,181, which emits fluorescent dyes.
Possible examples include puller. The couplers used in the present invention can be obtained by various known dispersion methods.
can be introduced into light-sensitive materials. An example of a high boiling point solvent used in the oil-in-water dispersion method is a U.S. patent.
It is described in No. 2,322,027 etc. below, and oil-in-water
The boiling point at normal pressure used in the droplet dispersion method is 175°C or higher.
Specific examples of high boiling point organic solvents include phthalate esters
(dibutyl phthalate, dicyclohexyl phthalate,
Di-2-ethylhexyl phthalate, decyl phthalate
, bis(2゜4-di-t-amylphenyl) phthalate
, bis(2,4-di-t-amylphenyl)isophthalene
bis(1,1-diethylpropyl) phthalate
), esters of phosphoric or phosphonic acids (triphenates),
Nyl phosphate, tricresyl phosphate, 2-ethyl phosphate
Tylhexyl diphenyl phosphate, tricyclohexyl
sylphosphate, tri-2-ethylhexylphosphate
tridodecyl phosphate, tributoxyethyl
Phosphate, trichloropropyl phosphate, di
2-ethylhexylphenylphosphonate, etc.), rest
Fragrant esters (2-ethylhexylbenzoate,
Decylbenzoate, 2-ethylhexyl-p-hydro
xybenzoate, etc.), amides (N,N-diethyl
Dodecanamide, N, N-diethyl laurylamide
, N-tetradecylpyrrolidone, etc.), alcohols or
or phenols (isostearyl alcohol, 2.4
-di-tert-amylphenol, etc.), aliphatic carbon
Bonic acid esters (bis(2-ethylhexyl) sebake
Dioctyl azelate, glycerol tributyl
Isostearyl lactate, trioctyl citre
), aniline derivatives (N. N-dibutyl-2-butoxy-5-tert-octyl, etc.),
aniline, etc.), hydrocarbons (paraffin, dodecylbene, etc.),
diisopropylnaphthalene, etc.).
It will be done. In addition, as an auxiliary solvent, those with a boiling point of about 30°C or higher,
Preferably an organic solvent at 50°C or more and about 160°C or less
Typical examples are ethyl acetate, butyl acetate,
Ethyl propionate, methyl ethyl ketone, cyclohexyl
Sanon, 2-ethoxyethyl acetate, dimethylform
Examples include Muamide. Latex dispersion process, effects and latex for impregnation
A specific example is U.S. Pat. No. 4,199,363,
Patent Application (OLS) No. 2.541゜274 and OLS No. 2.541゜274
41.230 etc. In addition, these couplers are compatible with the presence of the aforementioned high-boiling organic solvents.
under or in the absence of loader pull latex polymers (e.g.
For example, impregnated with U.S. Pat. No. 14,203,716),
or dissolved in water-insoluble and organic solvent-soluble polymers.
can be emulsified and dispersed in a hydrophilic colloid aqueous solution.
. Preferably, International Publication No. WO38100723
The homopolymer or copolymer described on pages 12 to 30 of the book
is used. In particular, the use of acrylamide polymers
This is preferable in terms of color image stabilization and the like. Suitable supports that can be used in the present invention include, for example, the above-mentioned
Search Disclosure (RD) NQ17643
28 page, and 64 from the left column of page 647 of Nα18716
It is written in the left column of page 8. The present invention can be applied to various color photosensitive materials.
. General purpose or movie color negative film, slide
Color reversal film for cards or televisions, color tape
paper, direct positive color paper, color positive film
and color reversal paper are representative examples.
Wear. Color reversal film uses so-called inner mold (coupler)
(contained in the photosensitive material) or external mold (contained in the coupler).
(contained in the developer) may also be used. (Examples) Below, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these. Example 1 On a cellulose triacetate film support subjected to undercoating,
A multilayer color photosensitive material consisting of each layer with the composition shown below.
Sample 101, which is a sample, was prepared. (Composition of photosensitive layer) The amount of coating is g/ for silver halide and colloidal silver.
rr! The amount of silver expressed in position i is also determined by the amount of coupler additive and
For gelatin, the amount expressed in g/rrf) l-
, and for sensitizing dyes, one mole of silver halide in the same layer
Expressed in moles per liter. 1st layer 2 antihalation layer Black colloidal silver Silver ratio weight 0.20 gelatin
2.20UV-10,
11 UV-20,20 Cp d -14,0X10-' pd-2 olv-1 olv-2 \ 2nd layer: Intermediate layer fine grain silver iodobromide 1.9X10-! 0.30 1.2X10-" (Ag 11.0 mol%, equivalent sphere diameter 0.07 μm) Silver ratio o, 15 1.00 6-OXIO-t 2.0X10-" Gelatin xC-4 pd-3 3rd Layer: First red-sensitive emulsion layer Silver iodobromide emulsion (Ag 15.0 mol%, surface height AgI type, equivalent sphere diameter 0.9 μm, variation in equivalent sphere diameter
Coefficient 21%, tabular grains, diameter/thickness ratio 7.5) Silver content o, 42 Silver iodobromide emulsion (Ag 14.0 mol%, internal high Agl, equivalent sphere diameter 0.4 μm, 1 sphere equivalent diameter Fluctuation
Coefficient 18%, dodecahedral particles) Amount of silver casing 0.40 1.90 4.5Xlθ-4 mole 1.5X 10-' mole 4.0Xlθ bow mole 0.65 1.0X10-'' 2,3 X 10-” 0.32 Gelatin xS-1 xS-2 xS-3 xC-1 xC-3 xC-4 olv-1 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (Ag18.5 mol%, Internal high Agl type, equivalent sphere diameter 1.0 μm. Coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 3.0) Amount of silver coating 0.85 0.91 3.0X10-'mol 1 .0X10-mol 3.0X10-'mol 0.13 Gelatin xS-I xS-2 xS-3 xC-1 ExC-26,2X10-"ExC-44,0xlO-" 5olv-]
0.10 No. 57ii: Third red milk layer silver iodobromide emulsion (Ag1 11.3 mol%, internal high gl
Mold, equivalent sphere diameter 1.4 μm, coefficient of variation of equivalent sphere diameter 28%, plate-shaped particles, diameter/thickness ratio 6.0) Amount of silver powder 1.50 Gelatin 1.20E
x S -12, Ox 10-'mol ExS 2
6.0 x 10-'mol ExS-32
,0x10-'Mole ExC-28,5xlO Bow ExC-57,3x 10-"5olv-10,12 Solv-20,12 6th N, Interlayer Gelatin 1.00Cp
d -48,0xlO-' S o ] V -18,0xlO-' 7th layer・
First green emulsion layer Silver iodobromide emulsion (Ag 15.0 mol%, surface height Agl type, equivalent sphere diameter 0.9 μm, variation in equivalent sphere diameter
Coefficient 21%, tabular grains, diameter/thickness ratio 7.0) Silver powder amount 0.28 Silver iodobromide emulsion (AgI 4.omol%, internal high Agl
Type, equivalent sphere diameter 0.4 μm, coefficient of variation of 1 sphere equivalent diameter 18%, dodecahedral particles) Shifan xS-4 xS-5 xS-6 xM-I xM-2 xM-5 olv-1 Amount of silver particles 0.16 1.20 5, OX 10-' mol 2, OX lo-' mol], OX 10-' mol 0.50 0.10 3.5X10 bow 0.20 S o 1 v -33,0X10-' 8th layer:
Second green-sensitive emulsion layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high Agl, equivalent sphere diameter 1.0 μm, variation in equivalent sphere diameter
Coefficient 25%, plate-shaped particles, diameter/thickness ratio 3.0) Silver powder amount 0.57 Gelatin 0.45ExS
-43,5X]O-'molExS-51,4X 10-'molExS-67
,0x10 mol ExM-10,12 ExM-27,1xlO-coExM-3s,5xto-" 5olv-10,15 So 1 v-31,0xlO-"9th layer: Intermediate layer gelatin 0.503 o
] v -12,0X10-'s 10th [:3rd green milk
Silver iodobromide emulsion CAg1 11.3 mol%, internal high Agl
Mold, equivalent sphere diameter 1.4 μm, coefficient of variation of 1 sphere equivalent diameter 28%, plate-shaped particles, diameter/thickness ratio 6.0) Amount of silver powder 1.30 1.20 2.0X10-'mol 8.0X10-'mol 8.0X10-'Mole 4.5X 10-' 1, OX 10-" 4, 5X 10-" 1.0XlO-1 0,25 Gelatin xS-4 xS-5 xS-6 xM-4 xM-6 ExC- 2 pd-5 olv-1 11th layer: yellow filter layer gelatin pd-6 olv-1 12th layer: middle layer gelatin 0.50 5.2X10-” 0.12 0.45 (: pd-30, 10th 13 layers 1st W-sensitive opalescent layer silver iodobromide emulsion (Ag 12 mol%, uniform-Agl type, equivalent sphere diameter 0.5'Bm, variation of equivalent sphere diameter)
Dynamic coefficient 25%, flat supported particles, diameter/thickness ratio 7.0) Silver coating amount 0.20 Gelatin 1.00ExS
-73.0 Zhou AgI
Mold, equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 16%, octahedral particles) Silver coating amount 0.19 Gelatin xS-7 0,35 2,0X10-'mol EXY-1'
0.22 SOIV I
7. OX]O-' 15th layer, intermediate layer with particle silver iodobromide (Ag 12 mol%, uniform-Agl type, equivalent sphere diameter 0.13 am) silver coating amount
0.20 μ fan 0.36 1st
6th layer: 3rd W-sensitive emulsion layer Silver iodobromide emulsion (Ag1 14.0 mol%, internal high Agl
Mold, equivalent sphere diameter 1.7 μm, coefficient of variation of equivalent sphere diameter 28%, plate-shaped particles, diameter/thickness ratio 5.0) Silver coating amount 1.55 Gelatin 1.00E x
S -8], 5x 10-L mol ExY-10,21 So] v -17,0XIO-' 17th layer, 1st protective layer gelatin l, 80UV-
10,13 0,21 1, OX 10-" 1.0X10-2 3, F-4, F-5, F-6, F-7, F-8, F-9
, F-10, F-11, F-12, F-13 and iron salts
Contains lead salts, gold salts, platinum salts, iridium salts, and rhodium salts.
is possessed. V-2 olv-1 olv-2 18th layer: 2nd protective layer fine particle silver chloride (equivalent sphere diameter 0.07 μm) Silver coating amount 0.36 Gelatin 0.70B-1
(Diameter 1.5 μm) 2. OX 10-'B
-2 (diameter 1.5μm) 0.15B -
33,OX 10-" W -12,OX 1O-2 H-10,35 Cp d -71,00 This sample contains 1,2-benzisothiapurin-3-ol
(average 200 ppm relative to gelatin),
thyl-p-hydroxybenzoate (approximately 1.000
ppm), and 2-' near z/xyethanol (
(approximately 10,000 ppm) was added. Furthermore B-4
, B, -5, W-2, W-3, F-1, F-2, F-U
V-1 ,C)l,5CHC02H C3iHoxM-4r)I. xM-5 I xM-6 ExY ExY-2 pc1 olv-2 olv-3 xS-1 X5-3 pd Cpc! -5 pd-4 C+H4+ P C+Hu cp Ruby pd-7 olv-1 xS-5 xS-6 xS-7 xS-8 B-2 COOCH+ -CH, -C Jin- SOj Island v. -2 n=2~4 ■ CH+ = CF, SO+ CH+ Co -C
H. CH+=CH Sex Olr CONH-CH
+OONa The prepared sample 101 was passed through an optical web, and the color temperature was 4.
Exposure to white light at 800'' and then processing as described below.
Processed in process. A cine-type automatic developing machine is used for processing.
, the cumulative amount of replenishment to each treatment bath is 2.5 of the tank capacity.
The process continued until it doubled. The processing performance shown below is
This is the result of the processing performed at this point. Processing process Processing time Processing temperature Replenishment amount 0 Tank capacity
Color development 3 minutes 15 seconds 38.0℃ 2:M 15/
Bleach 50 seconds 38.0℃ 5
d 51 bleach fixing 50 seconds 38.0℃
□ 51 fixation 50 seconds 38.0℃ 16
wl 51 water wash [11 30 seconds 38.
0℃ - 31Wash +2) 20 seconds 38
．． 0℃ 34d 31 stable 20 seconds
38,0℃ 20j 31 dry @ 1 minute
55 ℃ This replenishment amount is the amount per 1 m in 35 W. The washing water is from (2) in the direction of the opposite wave to Il+, and the washing water is
All of the overflow liquid was introduced into the hot spring bath. drift i4
p! ! The second is a saf for the bleach solution air lane 5'.
2! -Nagaratokoro
I did the trick. Each treatment bath is JP-A-62-18346.
Milk printing of photosensitive materials, which is equipped with the stirring means described in No. 0.
The jet is made to collide with the surface. Refilling the bleach-fixing bath is automatic.
The upper part of the bleach tank Q of the dynamic developing machine, the bleach fixing section, and the fixing section.
Connect the top of the tank and the bottom of the bleach-fix tank with a pipe, and
, overflow caused by supplying replenisher to the fixing tank.
All of the liquid was allowed to flow into the bleach-fix bath. still,
Bleaching process of developer solution, bleach-fixing process of bleach solution, focus on bleach window
The amount of fixing solution carried into the fixing process and washing process is 35
2.5i and 2, respectively, per 1 meter length of photosensitive material of fl width
．． 0af, 2°0-12. QMi was there. Also
, the crossover time is 5 seconds in each case, and at this time
The time period is included in the processing time of the previous step. The composition of the treatment liquid is shown below. (Developer solution) FFL solution (g) Replenisher solution (g) Zenaletriamine pentachorate]-Hydroxyacetic acid lidene-1,1~ Dipho2. Phonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroquinolamine sulfate 2-Methyl-4-[N-ethyl-N-(β-hydroxybutyl) Aminocoaniline Add sulfate water (bleach solution) 3 .3 3.9 37.5], 4 1.3 (2,4 39,0 0,4 3,3 4,5 6,] 1.0# 1.OA +0.05 10.15 Mother liquor (g) Replenisher (g> Compounds listed in Table 1 Ferric nitrate nonahydrate Ammonium bromide Ammonium nitrate Hydroxyacetic acid Acetic acid Add acid water to pH [Prepared with aqueous ammonia] (g White fixer mother liquor) With the above bleaching solution mother liquor Mixture of the following fixer mother liquor (fixer) 0.383 mol 0.370 mol 84.0 17.5 63.0 33.2 1.0! 3.60 Mother liquor (g) Ammonium sulfite 19.0 Thiosulfuric acid Ammonia 280j Water solution (700g/l> Imidazole 28.5 Ethylenediamine 12.5 0.547 mol 0.528 mol 120, 0 25.0 90.0 47.4 1.01 2.80 15 pairs 85 Replenisher (g) 57.0 840+d 85.5 37.5 Add water 1.07! 1.01
'pH7,407,45

[Prepared with ammonia water and acetic acid]

(Washing water) Mother liquor and replenisher Geido tap water were mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strongly basic anion exchange resin (Amberlite IRA-4 manufactured by Rohm and Haas).
Water was passed through a mixed bed column packed with 00) to reduce the cyclicity of carunium and magnesium ions to 3/e or less, and then 20 w/l of sodium isocyanurate dichloride and 150 w:/l of sodium sulfate were added. did. The pH of this solution was in the range of 6.5-7.5. (Stable solution) Both mother liquor and soybean solution have iIC units g) Formalin (37%) 2. OM! Polyoxyethylene-p-0,3 7-tononyl phenyl ether (average degree of polymerization 10) Ethylenediamine 4-node a 0.05 2) Add salt water 1.0fpH5,0-
8.0 Regarding sample 101 which was subjected to the above treatment, the amount of residual silver at the highest concentration portion was measured by X-ray fluorescence analysis, and the results are shown in Table 1. G in the Dmin club again? Measures 74 degrees, separately,
Differences between the Drr+in part of the sample treated by replacing the bleaching solution in the automatic processor with a bleaching solution made of the following bond that does not cause bleaching blade bleed (1 month of bleaching turnips are taken and shown in Table 1. (Basic bleaching Liquid) Sodium ferric ethylenediaminetetraacetate] 00g Lium trihydrate Ethylenediamine + l Nitrium 10g Ammonium chlorobromide 100g Ammonium nitrate 30 [Aqueous ammonia (27%)] 6.5 - Add water
1.01p8
6.0th 22nd trial month above 60t, 7o%
We investigated the increase in the degree of LDmin in 5 weeks after RH. The obtained results are shown in the table. Table 1 Comparative compounds A: Ethylenediaminetetraacetic acid B: 1.3-
Diaminopropanetetraacetic acid C: 1,4-diaminobutanetetraacetic acid From the results in Table 1, the solution containing the metal chelate compound of the present invention with bleaching ability can reduce the amount of residual silver compared to the solution containing the comparative compound. It can be seen that there is almost no bleaching blade blur or an increase in staining after treatment, indicating excellent performance. ／ ／ ／ ／ ／ ／ ／ Example 2 On a cellulose triacetate film support that had been dusted,
Sample 102, which is a multilayer color photosensitive material, was prepared by layering each layer having the composition shown below. (g Optical Layer Composition) The numbers corresponding to each component indicate the specific weight expressed in g/rd units, and for silver halide, the specific weight in terms of silver. However, for sensitizing dyes, the specific weight relative to 1 mole of silver halide in the same layer is shown in mole units. (Sample 101) 1st layer (antihalation layer) Black colloidal silver Silver o,]8 gelatin 1,4° 2nd layer (intermediate layer) 2.5-di-1-pentadecylhydroquinone 0.18EX-
10,070 EX-30,020 EX-12 U-1 B5-1 B5-2 Third layer of gelatin (first red-sensitizing milk stone) Emulsion A Emulsion B Sensitizing dye 1 Sensitizing dye ■ Sensitizing dye ■ EX- 2 E ] Dye ■ EX-2 EX-3 EX-10 Gelatin 5th layer (third red-sensitive emulsion layer) Emulsion sensitizing dye l Sensitizing dye ■ Sensitizing dye ■ EX-2 EX-3 EX-4 Silver 1, 00 5,lX]O-'1.4X]0-'2.3xlO-' 0,070 0,050 1.30 Silver 1.60 5.4X10-'! , 4X10-'2.4X10-'' 0,097 0.010 0,080 BS-1 B5-2 Sixth gelatin layer (intermediate layer) EX-5 BS-1 Seventh gelatin layer (ygl green emulsion layer). Emulsion A Emulsion B Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ EX-1 EX-6 EX-7 EX-8 BS-1 B5-3 Gelatin 0.22 0.10 1.63 0,040 0,020 0.80 Silver 0.15 Silver 0.15 3.0XIO-' 1, OX 10-'3.8X10-' 0,021 0.26 0,030 0,025 0.10 0.010 0.63 8th Layer (second edge-sensitive emulsion layer) Emulsion C Sensitizing dye■ Sensitizing dye V Sensitizing dye■ EX-6 EX-7 EX-8 B5-1 B5-3 Gelatin 9th layer (third green-sensitive emulsion layer) ) Emulsion E Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ EX-1 EX-11 X-13 B5-1 Silver 0.45 2, lX10-' ?, OX 10-'2.6X10-' 0,094 0,026 0.018 0.16 8.0X10-' 0.50 Silver 1,20 3.5X10-'8.0X10-' 3,OX]0-4 0,025 0.10 0,015 0.25 HBS-2 Gelatin 10th layer (yellow filter layer) Yellow colloidal silver X-5 HBS-1 Gelatin 11th layer (first blue-sensitive emulsion layer) Emulsion A Emulsion B Emulsion F Sensitizing dye ■ X-8 X-9 B5 -1 Gelatin 12th layer (second blue emulsion layer) Emulsion G Sensitizing dye ■ X-9 Silver 0,050 0,080 0,030 0.95 Silver 0,080 Silver 0.070 Silver 0070 3.5X 0-' 0,042 0.72 0.28 1.10 #! 0.45 2,lXl0-'' 0.15 E X -10 HBS-] Gelatin 13th layer (3rd W emulsion layer) Emulsion H Sensitization Dye ■ ) 7,0XIO-' Silver 077 2.2XIO-' 0,20 0,070 Silver 0.20 0.11 0.17 5.0X10-' 1.00 0.40 5.0XIO-2 0,10 0, 10 S-10,20 Gelatin 1.20 Furthermore,
W-1, W-2,
W-3, B-4, B-5, F-1, F-2, F-3, F
-4, F-5, F-6, F-7, F-8, F-9, F-
10, F-11, F-12, F-13, and iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt. X X-2 n)! (i) C, P,,0ChH 1: X-3 H X-7 X-8 X-9 Shi1 X 1H X CIH13(Il) E) Knee 6 X-10 H C (t)C+Ht (1)CJi (t)C,Hi Sensitizing dye l Sensitizing dye ■ Sensitizing dye ■ B5-1 Tricresylphosphnate BS Di-n-butyl phthalate sensitizing dye ■ Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ S-1 CH. C) It = CH-3ol CHI COh'HC
H. CHz =CH-5o= -CHI -CD surface-C)I
+n=2~4 DDH CODCli+ NHC+H,z(n) NHC,H. The prepared sample 102 was heated to a color temperature of 4 through an optical sea urchin sono.
It was exposed to white light at 800') t: and then processed through the processing steps shown below. For processing, an ultra-compact automatic processing machine was used, and the processing was continued until the cumulative value of replenishment 1 to each processing bath reached 2.5 times the tank capacity. The following results are the results of the processing performed at this time. Processing time Processing temperature Replenishment amount Tack capacity Color development 1 minute 45℃ ]Qm 2A bleaching ■40 seconds 43℃ 5Mi 1
l ■ 20 seconds fixation 40 seconds 3Qd
If wash with water 20 seconds 30
m lj drying 40 seconds 70°C *The amount of refilling lid is 351 per meter width Aeration in the bleaching bath and stirring means for each bath are the same as in Example 1, and the amount carried from each treatment bath to the next bath is:
The cross-over time was 2.2-per meter length of the photosensitive material having a width of 35 fl, and the crossover time was 6 seconds in each case. Color development 11 Blue diethylenetriaminepentaacetic acid 1-hydroxyethylidene-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium iodide Hydroxylamine sulfate 2-Methyl-4-[N-ethyl-N(β-hydroxyethyl) aminocoaniline sulfate Salt 2-Methyl-imidazole 5-nitrobenzimidazole 1-phenyl-4-methyl-4-hypoquinemethyl-3 Pyrazolidone Add water to mother liquor 2.2g 3.0g 4.1g 8g 1.3M 2.4g 13. 8g 20mg 30■ 50■ Replenisher 2.2g 3.2g 4.9g 0g 3.3g 17.0g 20wg 31■ 01mg 000d 000d pH (25℃)! The metal chelate compounds listed in Table 2: ammonium bromide, ammonium phosphate, acetic acid (90%), pH by adding water, ammonium thiosulfate (70%), ethylenediamine, and ammonium sulfite (water). The following samples are shown in Table 2. 80g 114g 15g 21.4g 42g 60g 1000IR11000,w( 4,54,5 Mother liquid, replenisher, both 1 28〇- 10,3010,51 Dan-phlegm Shiinukai 0.37 mol 0.50 mol 10g 8g 000d 7 As shown in Table 2, the bleached cypress containing the total pressure chelate compound of the present invention was shorter than the comparative bleaching method. The Comparative Compound E Comparative Compound E Comparative Compound E Comparative Compound E Comparative Compound E Comparative Compound I! 7iF Example 3 After corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin lower layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further distributed to form the layers shown below. A multilayer color photographic paper with the following composition was prepared.The specific gravity liquid was prepared as follows: 19.1 g of yellow coupler (EXY) and color image stabilizer (CPd-1) 4. 4g and color image stabilizer (Cp
d-7) Add and dissolve 0.7 g + 27.2 cc of Ji acid z-thyl and 4.1 g each of solvents (Solv-3) and (Solv-7), and dissolve this solution in 10% solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. Emulsified and dispersed Makinto was prepared by emulsifying and dispersing it in 185 cc of an aqueous gelatin solution. On the other hand, silver chlorobromide emulsion A (cubic, 3=7 mixture (silver molar ratio) of a large size emulsion with an average grain size of 0.88% and a small size emulsion with an average grain size of 0.70-. Variation in grain size distribution The coefficients are 0.08 and 0.10, respectively, and each size emulsion contains 0.3 mol% silver bromide locally on a part of the grain surface)
was prepared. This emulsion contains the following 1! r-sensitizing dye A. 2.B or silver per mole to large size emulsions, respectively. OX]0-' mol, and for small size emulsion A, 2.5XIO-' mol was added, respectively. Further, chemical ripening of this emulsion was carried out by adding a sulfur sensitizer and a gold sensitizer. Mix and dissolve the emulsion-dispersed Makito and this silver chlorobromide emulsion to obtain the composition shown below.
A ratio solution was prepared. The distribution liquids of the second to seventh layer phases were also prepared in the same manner as the phase distribution liquid of the first layer. As the gelatin hardening agent for each layer, l-xy-3,5-dichloro-5-triazine sodium salt was used. Further, Cpd-10 and Cpd-11 were added to each layer in total amounts of 25.0 mg/rd and 50.0 mg/m, respectively. The following five spectral enhancement dyes were used in each of the silver chlorobromide emulsions. Blue (sensitizing dye for the milk sting layer. SO1θ SO, H-N (C2HI). Blue-sensitive blue-sensitive milk layer 11 layer dye B (1 mole of silver halide, large size milk 1F B +
= 4.0:':10-'' mol for small size emulsion B
For L+, 5.6 Sensitization for green-sensitive emulsion layers Dye C 3O 'E' SO, To N (CJ
s ) s (per mole of silver halide, large-sized milk E)
! 1: versus 7. OX 10-' mol, and 1. for small size milk 6B. cl: '10-' mol) Red sensitivity y1 Sensitizing dye for the dark layer E C, Hl 19 C, H (per 1 mol of silver halide, 0.9X 1 for large size emulsion C)
0-' mole, and for small size emulsion C 1. ]
X 10-L mol) The following compound was added to the red-sensitive emulsion layer in an amount of 2.6X 10-'' mol per mol of silver halide. and 1-(5-methylureidophenyl)-5-mercaptotetrazole per mole of silver halide, respectively.
．． 5X10-'mol, 7.7X]0-'mol, 2.5
X10-' moles were added. In addition, for the W-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added per mole of silver halide to lXl0-'
mol and 2X10-' mol were added. In addition, the following dyes (specific weights are shown in parentheses) were added to the emulsion layer to prevent irradiation. (lomg/m') (Layer structure) The composition of each layer is shown below. The numbers are direct weight t(g,・rrI
'! represents. Silver halide emulsions have a reduced weight in terms of silver. Support polyethylene laminate paper C Polyethylene on the wi side contains a white pigment (Tie) and a bluish dye (containing groups) Layer 2 (W-sensitive pore side layer) The silver chlorobromide pore side described above, 0430 Gelatin 1・ε6 yellow coupler (ExY>0.82 Color image stabilizer (Cpd-1) 0119 solution H (Soiv-3) 0.1
8 Solvent (Solv-7) 0
．． 18 color image stabilizer (Cpd-7)
0.06 Fifth layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Solv-1) 0.1
6 solvent (Solv-4) 0
．． 08 Fifth layer (green-sensitive emulsion layer) Silver chlorobromide hole side (cubic, large size emulsion B with average grain size 055 and small size emulsion B 039-1/3
Mixture (Ag molar ratio). The coefficient of variation of grain size distribution is 0.10 and 008, respectively, and each size emulsion is AgBr.
0.8 mol% was localized on a part of the particle surface)01
2 Gelatin 1.24 Magenta coupler (E): 11ri 0.23
Color image stabilizer (Cpd-2) 0.
03 color image stability law (Cpd-3)
0.16 color image stabilizer <Cpd-C)
0.02 color image stabilizer (Cpd-9)
0.02 solvent (Soiv-2)
0.40 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (LIV-1) 0.47
Color mixing prevention grinding (Cpd-5) o,
os solv (Solv-5)
0.24 Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, large size emulsion C with an average grain size of 0.58μ and small size emulsion C with an average grain size of 0.45μ):
4 mixture (Ag molar ratio). The coefficient of variation of grain size distribution is 0.09 and 0.11, and each size emulsion has AgBr 0.
6 mol% was locally contained in a part of the particle surface.
0.23 gelatin
1.34 cyan coupler (EXC)
0.32 color image stabilizer (Cpd-2)
0.03 color image stabilizer (Cpd-4
) 0.02 color image stabilizer (Cpd
-6) 0.18 color image stabilizer (C
pd-7) 0.40 color image stabilizer (Cpd-8) 0.05 solvent (
Solv-6) o, 14 6th layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing inhibitor (Cpcl-5) 0.0
2 Solvent (Solv-5) 0
．． 08 Seventh layer (protective layer) Acrylic modified copolymer of gelatin polyvinyl alcohol (degree of modification 17%) Liquid paraffin 1.33 0.17 0.03 1: ] mixture (molar ratio) with (ExY) yellow coupler EXM magenta coupler (EXC) Noan coupler! Mixture of 1 to 1 (molar ratio) (Cpd-5) Color mixture inhibitor H (Cpd-6) Color image stabilizer CJ* (t) caHs (t) 2 : :4 mixture (quantity ratio) (Cpd-7) Color image stabilizer - (CHz-CH) -- C0N) IC, H, (t) Average molecular weight 60.000 (CpC-]) Color image stabilizer ( Cpd-2) Color image stabilizer drop 2 COOC, I(S (Cp6-3 Color image stabilizer (Cpd-4) Color image stabilizer SO, Na 5H 7(t) 5H (r) (Cpd-8) Color 1:1 mixture with image stabilizer (tl ratio) (Cpd-9) Color image stabilizer (Cpd-10) Preservative 'δ (Cpd-11) Preservative? 424 mixture (weight ratio) <5oiv-]) Solvent, C00C,H. ,H,.ゝ,1 80:20 mixture (volume ratio) (Sol~・-7)Solution C,H,,CHCH(CH2),C00C,)!,.CH,・GoQl (Sci+・− 3\Solution 1 mixture (volume ratio) Solvent (Sclv-4) Solvent (Sol An optical wedge was attached to the photoresist material prepared in this way, and a stepwise exposure was carried out using a light source at 3800°, and this was processed using an automatic developing machine. The results of the treatment performed at this point are shown in Table 3. The remaining 11 pairs of the maximum growth area were measured by fluorescent X-ray method. V, Gfa of Dmin part of food
D
m r n u Gγ: Obtained as a difference in degrees. In addition, the sample after the above treatment was aged at 80" 70% for one week,
Color development to check for stain increase over time 39℃ bleach-fix 35℃ rinse■ 35℃ rinse■ 35℃ rinse■ 35℃ 45 seconds 70m 201 45 seconds 6QwL" 201 20 seconds □ 10ffi 20 seconds □ 10f 20 seconds 36M 10 f dry drying
80℃ 60 seconds (*oH charge per 141 m of photosensitive material) (Rinse ■-■
-・ 3 tanks countercurrent system closed) (* 6014m above the tree)
In addition, 120 M1 per photosensitive material IM from S/S
(I poured it)
K-jo Kaisui τ 0C
Jd 700m diethylenetriaminepentaacetic acid 0.4g 0.4gN
, N, N-tetrakis (methylenephosphonoic acid) 1,2-di-andotoxohenbon-4,6-disulfonic acid disodium salt triethanolamine potassium chloride potassium bromide potassium carbonate optical brightening iJ (h) IITEX 4B (manufactured by Sumitomo Chemical) 0.5g 4.0g 27,0g 3.0ε 12.0g 0g 1.0g C,5g 12,0g 6.5g 0.03g 27,0g Slurium sulfite\,\- Hys(sulfoethyl)pidroquinolamine N-ethyl-N-(β-notanesulfonamideyutyl)-3-methyl-4 Aminoayu 1 Add water and pH (25°C) /A) Ammonium sulfite, ethylene diaminoacetic acid, ferric nitrate, nonahydrate, ammonium bromide, hexahydrate (67%) Add water and pH (25°C) (acetic acid and 0.1 g 10.0 g 000m) Ol O l long envelope η precept 600, t 100, wf 0g 0, 155 mole 0, 138 mole, log 1000, d 5.8 01 ε 30g, 0 000m 1 +, ! 0 publication j; scatter] 501 250〆 00g 0.383 mol 0.340 mol 75 g 000ml 5.6 and ammonia water) (Standard bleach-fix solution for evaluation of bleach blades) Ammonium water thiograte (70%) Ammonium sulfite ethylenediaminetetraacetic acid iron (I I + ) Ammonium ethylenediaminetetraacetic acid Ammonium bromide acetic acid (67%) Add water to pH (25℃) 600w! 10 〇- 0g 0g g 0g 0g 1 0 0 (11d 5.8 Table 3 Comparative Compound 8: Ethylenediaminetetraacetic acid B: 1.3-diaminopropanetetraacetic acid C: 1 Noaminobutanetetraacetic acid Table 3 C・-ms J A-Invention C) Bleaching solution containing a metal chelate compound: = Contains a comparison compound 〇2:
In comparison, it can be seen that residual forceps are greatly eliminated, and there is almost no increase in bleaching blade burr or staining after treatment, indicating excellent performance. Immediately after preparing the bleaching solution containing Compound B: ; Even though it showed sufficient bleaching ability, it was running without any trouble! 22 It causes a decline in ability, and it is caused by
・Soaking is recommended, but is bleach-fixing containing an uninvented metal chelate compound? 8. Smiling turbidity C) The appearance was almost constant and stable. Practical example 4 Practical example 30 Passing 7 optical fibers through the photosensitive material, 3200
Stepwise exposure was carried out using a light source of ;BI of degree;Measure the slurp at 80°, 7
The sample was allowed to age for 8 days under 0% RHO conditions, and the amount of staining generated over time was determined as the difference between the two. 2 poems of the place l-1-no 1-12 color development
40 @ 15 seconds bleach fixing 30~35°
$20 7'! ' Rinse for 10 seconds ■ Rinse for 7 seconds ■ Rinse ■ Rinse ■ Dry 70-80''' Rinse for 15 seconds ■
The 4-tank counterflow direction from to the rinse ■ was set. ) Next, the composition of each treated eye is shown. Tateri Niyo 1st water
QQs+f noethylenetriaminepentavinegar is 0.4g N, N, N-4 lith (methylene phosphonic acid)
4. '0g 1-Hydroquinethylidene-1.1-nophosphonic acid 0.4g Triethanolamine 12.0g Potassium chloride 4.9g Potassium bromide 0.015g Potassium carbonate 29g Optical brightener (WH
ITEX 4B Sumitomo Chemical) 1.0g Sodium sulfite 0.1gN, N
-Bis(sulfoethyl)hydroquinocyamine N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 10.5 g Add water to 1000-(pH
(25℃) 10.151 Wataashi Kookasui
40 (ld ammonium thiosulfate (700g/Z) 1
00m ammonium gramite 15
g Compounds listed in Table 4 of this book 0.21 mole ratio Ferric nitrate nonahydrate 0.19 moles Ammonium bromide 40 g Add water 1000° pH<25°C
) 62 (Compounds marked with * were mixed with 200 d of water separately and this was used.) Yunosukai ion-exchanged water (calcium, magnesium 3 pp each)
m or less) was used. Table 4 As shown in Table 4, when the compound of the present invention was engraved on a bleaching stone and compared to a comparative one, it showed excellent silver resistance, less brittleness on the bleaching edge, and an O status of 4 over time. It can be seen that it exhibits excellent performance with less occurrence of fumes. (Effects of the Invention) The treated composition containing the metal chelate compound of the present invention improves bleaching edge burr, post-treatment stain, and desilvering properties. Patent applicant: Fuji Photo Film Co., Ltd. - Hon Co., Ltd. Comparative compounds R, E, and F are the same as in Example 2. Written amendment of 1991, ``Claims'' tree of the specification to be amended, column of ``Detailed description of the invention'' Invention disclosed in the case Address related to the case (520) 1990 Japanese Patent Application No. 258539 Processing composition and processing method for silver halide color photographic light-sensitive materials

Claims (6)

[Claims] (1) A compound represented by the following general formula (I) or a salt thereof, and Fe(III), Mn(III), Co(III), Rh
(II), Rh(III), Au(III), Au(II) and C
A processing composition for a silver halide color photographic light-sensitive material, which contains a metal chelate compound formed from a metal salt selected from e(IV). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1_1, R_1_2, R_1_3, R_1
_4, R_1_5, R_1_6 and R_1_7 represent a hydrogen atom, an aliphatic group or an aromatic group. R_1_8 and R_1_9 are a hydrogen atom, an aliphatic group, an aromatic group, a halogen atom, a cyano group, a nitro group, an acyl group,
Represents a sulfamoyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfonyl group or sulfinyl group. However, R_1_8 and R_1
_9 is not connected to form a ring. L_1 represents a divalent linking group containing an aliphatic group, an aromatic group, or a group consisting of a combination thereof. A_1 represents a carboxyl group, a phosphono group, or a hydroxy group. t and u represent 0 or 1. (2) A processing composition for a silver halide color photographic light-sensitive material, wherein at least one of t and u in general formula (I) according to claim (1) is 1. (3) A processing composition for a silver halide color photographic light-sensitive material, wherein t and u in the general formula (I) according to claim (1) are 1. (4) A method for processing a silver halide color photographic material, which comprises processing the imagewise exposed silver halide color photographic material with the processing composition according to claim (1). (5) A claim characterized in that the silver halide emulsion of the silver halide color photographic light-sensitive material contains 0.1 to 30 mol% of silver iodide, and is processed with the processing composition for 10 to 40 seconds. The method for processing a silver halide color photographic light-sensitive material according to item (2). (6) Claim (2) wherein the silver halide emulsion of the silver halide color photographic light-sensitive material is a silver chloride or silver chlorobromide emulsion, and the processing is performed with the processing composition for 5 to 30 seconds. ) A method for processing a silver halide color photographic light-sensitive material.