JPS62135835A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable sufficient desilvering in a short time without impairing photographic characteristics and improved processing with a small amount of waste water by using a desilvering step composed of a bleaching bath and the following bleach-fixing bath in a processing method of delivering in the presence of a specific compound. CONSTITUTION:The silver halide color photographic sensitive material is desilvered in the presence of one of the compounds represented by the formula shown on the right in the desilvering step composed of the bleaching bath containing at least one of a compound having a mercapto group or a disulfide bond, an isothiourea derivative, and a thiazolidine derivative, and the following bleach-fixing bath. In the formula, A is an n-valent aliphatic, aromatic, or heterocyclic bonding group, such as 3-12C alkylene or 6-18C arylene; X is -O-, -S-, or the like; and Y is an anion, thus permitting rapid sufficient desilvering to be executed in a short time.

Description

[Detailed Description of the Invention] (Industrial Field of Application) The present invention relates to an exposed silver halide color photographic light-sensitive material (
This invention relates to a processing method for color A optical materials (hereinafter referred to as color a-optical materials), and in particular, to a processing method that enables sufficient desilvering in a short period of time without impairing photographic properties, and an improved processing method that reduces the amount of waste liquid. .

(Prior Art) Generally, the basic steps in processing color photosensitive materials are a color development step and a desilvering step. In the color development step, the exposed silver halide is reduced by a color developing agent to produce silver, and the oxidized color developing agent reacts with a color former (coupler) to provide a dye image. In the next desilvering process,
By the action of an oxidizing agent (commonly referred to as a bleaching agent), the silver produced in the color development process is oxidized and then dissolved by a silver ion complexing agent, commonly referred to as a fixing agent. By going through the desilvering process, only a dye image is created on the color photosensitive material.

The above iron removal process is carried out in two baths, a bleach bath containing a bleaching agent and a fixing bath containing a fixing agent, and in a bleach-fixing bath containing a bleaching agent and a fixing agent. There is.

In addition to the basic steps mentioned above, the actual development process includes various auxiliary steps to maintain the photographic and physical quality of the image, or to improve the preservation of the image. For example, hardening. These include membrane baths, stop baths, image stabilization baths, and water washing baths.

Commonly used bleaching agents include red blood salt, dichromate, and ferric chloride.
Iron, aminopolycarboxylic acid ferrous complex salts, persulfates, and the like are known.

However, red blood salt and dichromate have pollution problems related to cyanide compounds and hexavalent chromium, and their use requires special treatment equipment. Furthermore, ferric chloride has problems in the production of iron hydroxide and staining during the subsequent washing process, which poses some practical problems. Persulfates have the disadvantage that their bleaching action is very weak and require a significantly long bleaching time. Regarding this, a method has been proposed to increase the bleaching effect by using a bleaching accelerator in combination, but persulfate itself is regulated as a dangerous substance under the Fire Service Act and requires appropriate storage measures, making it difficult to put into practice in general. There are drawbacks.

Aminopolycarboxylic acid ferric complex salt (% ethylenediaminetetraacetic acid ferric complex salt) is currently the most widely used bleaching agent because it has few pollution problems and does not have storage problems like persulfates. It is a drug. However, the bleaching edge of the ferric aminopolycarboxylic acid complex salt is not necessarily sufficient, and those using this as a bleaching agent cannot be used to produce low-sensitivity silver halide color light-sensitive materials based on silver chlorobromide emulsions. In the case of bleaching or bleach-fixing, it is possible to achieve the desired purpose, but it is difficult to use high-sensitivity color light-sensitive materials that are mainly composed of silver chlorobromoiodide or silver iodobromide emulsions and are color sensitized. When processing color reversal photographic materials and color negative photographic materials using high-silver food emulsions, there are disadvantages in that desilvering failure occurs and bleaching takes a long time.

For example, aminopolycarboxylic acid is used as a color negative photosensitive material for photography! When bleaching using an iron complex bleaching solution, the bleaching time is at least ≠ minutes, and in order to maintain the bleaching blade, it is necessary to control the pH of the bleaching solution and perform aeration. This requires complicated management. Even if such management is carried out, the reality is that there are still cases where defective bleaching occurs.

Furthermore, in order to desilver the trap, it is necessary to treat it with a fixing solution for at least 3 minutes following the bleaching process, and it is strongly desired to shorten the time required for such a long desilvering process. .

On the other hand, as a means of speeding up the desilvering process, a method of bleaching in which a ferric minopolycarboxylic acid complex salt and a periosulfate salt are contained in the solution as described in German Patent No. A fixing solution is known, but when a ferric minopolycarboxylic acid complex salt, which originally has a weak oxidizing power (S white blade), is combined with a thiosulfate salt, which has a reducing power, its bleaching power is significantly weakened. It is extremely difficult to sufficiently desilver color photographic materials with high sensitivity and high silver content, and the situation is such that they cannot be put to practical use. Of course, various attempts have been made in the past to improve the drawbacks of bleach-fix solutions, such as those described in British Patent Nos.
/degree! A method of adding iodide or bromide as described in ≠ publication, a method of adding iodide or bromide as described in JP-A No. Methods such as incorporating ferric iron complex salts are mentioned, but the effects of these methods are insufficient;
It cannot serve any practical purpose.

In addition to the lack of desilvering ability in bleach-fix solutions, cyan dyes formed during color development are treated with leuco dyes (Leuco dyes).
)ye), which has the major disadvantage of impairing color reproduction. This drawback, as described in US Pat. No. 3,773, No. 10, etc., is that increasing the pH of the bleach-fixing solution results in further weakening of the bleaching blade, which is an impractical condition. Also, U.S. Patent No. 3. /♂ji, Hiromu! Specification No. R2 discloses a method of oxidizing the leuco dye to cyan dye using a red blood salt bleaching solution after bleach-fixing, but the use of red blood salt has the above-mentioned pollution problem. Furthermore, even if bleaching is performed in the bleach-fix solution, it has little effect on reducing the amount of residual silver.

Another method of increasing the bleaching power of ferric aminopolycarboxylic acid complexes has been proposed by adding various bleaching accelerators to the bleaching bath, bleach-fixing bath, or their pre-bath.

For example, US Pat. ≠2 Specification, JP-A-Shoj3-/≠7623
Various mercapto compounds as described in the publication No.
Compounds having a disulfide bond such as those described in JP-A-53-TAJLS30, 1% azolidine derivatives as described in JP-A-Shoyu 3-TAR≠ Publication
Kaisho j3-ta lA'? Isothiourea derivatives such as those described in Publication No. 27, Japanese Patent Publication No. 4TJ-♂RotG,
Tokuko Akihiro ≠ Day 2 Otsu 5g Thiourea derivatives such as those described in Otsu No. Akihiro? - A thioamide compound as described in tA23 Hiroki Publication, I# Kaisho! Examples include dithiocarbamates such as those described in J-2 Ota No. 06.

Some of these bleach accelerators do have a bleach accelerating effect, but the effect is not necessarily sufficient.
Moreover, especially in a bleach-fix solution, the stability is extremely poor and the effect is lost in a short period of time, making it impossible to put it into practical use.

Particularly in image formation, color photosensitive materials containing tabular grains with excellent properties have been conventionally desilvered quickly to make full use of their properties.

Known accelerators cannot be said to be sufficient.

Furthermore, from the perspective of preventing environmental pollution, biochemical oxygen demand-1
Photographic processing liquids with high (BOD) and chemical oxygen demand (COD) need to be recovered and processed, and as the cost of recovery and processing is low, there is a strong demand for the development of processing methods that reduce the amount of waste liquid. There is.

<Object of the present invention>> The first object of the present invention is to improve color photosensitive materials (especially high sensitivity,
The object of the present invention is to provide a rapid processing method capable of sufficiently desilvering silver in a short period of time without impairing photographic properties (even for those with a high silver content). A second object of the present invention is to provide a processing method which is particularly suitable for the characteristics of color light-sensitive materials containing tabular grains without being sufficiently tedious. A third object of the present invention is to provide an economical treatment method that reduces the amount of waste liquid and requires less recovery and treatment costs.

Means for Achieving the Objects of the Invention The present inventors have discovered that in a processing method of desilvering in the presence of a compound represented by the following general formula [1] after color development, the desilvering step improves bleaching ability. and a bath having bleach-fixing ability provided after the bath, and at least seven bleach accelerators selected from compounds having a mercapto group or disulfide bond, isothiourea derivatives and thiazolidine derivatives are added to the bath having bleaching ability. Alternatively, the silver halide color photographic light-sensitive material can be processed by a processing method characterized in that the overflow liquid from the bath having bleach-fixing ability is introduced into the bath having bleach-fixing ability. The object of the present invention can be achieved by the processing method, which is characterized by having at least one layer or more of a silver halide emulsion containing tabular silver halide grains with a thickness of 5 times or more the grain thickness on a support. I found out.

That is, in response to the recent strong demand for faster processing, the desilvering step, which occupies most of the processing time, is added to the use of the compound represented by the following general formula [1].

By combining a bath having bleaching ability and a subsequent treatment method with a bath having bleach-fixing ability, the processing time can be significantly shortened, and furthermore, bleaching accelerators represented by general formulas (1) to (■) described below can be used. It has been found that further speeding up can be achieved by using the above process in combination with the above process.

It is noteworthy that this processing method enables rapid desilvering even for color light-sensitive materials containing tabular grain emulsions, where residual silver is a particular problem, and that its characteristics can be fully utilized. It is the right thing to do.

General formula [1] showing the general formula (1) of the compound here A is an n-valent aliphatic linking group, an aromatic linking group, a heterocyclic linking group, and (when n-/, A is a simple represents an aliphatic group, aromatic group, or heterocyclic group.) The aliphatic linking group represented by A includes an alkylene group having 3 to 2 carbon atoms (
Examples include trimethylene, hexamethylene, cyclohexylene, etc.). As the aromatic linking group, an arylene group having 6 to 1 g of carbon atoms (for example, phenylene,
naphthylene, etc.).

Examples of the heterocyclic linking group include heterocyclic groups (e.g., thiophene, furan, triazine, pyridine, pyridine, etc.) consisting of seven or more heteroatoms (e.g., oxygen atom, sulfur atom, nitrogen atom). can.

Here, the number of aliphatic linking groups, aromatic linking groups, and heterocyclic linking groups is usually seven, but two or more may be linked, and the linking format may be direct or a divalent linking group (for example, -〇-1-S-1-N-1-SO2-1-CQ- or a connecting group that can be formed from these connecting groups (R5 represents a lower alkyl group) may be connected via In addition, this aliphatic aromatic group, aromatic linking group, and heterocyclic linking group may have a substituent. Examples of the substituent include an alkoxy group, a halogen atom, an alkyl group, a hydroxy group, a carboxy group, and a sulfo group. , a sulfonamide group, a sulfamoyl group, and the like.

X represents 10-1-S-1 -N-, R represents a lower alkyl group (e.g. methyl group, ethyl group, etc.), R1 and R2 are substituted or unsubstituted lower alkyl groups (e.g. methyl group, ethyl group,
propyl group, isopropyl group, pentyl group, etc.), and substituents include hydroxy group, lower alkoxy group (for example, methoxy group, methoxyethoxy group, hydroxyethoxy group, etc.), amino group (e.g., unsubstituted Amino group, dimethyl terimino group, N-hydroxyethyl-N
-methylamino group, etc.) are preferred. Here, when there are two or more substituents, they may be the same or different.

R3 represents a lower alkylene group having 7 or more carbon atoms (methylene, ethylene, trimethylene, methylmethylene, etc.), and Y represents an anion (halide ion (chloride ion, bromide ion, etc.), nitrate ion).

sulfate ion, p-toluenesulfonate, oxalate, etc.).

In addition, R1 and R2 are connected via a carbon atom or a hetero atom (e.g., an oxygen atom, a nitrogen atom, a sulfur atom), and a 5- or 6-membered heterocycle (e.g., a pyrrolidine ring, a piperidine ring, a morpholine ring, a triazine ring) ring, imidazolidine ring, etc.).

R1 (or R2) and A are carbon atoms or heteroatoms (
For example, connected via oxygen atoms, nitrogen atoms, sulfur atoms),! A 6-membered heterocycle (eg, hydroxyquinoline ring, hydroxyindole ring, isoindoline ring, etc.) may also be formed.

Furthermore, R1 (or R2) and R3 are connected via a carbon atom or a heteroatom (for example, an oxygen atom, a nitrogen atom, a sulfur atom), and! A 6-membered or 6-membered heterocycle (eg, piperidine ring, pyrrolidine ring, morpholine ring, etc.) may be formed.

2 is 0 or /, m is 0 or /, n is /, 2 or 3, p is O or l, and q is 0. /, 2. Or represents 3.

Specific compounds included in the present invention are described below, but are not limited thereto.

CH2N(CH2CH20H)2 CH2N(CH2CH2OH)2 CH2N(CH2CH20H)2 CH2NCH2CH20H CH3 α2 2(H( CH2N NCH2CH20H --) CH2N(CH2CH20CH2CH20H)2aS H Cle αe 2(M(J, R2, M2) to H2← N (shil(2
R2(Jl-1)2H6H The compound of general formula (I) can be synthesized by the generally well-known method described in the following literature.

U.S. Patent Gill! 32, lr3 Hiroshi reference public Akihiro -
No. 72,03, Tokukai Sho! 7-/ri2. No. 3 When these compounds are present in the sensitive material, 7 m
The content is preferably 2 x 10-5 - /X 10-2 molar amount per 2 x /
It is preferable to contain a molar amount.

When present in the bath for the desilvering process, it is preferably contained in a molar amount of /X10-5 to /x10-'' per /L, preferably in a molar amount of /X10-' to 5x10-2. good.

In the present invention, the bleaching accelerator that can be contained in the bath having bleaching ability is selected from compounds having a mercapto group or disulfide bond, 1,000 plydine derivatives, thiourea derivatives, and isothiourea derivatives. , as long as it has a bleaching accelerating effect,
Preferably, those represented by the following general formulas (I) to (■) are preferred.

General formula (I) In the formula, R1 and R2 may be the same or different, and include a hydrogen atom, a substituted or unsubstituted lower alkyl group (preferably carbon number/~!, and a methyl group, an ethyl group, and a propyl group are particularly preferred). ) or an acyl group (preferably carbon number/~3, e.g. acetyl group, propionyl group, etc.), and n is /~
It is an integer of 3.

R1 and R2 may be linked to each other to form a ring (1° R1 and R2 are preferably substituted or unsubstituted lower alkyl groups.

Examples of the substituents R1 and R2 include a hydroxyl group, a carboxyl group, a sulfo group, and a ryomino group.

General formula (II) In the formula, R3 and R4 have the same meanings as R1 and R2 in general formula (I). n is an integer from / to 3.

R3 and R4 may be linked to each other to form a ring.R3 and R4 are preferably substituted or unsubstituted lower alkyl groups.

Here, examples of the substituents possessed by R3 and R4 include a hydroxyl group, a carboxyl group, a sulfo group, and a ryomino group.

General formula (1) General formula (V) In the formula, R5 is a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), an amino group, a substituted or unsubstituted lower alkyl group (preferably carbon number/xJ, % represents a methyl group, ethyl group, or propyl group (preferably a methyl group, an ethyl group, or a propyl group), or an alkyl group (such as a methylamino group, ethylamino group, dimethylamino group, or diethylamino group).

; Examples of the substituent that C iron R5 has include a hydroxyl group, a carboxyl group, a sulfo group, and an amino group.

General formula (Vl) In the formula, R6 and R7 may be the same or different.

Each has a hydrogen atom, an alkyl group that may have a substituent (preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, etc.), a phenyl group that may have a substituent, or a phenyl group that may have a substituent. (more specifically, a heterocyclic group containing at least 7 or more heteroatoms such as a nitrogen atom, an oxygen atom, or a sulfur atom, such as a pyridine ring, a thiophene ring, a thiacyridine ring, a benzoxazole ring, benzotriazole ring, thiazole ring, imidazole ring, etc.)
, R8 has the same meaning as R6, and R6 is a hydrogen atom or a lower alkyl group that may have a substituent (for example, a methyl group, an ethyl group, etc.).

It preferably represents the number of carbon atoms/~3°).

Here, the substituents that R6-R8 have include a hydroxyl group, a carboxyl group, a sulfo group, an amine group, and a lower alkyl group.

R9 represents a hydrogen atom or a carboxyl group.

General formula (■) In the formula, R□. , R1, and R1□ may be the same or different, and each represents a hydrogen atom or a lower alkyl group (for example, a methyl group, an ethyl group, etc., preferably an alkyl group having 1 to 3 carbon atoms).

RIO and R1□ or R12 may be linked to each other to form a ring.

X is a substituent (for example, a lower alkyl group such as a methyl group,
alkoxyalkyl groups such as acetoxymethyl groups)
Represents an amino group, a sulfonic acid group, or a carboxyl group that may have the following.

R10"" R12 is particularly preferably a hydrogen atom, a methyl group or an ethyl group, and X is preferably an amino group or a dialkylamino group.

General formula (■) R' In the formula, R1 and R2 represent a hydrogen atom, a hydroxyl group, a substituted or unsubstituted amide group, a carboxy group, a sulfo group, or a substituted or unsubstituted alkyl group, and R and R are hydrogen atoms. , represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted acyl group, and R and R may be connected to form a ring. M represents a hydrogen atom, an alkali metal atom or an ammonium group, and n represents an integer from 2 to 1.

General formula 1) In the formula, X represents N or C-R, and R, R1, R2, and R are a hydrogen atom, a halogen atom, an amide group, a hydroxyl group, a carboxy group, a sulfo group, or a substituted or unsubstituted alkyl group. , R4 and R5 represent a hydrogen atom, a substituted or unsubstituted alkyl group, or an acyl group, and R4
and R5 may be connected to form a ring. However, R4
and R5 cannot both be hydrogen atoms. 6n is O
Represents an integer from to o.

Preferred specific examples of the compounds represented by formulas (1) to (■) are shown below.

H2N−(CH2)2−8H (I)−+2+ (I) −(31 (I) −(4) (I) −(51 (I) −(6) (I) −(71 (1) −+9 ) (I) −(t) ([) −+2) (II) −(3) (If) −+41 (If) −(5) ([[) −+61 (n) −(7) (It) − (8) (It) −(9) ([[)−α1 (1) −(2j ([) −(3) (IV) −(1) (V) −(1) (V)=(2) H (VI) -(1) (VI) -(2) (Vl) -(3) (■) -(11 (■) -(21 (■) -+3) (■) -(6) (■) -(11 (Vl) -t2) (Vl) -(3) ([) -(1) (ff) -(3) (■) -(41 All of the above compounds can be synthesized by known methods. , in particular for compounds of general formula (I), U.S. Pat.
2♂! , Ri♂≠ Specification, G, Schwarzeenbach et al., Helveti force, Kimi force, Acta (G, Schwarze
nbach et al,) (elv.

Chim, Acta,), 31, //≠7(/ri!
! r3>, Roo, Clinton et al., Journal of
American Chemical Society (R,0,C11n
tone al,,J,Am,Chem,SOC,
), 70.9J″0 (/9 Hirodo), the compound of general formula (If) is disclosed in Japanese Patent Application Laid-Open No. 3-Tata Otsu No. 30, and the compound of general formula ([), (IV) is disclosed in Kaisho jlA-
Regarding the compound of general formula (V) in Publication No. 2j3≠,
Tokukai Shoj/-Otsur! rl, ♂ No., 3-/-707 Otsu No. 3, Otsu No. 33-30/Otori No. 3, No. 33-30/Otsu No. 3, No. 33-30/Otsu No. 3, No. 33-30/Otori No. 3, No. 33-30/No. !
♂-♂♂73g specification, the compound of general formula (■) is disclosed in JP-A-Sho! 3-9 Kori No. 27, the compound of general formula (~1) is published by Advanced In Heterocyclic Chemistry (Advancedin) (etero
cyclic Chemistry), 7, /Otsuj
-20 ri (/riotdo) as a reference, 2°! - Dimercapto/, 3. The compound represented by general formula (II), which can be easily synthesized by alkylation of ≠-thiadizole, can be synthesized by A, Wohl, W, Marzwald, Berichte (A, Wohl).

W, Marckwald, T3er), 22, rg
了(/to,!r?), M, 70 India, Berichte (M,
Freund, Ber, ), 2ri, 21AI3C/,
5'? A), A, P, T, Eerson et al., Journal of the Chemical Society (A, P, T,
Easson et al., J.Chem.Soc.), /ri3.
! ,/Ryo Otsuya, R.G., Johns et al., Journal of the American Chemical Society (R.G., Jon
es et al.

J,Am,Chem,SOC,,ヱヱ,≠000
It can be synthesized according to the method described in (/ri≠ri)).

When adding a compound having a mercapto group or a disulfide bond in the molecule, a thiazoline derivative, or an isothiourea derivative to a bleaching solution, the amount to be added depends on the type of photographic material to be processed, the processing temperature, and the amount required for the intended processing. Although it varies depending on the time etc., it is appropriate to have /x no θ ~ no 0-1 mol per 72 of the treatment liquid, preferably /x7
0 −J'×70 moles.

When adding these compounds to the treatment solution, it is common to dissolve them in water, alkaline organic acid organic solvents, etc. beforehand. However, it has no effect on the withdrawal promotion effect.

In the present invention, a bath mainly having bleaching ability (hereinafter simply referred to as "bleaching bath") is a bath containing a bleaching component and having the ability to bleach developed silver.

Specifically, it is a bath capable of bleaching at least 2/2, preferably 2/3 or more, and more preferably 'A/r or more of the maximum developed silver amount contained in the color photosensitive material. This bath is a processing bath that desilveres less than 772 of the total coated silver amount of the color light-sensitive material, preferably //3 or less, more preferably //j or less.

In addition, a bath having bleach-fixing ability (hereinafter simply referred to as a "bleach-fixing bath")
) is a bath capable of bleaching the developed silver that remained unbleached in the bleaching bath, and desilvering this together with the silver salt that remained undesilvered in the bleaching bath, and containing O per 72, This is a processing bath containing bleaching agent in an amount of OS moles or more.

For details, please refer to the maximum amount of developed silver contained in color photosensitive materials.
A bath that bleaches less than 72%, preferably //3
Below, a bath that bleaches less than //j is more preferable. The amount of this bath exceeds at least 2/2, preferably 2/3 or more, and more preferably ≠/! of the total amount of silver coated on the color photosensitive material. This treatment bath is capable of desilvering as described above.

The bleaching bath and bleach-fixing bath described above may each be composed of two or more baths, as long as the total bath is less than the total bath.

Further, a washing step (including a small washing step in which the amount of washing water is reduced) may be included between the bleaching bath and the bleach-fixing bath.

Furthermore, the overflow liquid resulting from replenishment from the bleach bath may be introduced directly or indirectly into the subsequent bleach-fix bath. In particular, direct introduction is preferred. This makes it possible to reduce part or all of the bleach that needs to be replenished into the bleach-fix solution.

In the present invention, the bleaching bath and bleach-fixing bath contain red blood salt monodichromate, persulfate, inorganic ferric salt,
Can all known products such as organic acid ferric salts be used?
Ferric complex salts of minopolycarboxylic acids are preferred because they cause less water pollution and metal corrosion and have good stability. Aminopolycarboxylic acid ferric complex salt is a complex of ferric ion and aminopolycarboxylic acid or a salt thereof.

Representative examples of these minopolycarboxylic acids and their salts include: A-/Ethylenediaminetetraacetic acid A-2 Ethylenediaminetetraacetic acid disodium salt A-3 Ethylenediaminetetraacetic acid diammonium salt A-≠ Ethylenediaminetetraacetic acid tetra(trimethylammonium) ) Salt A-J' Ethylenediaminetetraacetic acid tetrapotassium salt A-
A Ethylenediaminetetraacetic acid tetrasodium salt A-7 Ethylenediaminetetraacetic acid disodium salt -♂ Diethylenetriaminepentaacetic acid A-ta Diethylenetriaminepentaacetic acid pentasodium salt A-70 Ethylenediamine-N-(β-oxyethyl)
-N,N',N'-Triacetic acid A-// Ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid trisodium salt A-/2 Ethylenediamine-N-(β-oxyethyl )-N, N', N'-Triammonium triacetic acid salt A-73 Propylenediaminetetraacetic acid A-/IA Propylenediaminetetraacetic acid disodium salt A-/j Nitrilotriacetic acid A-/A Nitrilotriacetic acid trisodium salt A-/7-
Cyclohexanediaminetetraacetic acid A-/♂ Cyclohexanediaminetetraacetic acid dinatrilam salt A-meta-iminodiacetic acid A-20 Dihydroxyethylglycine A-2/ Ethyl etherdiaminetetraacetic acid A-22 Glycol etherdiaminetetraacetic acid A-23 Ethylenediaminetetrapropionic acid etc., but of course the compounds are not limited to these exemplified compounds.

Among these compounds, A-/~A-3, A-♂
and A-/7 are preferred.

Aminopolycarboxylic acid number! Iron complex salts may be used in the form of complex salts, or ferrous salts such as ferric sulfate, ferric chloride,
A ferric ion complex salt may be formed in a solution by using an aminopolycarboxylic acid with ferric nitrate, ferric ammonium sulfate, ferric phosphate, or the like. When used in the form of complex salts, seven types of complex salts or two or more types of complex salts may be used. On the other hand, when forming a complex salt in a solution using a ferric salt and an aminopolycarboxylic acid, the ferric salt is
One type or two or more types may be used. In addition, there are 7 types of aminopolycarboxylic acids or! More than one type may be used. In any case, the aminopolycarboxylic acid may be used in excess of the amount required to form the ferric ion complex.

Further, the bleach solution or bleach-fix solution containing the above-mentioned ferric ion complex may contain a metal ion complex salt other than iron, such as cobalt or copper.

In the present invention, a water-soluble bromide can be used as a rehalogenating agent in the bleach bath and/or bleach-fix bath.

Here, water-soluble bromide refers to a compound that releases bromide ions when dissolved in a bleach bath or bleach-fix bath, and specifically includes alkali metal bromides such as potassium bromide, sodium bromide, lithium bromide, etc. , ammonium bromide, hydrobromic acid, and alkaline earth metal bromides such as magnesium bromide, calcium bromide, strontium bromide, etc., but ammonium bromide is preferred.

These water-soluble bromides are present in the bleach bath at 0.0%. ! r～ノ、3
Contains mol/2, preferably 0.7 to 3 mol/2,
Also, in the bleach bath and bleach-fix bath, 0°/~o, rmol/
2, preferably 0.2 to 0. Tumol/fL included.

The bleaching bath and bleach-fixing bath of the present invention also contain nitric acid (I).
pH buffers such as nitrates such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. seven or more inorganic acids, organic acids, and salts thereof, as well as thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium thioaR ammonium, and potassium thiosulfate, sodium thiocyanate, and ammonium thiosiophosphate. , thiocyanates such as potassium thiocyanate, thioureas, thioethers, and the like.

In addition to the above, the bleaching bath and bleach-fixing bath according to the present invention may contain various additives as necessary.

For example, it may contain sulfites such as sodium sulfite, ammonium sulfite, etc., various antifoaming agents, or surfactants, iodides such as potassium iodide, sodium iodide, ammonium iodide, etc. Hydroxylamine, hydrazine, and bisulfite adducts of aldehyde compounds can also be included.

In the present invention, the bleaching solution lJ! The amount of bleach per serving is 0.
The amount is 7 mol to 1 mol, preferably 0.2 mol to O0j mol. Also, the pH of the bleaching solution should be ≠, 0~? ,
It is preferable that it be 0.

In the present invention, the amount of bleach per bleach-fix solution/2 is o
, or mol to 0.5 mol, preferably 0.7 mol to 0.5 mol.
3 mol, and the amount of fixing agent is 0.3 mol to 3 mol, preferably 0.3 mol. j moles to λ, tamol. Also, is the pH of the bleach-fix solution 5~? , preferably 6 to 7. It is evening.

In the present invention, the bleaching time is 20 seconds to ≠ minutes, and when a bleach accelerator is used, preferably 2Q seconds to ≠ minutes.
It is minute 30 seconds. If not used, preferably IAO
Seconds to seconds and minutes.

Further, the bleach-fixing time is preferably /min to j minutes,
More preferably, the time is 7 minutes 30 seconds to 3 minutes 3°-seconds.

After the fixing step or the bleach-fixing step, processing steps such as washing with water and stabilization are generally performed.

In the washing process and the stabilization process, various known compounds may be added for the purpose of preventing precipitation and stabilizing the washing water. For example, chelating agents such as inorganic phosphoric acid, monopolycarboxylic acid, and organic phosphonic acid.

Disinfectants and anti-inflammatory agents that prevent the growth of various types of bacteria, algae, and mold (e.g., Journal of Antibacterial and Antibacterial Agents (J.
Antibact, Antifung.

Agents) vol, / /, 16! , p
207～. 223 (/g3) and the compounds described in "Chemistry of Antibacterial and Antifungal" by Hiroshi Horiguchi), metal salts represented by magnesium salts, aluminum salts, bismuth salts, alkali metal and ammonium salts, Alternatively, a surfactant or the like may be added as necessary to prevent drying load and unevenness. Or West, Photographic Science and Engineering (Phol.

3ci, Eng,), Volume 6, 31AtA ~j59'
Compounds described on the page (/Riotyo) etc. may be added.

Addition of a special chelating agent or a sterilizing cutting agent is effective.

In the washing process, it is common to perform multistage countercurrent washing with two or more tanks (for example, one tank to two tanks) to save washing water. Furthermore,
JP-A-57-T instead of the washing process! ; A multi-stage co-current stabilization treatment process as described in No. 143 may be carried out. In addition to the above-mentioned additives, various compounds are added to this stabilizing bath for the purpose of stabilizing images. For example, adjusting membrane pH (
various buffering agents (e.g. borates) for pH 3-9).

Metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid,
Typical examples include dicarboxylic acids, polycarboxylic acids, etc.) and aldehydes such as formalin. In addition, chelating agents (inorganic phosphoric acid, polyminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), fungicides, anti-piping agents (
thiazole series, intinazole series, halogenated phenols, sulfanilamides, benzotriazoles, etc.),
Various additives such as surfactants, optical brighteners, hardener metal salts, etc. may be used, and two or more compounds for the same or different purposes may be used in combination.

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

Furthermore, in the case of color sensitive materials for photography, the normally performed post-fixing (washing-stabilization) process can be replaced with the above-mentioned stabilization process and water-washing process (water-saving treatment). At this time, if the magenta coupler is double-durable, the formalin in the stabilizing bath may be removed.

The washing and stabilization processing time of the present invention varies depending on the type of sensitive material and processing conditions, but is usually 20 seconds to 1Q minutes, preferably 20 seconds to j minutes.

Various treatment liquids in the present invention are used at 10°C to 10°C. It's not 33°C! Although the r'c temperature is standard, it is possible to increase the temperature to a higher temperature to accelerate the processing and shorten the processing time, or conversely to a lower temperature to improve image quality and stability of the processing solution. In addition, West German Patent No. 2.221. ．． No. 770 or U.S. Patent No. 3. The treatment using cobalt intensification or hydrogen peroxide intensification as described in Otsu 74L, ≠Tata, or the one-bath development bleach-fixing treatment described in U.S. Pat. No. 3,23,511 may be carried out.

Furthermore, each processing time can be made shorter than the standard time within a range that does not cause any problems, if necessary, in order to speed up the process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent or a precursor thereof for the purpose of simplifying and speeding up processing. 6 Specific examples of developer precursors are described in U.S. Pat.
, 3 Hiroko, Indoaniline compounds described in No. 577, No. 3゜3≠2. Tatata issue, Research Disclosure/lA250 (/ri 76th year) and the same/! /j
Schiff base-type compounds described in No. 3 (July 711), aldol compounds described in No. 2tA, U.S. Patent No. 3,7/9. ≠Metal salt complex described in No. 22, JP-A-33
-/There is a urethane compound described in No. 3jls2r,
Unexamined Japanese Patent Publication No. 233, J-1, 4. -/Otsu/33
No., rt-rri No. 232, same j Otsu-67♂lA2,
Same j6-♂373≠ issue, same evening issue 373, same j6
-Go No. 3736.

31. -f973ta issue, same j otsu-♂/ryo37 issue, same!
i′ Otsu-54Z Hiro 30, same j Otsu-/θ Otsu 2≠/, same j Otsu-107236, same Tahu Tafuta 3/ and same! Various salt type precursors described in No. 7-43jlj etc. can also be used in the present invention.

The silver halide color light-sensitive material of the present invention may contain various /-phenyl-3-pyrazolidones in order to promote color development. Typical compounds are JP-A No. 337, Tahu/≠Hiroyo≠7, Same! 7-. 2/
//≠ No. 7, same ♂-30! No. 32, same! ♂－! ;0!
No. 36, same g-ta 0! No. 33, same! ;f-! ;0j3
1A, jK-jOjf33 and J-1-//
J'A31 and other issues are listed.

Further, during continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the solution composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs.

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

When the light-sensitive material of the present invention is a color photosensitive material, it can be bleach-fixed if necessary, very generally, and even when it is a color photographic material for photographing.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Although amine phenol compounds are also useful as color developing agents, p-fuynylenediamine compounds are preferably used, typical examples of which include 3-methyl-≠-amino-N, N-diethylaniline, 3- Methyl-≠-amino-N-ethyl-N-
β-hydroxylethyl ester, 3-methyl-≠-T
Mi) -N-ethyl-N-β-methanesulfone, midoethylaniline, 3-methyl-Hiro-ami/-N-ethyl-N
-β-methoxyethylaniline and their sulfates,
hydrochloride, phosphate or p-toluenesulfonate,
Examples include tetraphenylborate, ~p-(t-octyl)benzenesulfonate, and the like. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

Examples of aminophenol derivatives include 0-aminophenol, p-aminophenol, and guamino-2-
These include methylphenol, λ-minnow 3-methylphenol, nioxy-3-minnow/, 44-dimethylbenzene, and the like.

In addition, "Photographic Processing Chemistry" by F. A. Mason, Focal Press (/A, 4th year) (L. F. A. Mason.

”photographic processingC
hemistry', Focal Press
)'s 226~! 29 pages, US Patent λ, /ri3,0/! It is also possible to use those described in No. 1, No. 36≠, JP-A No. 733, JP-A No. 733, and the like. If necessary, two or more color developing agents may be used in combination.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates; development inhibitors or capri-inhibitors such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. agent; hydroxylamine, triethanolamine, West German Patent Application (OLS) No. 21s2.2'? ! Preservatives such as compounds described in No. 0, sulfites or bisulfites; organic solvents such as diethylene glycol; benzyl alcohol;
Polyethylene glycol, Shitaku ammonium salt, amine, 1000 ocyanate, 3. Otsu-chiryo octane/,? −
Development accelerators such as diols; dye-forming couplers; competitive couplers; nucleating agents such as sodium boron hydride; auxiliary developers such as /-phenyl-3-pyrazolidone; viscosity-imparting agents; ethylenediaminetetraacetic acid, nitrilotriacetic acid , cyclohexanediaminetetraacetic acid, iminodiacetic acid,
N-Hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and 轡海昭子♂-/! 7! Ryominopolycarboxylic acid, /-hydroxyethylidene-/, /'-diphosphonic acid, research
Organic phosphonic acids described in Disclosure/I/70 (Yuzuki, 1997), aminophosphonic acids such as Ryominotris (methylene phosphonic acid), ethylenediamine-N, N, N', N'-tetramethylene phosphonic acid, JP-A No. 2-102'726, JP-A No. 3-≠2730, JP-A No. ≠-/2//27, same! −≠02≠ issue, same as left 14
tO2j issue, the same one! -/21s2Hiroshi/issue, same yoyo Ichiotata j,! R issue, same as left! 56, and Research Disclosure No. 71170 (J. 15'77).

Color developing agents are generally used in amounts of about 0.000000000000000000000000000000000000000000 have
/concentration of about 30y, more preferably a color developer /
It is used at a concentration of about /y - about /jP per 2. In addition, the pH of the color developer is usually 7 or higher, and most commonly,
It is used at about 1/3 to about 1/3. Furthermore, the amount of replenishment of the color developer can be reduced by using a replenisher with adjusted concentrations of halides, color developing agents, and the like.

In the development process for reversal color photosensitive materials, black and white development is usually performed followed by color development. This black-and-white developer includes dihydroxybenzenes such as hydroquinone and hydroquinone monosulfonate, 3-pyrazolidone systems such as /-fuynyro-3-pyrazolidone, or monophenols such as N-methyl-p-aminephenol, and other known black-and-white developers. Drugs can be used alone or in combination.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. Preferred silver halides are silver iodobromide or silver iodochlorobromide containing up to 30 moles of silver iodide. Particularly preferred is silver iodobromide containing from 2 to 2j moles of silver iodide.

The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. It may be one with crystal defects such as twin planes or a composite form thereof.

The grain size of the silver halide may be fine grains of 0.07 microns or less, dog-sized grains with a projected area diameter of up to 70 microns, a monodisperse emulsion with a narrow distribution, or a polydisperse emulsion with a wide distribution. good.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Beaumontel (P.

Glafkides, Chimie et phys
iquephotographique paul M
ontel, /riA7), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (Q, ):', puffi
n, Photographic Emulsion C
hemistry (Focal Press, /ri6o), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L, Zelikmanet
al, Making and Coating P
Photographic Emulsion, Foca
l Press, /! It can be prepared using the method described in I'OtA).

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). A method of keeping pAg constant in the liquid phase in which silver halide is produced as a form of simultaneous mixing method,
That is, a so-called Chondral double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Separate buttons formed. ! More than one type of silver halide emulsion may be mixed and used.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling pAg and pH during grain formation. For more information, see 7 Photographic Science and Engineering.
3science and Engineering) No. z
Volume, /jri~/Otsu! Page (/P4.2'): Journal
Of Photographic Science (Journal
of Photographic Science
), / Volume 2, 2'l-2~, 2! / page (/ri otsu≠
), U.S. Patent No. 3.6! ! , 3P41 and British Patent No. 1. It is described in 1Al3.7 Hiro issue.

A representative example of a monodispersed emulsion is an emulsion in which silver halide grains have an average grain diameter larger than about 097 microns, and at least about 5 times 1 inch of the silver halide grains are within ±≠0 inches of the average grain diameter. . The average particle diameter is approximately 0.23-. silver halide grains having an average particle diameter of ±2 microns and having a particle weight of at least about 9 cm or a quantity of at least about 9 cm;
Emulsions within the range of .o.

A method for producing such an emulsion is described in U.S. Patent No. 3. j7 Hiroshi.

Otsu Jr. No. 3 and 6! J, 3 references and British Patent No. 1. ! /j, 7! A? listed in the number.

Also, Tokukai Akihiro 1-41s00, same! /-3ri No. 927, same j/-♂3077, same evening 3-/37/33, same 311--IArj2/ No., same! Monodisperse emulsions such as those described in ≠-Tata≠/R No., J♂-3763J, and No. 773 may also be preferably used in the present invention.

By using tabular grains in the silver halide photographic emulsion used in the present invention, improvements in sensitivity including improvement in color sensitization efficiency by sensitizing dyes, improvement in the relationship between sensitivity and graininess, improvement in sharpness, and progress in development are achieved. Improvements in performance, covering power, crossover, etc. can be achieved.

Here, tabular silver halide grains have a diameter/thickness ratio of 5 or more, such as those exceeding 1 g or those having a diameter/thickness ratio of 5 or more and less than 5 g.

Further, the diameter of a silver halide grain refers to the diameter of a circle having an area equal to the projected area of the grain. In this technique, the diameter of the tabular silver halide grains is 0.3 to S, Oμ, preferably O1j to 3.0μ.

The thickness is less than o,ti-μ, preferably less than 0.3μ, more preferably less than 0.2μ.

Generally, tabular silver halide grains are tabular with two parallel planes, and therefore the above-mentioned "thickness" is expressed as the distance between the two parallel planes constituting the tabular silver halide grain. .

These tabular silver halide grains are
As described in No. 6, etc., it is also possible to use silver halide grains in a monodisperse state of grain size and/or thickness.

Here, the monodisperse of tabular silver halide grains refers to a dispersion system in which j% of grains fall within ±6o4 of the number average grain size, preferably within ±4L0% of the number average grain size. Here, the number average grain size is the number average diameter of the projected area diameter of silver halide grains.

Regarding the proportion of tabular silver halide grains in the emulsion containing tabular silver halide grains used in the present technology, it is preferable that the ratio of tabular silver halide grains to the total projected area is equal to or greater than j0, and should be equal to or greater than 70%. is more preferable, particularly preferably 90% or more.

The halogen composition of the tabular material is preferably silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, silver chloride, or silver iodochloride. Silver iodochloride is particularly preferred for use in high-sensitivity photosensitive materials. In the case of silver iodochloride, the silver iodide content is usually Hiromi/I/
% or less, preferably 20 mmol or less, more preferably 15 mmol or less. Furthermore, silver chlorobromide and silver bromide are particularly preferred for photosensitive materials for printing.

The tabular grains may have a uniform halogen composition or may consist of two or more phases having different halogen compositions.

For example, when silver iodobromide is used, the silver iodobromide tabular grains may have a layered structure consisting of a plurality of phases each having a different iodide content. Tokukai Showa 5g
Preferred examples of the halogen composition of tabular silver halide grains and the intra-grain distribution of halogen are described in No. 113121 and Japanese Patent Application Laid-Open No. 57-77-1993. In general, the desirable relationship between the relative iodide contents of each phase of tabular silver halide grains is determined by the details of the development process (for example, developer (amount of silver halide solvent contained in)
It is desirable to select the most suitable one.

Tabular silver halide grains include, for example, bonded silver halide crystals in which an oxide crystal such as PbO and a silver halide crystal such as silver chloride are combined, or epitaxially grown silver halide crystals (for example, on silver bromide). crystals grown epitaxially with silver chloride, silver iodobromide, silver iodide, etc., or hexagonal or octahedral silver iodide with silver chloride, silver bromide, silver iodide, etc.
Crystals obtained by epitaxially growing silver chloroiodobromide may also be used. Examples of these are U.S. Pat.
No., 1A63.0?7, etc.

Regarding the latent image formation size I-, the particles may be such that the latent image is mainly formed on the surface of the particle, or the particle may be such that the latent image is mainly formed inside the particle. This can be selected depending on the purpose of the photosensitive material using the tabular silver halide grains and the depth within the grain of a latent image that can be developed by a developer for processing the photosensitive material.

A preferred method of using the tabular silver halide grains of the present technology is as described in Research Disclosure/l622j3
1. t(lg3 years/ri), rotten coj330(/riza5
(May 2013), which discloses a method of use based on the relationship between the thickness and optical properties of tabular grains, for example.

The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. 1,027. /
Hirotsu No. 3, U.S. Patent No. 3. jor, ootg, maid, ≠≠
≠, No. ♂77 and Japanese Patent Application No. Shoj♂-21A♂1A67.

Further, silver halides having different compositions may be joined by epitaxial joining, and for example, silver halides, rhodan silver,
It may be bonded with a compound other than silver halide, such as lead oxide. These emulsion grains are described in U.S. Pat.
, 6g≠No., Intermediate, /≠2,900, IA Tata, 3j3, British Patent No. 1,03g, 792, U.S. Patent No. ≠, 3≠P, 622, Same≠, 3 Tata, 1It
No. 7♂, same≠.

≠, 33. ! 0/No., IA, IAlj3, 0♂ No. 7,
Same 3, Otsuyu Otsu, Ri No. 42, Same 3. ♂No. 32,067, Japanese Patent Publication No. 55'-/62! ; disclosed in IAO No. etc.

Also, mixtures of particles of various crystal forms may be used.

Silver halide solvents are useful to accelerate ripening. For example, it is known to have an excess of halogen ions present in the reactor to promote ripening. It is therefore clear that ripening can be accelerated simply by introducing a halide salt solution into the reactor. Other ripening agents can also be used and these ripening agents can be incorporated into the dispersion medium in the reactor prior to addition of the silver and halide salts, and/or two or more ripening agents can be used. can also be introduced into the reactor along with the addition of halide salts, silver salts or peptizers. As a further variant, the ripening agent can also be introduced independently at the halide salt and silver salt addition stages.

Ripening agents other than halogen ions include ammonia, amine compounds, and thiocyanate salts.

For example, 1% alkali metal thiocyanate salts, sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. The use of thiocyanate ripening agents is described in U.S. Pat. The teaching can be found in ≠Ko 1, 33≠ issue and Ko 3,320.0 Otori issue.

Also, US Pat. No. 3.27/, 137, 3. tough 4
Commonly used 1,000-onythyl ripening agents can also be used, such as those described in US Pat. Or Tokukai Showa 3-? 2≠0♂, same as left 3
It is also possible to use thione compounds as disclosed in No. 3/7.

By having various compounds present during the silver halide precipitation process, the properties of the silver halide grains can be changed. Such compounds may be initially present in the reactor or may be added along with one or more salts in accordance with conventional methods. US patent r
px, t1. ti-r, otsu no. 0, same 2. Otsu 2♂, / Otsu No. 7, 3, 737.

No. 373, No. 3,772,03/, and Research
Disclosure, /Volume 31A, /Z month, 1997, /
31A! ? Steel, iridium, lead, as described in 2.
Control of the properties of the arsenic halide by the presence of compounds such as bismuth, cadmium, zinc, (chalcogenic compounds such as sulfur, selenium and tellurium), gold and compounds of group II noble metals during the silver halide precipitation process. can.

Special public Akira! I-/lA No. 10, MOiser
r) et al., Journal of Photographic
As described in Science 1.2, Vol. 77, pp. 9-27, silver halide emulsions can be sensitized by internal reduction of grains during the precipitation formation process.

Silver halide emulsions are usually chemically sensitized.

Chemical sensitization is described in The Photographic Process, by T. H. James, 1st edition, Macmillan Publishing Co., Ltd., 1977, (T. H. James).

'l'he 'feory of the ph
otographic process, Hiroth ed.
It can be carried out using activated gelatin as described in MacNlan, / 77) 6, page 76, and also in Research Disclosure, Vol. 3≠Volume, /7/June, 13≠32, U.S. Patent No. 2,6≠2,36/, 3.2P7. ≠≠No. 6,
3゜772.037, 1!7.7//, 3, ri0/, 7/IA, μ2.2, 0/I
issue.

and 3. ri0≠, tA15, and moxibustion national patent No. 1
,3/r,7! ! pAgj~1 as described in the issue
0, pH! sulfur, selenium, tellurium, gold, platinum, /1 at r-f and temperature 30-40°C! Radium, iridium or a combination of these sensitizers can be used. Chemical sensitization is optimally carried out in the presence of a gold compound and a thiocyanate compound and as described in US Pat. ? 37,
7// issue, same≠.

2 otsu otsu, 01r oyo bido 44, 0! 'A, lA
Chemical sensitization can be carried out in the presence of a sulfur-containing compound such as a sulfur-containing compound or a hypo-, thiourea-based compound, or rhodanine-based compound described in No. 3, No. 7. The chemical sensitization aid used is a compound known to suppress fog and increase sensitivity in the process of chemical sensitization, such as azaindene, azapyridazine, and azapyrimidine. Examples of sensitizer modifiers include U.S. Pat.
．． ≠//.

ri/≠ issue, same 3. j! ≠, No. 757, Tokukai Shoj? -/2
Otsu! No. 2 Otsu and the aforementioned “Photographic Emulsion Chemistry” by Duffin, 7
3r~/lA, page 3.

In addition to or in place of chemical sensitization, U.S. Pat.
For example, reduction sensitization can be performed using hydrogen as described in U.S. Pat. No. 9/, ≠tA No. ! / Ryo, No. 62♂, Same 2
, 71A3, / r, , No. 2 O, J: Hidou λ, 7t
A3. using reducing agents such as stannous chloride, thiourea dioxide, polyamines and
Reduction sensitization can be achieved by pH treatment (for example, male to dog). Also, U.S. Patent No. 3. ri/7. ≠♂j and 3. It is also possible to improve color sensitization by the chemical sensitization method described in Ritsu Otsu, No. 76.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. The dyes used include cyanine dyes, merocyanine color 8.8-coated cyanine dyes, complex merocyanine color Particularly useful dyes are those belonging to the cylindrical, merocyanine, and complex merocyanine dye classes. Any of the nuclei commonly used for synergine pigments as basic heteroartic ring nuclei can be applied to these pigment cells. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied. These nuclei may have substituents on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a pyrazoline-yone nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,
It can be applied to j-member heteroartic ring nuclei such as IA-dione nucleus, thiazolidine-,2,lA-dione nucleus, rhodanine nucleus, and thiobarbic acid nucleus.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, a substituted aminostilbenzene compound with a nitrogen-containing heterocyclic ring group (for example, U.S. Pat. Nos. 2.33,370 and 3,633.7)
．． 2/), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3,7≠3.310), cadmium salts, azaindene compounds, and the like. U.S. Patent No. 3. Otsu/j, Otsu No. 73, Otsu No. 3
．． lI/! , l, IAI No. 3. Otsu/7, 2ri No. 5,
The combination described in No. 3, 1.33.7/No.

Spectral sensitization of the emulsion of the invention can be carried out at any stage of emulsion preparation.

Spectral sensitizing dyes are generally added to chemically sensitized emulsions before coating. U.S. Patent No. ≠, ≠2.

Hiro! No. 6 discloses a method of adding it to an emulsion before or during chemical sensitization. Further, methods of adding a spectral sensitizing dye to an emulsion before the formation of silver halide grains are completed are disclosed in U.S. Pat. Otsu 2♂, No. 760.

U.S. Patent≠, /do3, 7j1. No., and U.S. Patent≠
, 22 Ta, Otsu 6 No. Otsu.

In particular, U.S. Pat.

On the 22nd, 6 Otsu No. 6, by adding a spectral sensitizing dye to the emulsion after the formation of stable nuclei for silver halide grain formation, the photographic sensitivity was increased and the spectral sensitizing dye was adsorbed by the silver halide grains. It has been disclosed that there are advantages such as strengthening of

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

For the purpose of increasing sensitivity, increasing contrast, or promoting development, the photographic emulsion layer of the photographic light-sensitive material of the present invention may contain, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, 1,000 onythyl compounds, thiomol-7 oleins, quaternary It may also contain ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. For example, US patent λ, l100.33
No. 2, same λ, 1A23. ! ≠ No. 2, 7/Otsu, 06
No. 2, No. 3,6/7.2♂0, No. 3.772゜02/
No. 3. Ryo O♂, No. 003, IAI for UK patent! ,
Those described in No. 9-7 can be used.

The silver halide photographic emulsion used in this technology is used to prevent fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or to stabilize photographic performance.
Various compounds can be included. namely azoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles.

Mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (4-phenyl-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotridines ; thioketo compounds such as oxadorinthione, niazaindenes, e.g. doriazaindenes, tetraazaindenes (with % Hiro-hydroxy substitution (/
.

3.3a, 7) tetraazaindenes), hantaasaindenes, etc.; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can be added.

A variety of color couplers can be used in the present invention. Here, the term "color coupler" refers to a compound capable of coupling with an oxidized product of an aromatic primary amine developer to produce a pigment. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers which may be used without invention are given in Research Disclosure (RD)/71, 'A3.
C/ri7! R year/February) VI I-D section Oyohi same/♂
It is described in the patent cited on 7/7 (/?7P/July).

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-equivalent noble coupler substituted with a coupling-off group is preferable to a four-equivalent coupler in which the coupling active position is a hydrogen atom, since the amount of coated silver can be reduced. Further, a coupler in which the coloring dye has appropriate diffusivity, a colorless coupler, a DIR coupler that releases a development inhibitor or a coupler that releases a development accelerator upon coupling reaction can also be used.

Typical examples of yellow couplers that can be used in the present invention include oil-protected acylacetamide couplers. A specific example is US Patent No. 2. ≠
No. 07,270, same No. 2. ♂7! , No. 017 and Nos. 3 and 2! , J″06, etc. In the present invention, the use of two-equivalent yellow couplers is preferred, and is described in US Pat.
7.221, same No. 3. Oxygen atom separation type yellow couplers described in No. 33,301 and No. 022゜Otsu 2θ of the same Gil, or Tokuko Shoudo No. 1073,
U.S. Patent No. ≠, Hiro 0/, No. 712, U.S. Patent No. ≠, 3.2 B,
No. 02≠, RD/♂0j3 (Hirotsuki, 1997), British Patent No. 1. lA2! ;, No. 020, West German Application Publication No. 2, 2
/9. ri No. 77, 2nd, 2nd/, 3rd! No. 2,
327. ! ,! r7 and the same No. 2゜'A33. ♂/2
A representative example of this is the nitrogen atom dissociative yellow coupler described in No. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as yoichi pyrazolone and pyrazolotriazoles. A terpyrazolone coupler in which the 3-position is monochromated with an arylamino group or an acylamino group is preferable from the viewpoint of the hue of the coloring dye and the coloring density. 0♂ No. 2, same No. 2゜317-3.703, same No. 2. Otsu 00.71 #, same No. 2. Of, No. 373, No. 3,062,653, No. 3. /! 2. Go 9 Otsu No. 3 and No. 3 31. ．．
It is written in the 0/evening issue, etc. As a leaving group for two-equivalent yo-pyrazolone couplers, U.S. Pat.
1. /9 or the nitrogen atom leaving group described in US Patent No. ≠, 337. The arylthio group described in No. 7 is particularly preferred.

Also, European Patent No. 73. Otsu 3 The pyrazolone coupler having a pallast group described in No. Otsu can provide high color density.

As a pyrazolorozole coupler, U.S. Patent No. 3,
The pyrazolobenzimidazoles described in US Pat. Research Disclosure 2'A22
Pyrazolotetrazoles and Research Disclosure 2≠230 (/rirlA June 2008) and JP-A No. 1972-33-52 and Research Disclosure 2≠230 (/rirlA June 2009) and JP-A-1972-33-52 Examples include pyrazolopyrazoles described in Tata issue. U.S. Pat.
The imidazo(/,2-b)pyrazoles described in U.S. Pat. Otsuyo≠ Nogi Lazoro [/,! -b) (/, 2゜Hiro) triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include:

There are oil-protected naphthol-based and phenolic couplers, and U.S. Patent No. 2. ≠7≠.

No. 173, preferably the naphthol couplers described in US Patent No. ≠, 0! ; No. 2,272, same Gill.

/4' Otsu, 3rd No. 6, same No. ≠, 22g, 233 and same No. ≠, 2?1. ．． ．． ! A representative example is the oxygen atom dissociating type two-equivalent naphthol coupler described in No. 00. Further, specific examples of phenolic couplers include U.S. Pat.
No. i, same No. 2,772. /No. 62, No. 2. ♂ri! ,
It is written in No. 12 Otsu, etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention;
A typical example is U.S. Patent No. 3.712.002.
A phenolic cyan coupler having an alkyl group equal to or higher than ethyl group at the meta-position of the phenol nucleus, described in US Pat. No. 2,772. / Otsu No. 2, Otsu No. 3.7j♂, 30
g issue, same number hiro, /,! Otsu, No. 376, same No. ≠, 33'A
, No. 0/ /, No. 3.27゜773, West German Patent Publication No. 3,327,727 and European Patent No. 12/
, 2, which was written in 3 otsu j issue etc. -Diacylamino-substituted phenolic couplers and U.S. Patent No. 3. ≠IA Otsu, No. 622, same No. ≠, 333. ? It has a phenylureido group at the 2-position as described in No. 2, No. 2, No. 27,767, etc., and! These include phenolic couplers having an acylamino group at the - position. % Ganshojter93AO! , m59-26≠27
7 and 1 Tsukasa! 7-2 Otsu♂73! A cyan coupler in which a sulfonamide group, a ryomido group, etc. is substituted at the first position of the naphthol shown above also has excellent fastness of a colored image, and can be preferably used in the present invention.

Magenta and cyan couplers are used to correct unnecessary absorption in the short wavelength range of the dyes produced.

It is preferable to use a colored coupler in combination with a color negative photosensitive material for photography. Yellow-colored magenta couplers described in U.S. Pat.
i-,7,2? No., same No. ≠, /3 etc.

No. 2j and British Patent No. 1. /≠Otsu, No. 36♂, etc. are cited as typical examples of magenta-colored cyan couplers.

Granularity can be improved by using a coupler whose coloring dye has an appropriate diffusivity χ. Such blur couplers are described in U.S. Patent No. 3, No. 237 and British Patent No. 2. /23-, a specific example of a magenta coupler is given in No. J'70, and European Patent No. 2 is also given.

Specific examples of yellow, magenta or cyan couplers are described in No. 570 and West Germany Application Publication No. 3,23≠, No. 533.

Dye-forming couplers and special couplers listed above.

A polymer with more than a dimer? may be formed. A typical example of a polymerized dye-forming coupler is U.S. Pat.
/, No. 120 Oyo and No. 1A, 010.

It is described in No. 277. Specific examples of polymerized magenta couplers are described in British Patent No. 2. io, 2. i73, U.S. Patent No. 3A7. It is described in λg2, patent application Sho-Otsu 0-7!0 Hiro/, and m6Q-//33 Ri-O.

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

Standard stool dosages for color couplers range from o,ooi to 1 mole per mole of photosensitive silver halide, preferably from 0.07 to 00 for yellow couplers.
5 mole, 0.003 to 0.3 for magenta coupler
moles, and for cyan couplers 0.002 to 0.3
It is a mole.

The present invention may also include a coupler that releases a development inhibitor upon development, a so-called DIR coupler.

As a DIR coupler, for example, U.S. Pat. No. 3.227
, j, fIA, etc.; those that release a benzotriryozole derivative described in Japanese Patent Publication Shoj♂-Tata No. 4T2, etc. as a development inhibitor; Special public Akira! The so-called colorless DIR coupler described in /-/Otsu/IA/ etc.; the nitrogen-containing heterocyclic development inhibitor with the decomposition of washed methylol described in JP-A No. 2-TA-0RI-3; emitting: U.S. Patent No. 4'
, 2IAf, P Otsu No. 2 and JP-A-Shoj7-J-4g37
Those that release a development inhibitor with an intramolecular nucleophilic reaction after separation as described in No. 7;
-/j-lA2JtLt issue, same j7-/♂♂03! issue,
Same j♂-9 Go 72 No., same left No. 20773 Otsu, same Ta? -207737, same jr-20973g, same! l
JP-A-2073-73 and the same No. 1-2077≠0, which release a development inhibitor due to electron transfer via a conjugated system after separation; JP-A-37-1! /ri≠sign and the same! ? - Those that release a diffusible development inhibitor whose development inhibiting ability is deactivated in the developer described in Item 3 of 2/7, etc.; Patent Application Shoj
No. 263 on Ta 3, Ta 9-321. Examples include those which release the reactive compound described in No. j3, etc., and generate a development inhibitor or deactivate the development inhibitor by reaction in the film during development. Among the above-mentioned DIR couplers, those that are more preferable in combination with the present invention are the developer-deactivated type represented by JP-A No. 1999-1993; U.S. Patent Gill.

2'A♂, ri62 and JP-A-37-/j'A23
Timing type represented by ≠ issue; Tokugan Shojter 37 Otsu!
The reaction type represented by No. 3 is particularly preferable among them. ;/Yhiro≠ No., same 5g-2
/7ri No. 32, Tokuhan Sho Otter No. 7jlA7'A, 1i1
Developer deactivation type DIR couplers and patent application Sho J-9-3' described in I1 E9422/1A, F9-42.2/'A, and J Tata 0≠3r, etc. This is a reactive ff1DIR coupler described in Otsu No. 53, etc.

In the light-sensitive material of the present invention, a compound that releases a nucleating agent, a development accelerator, or a precursor thereof (hereinafter referred to as "development accelerator, etc.") in an image form during development can be used. A typical example of such a compound is British Patent No. 2,0
97. /≠O No. and No. 2. /3/, /I♂, and is a coupler that releases a development inhibitor etc. by a coupling reaction with an oxidized product of an aromatic primary amine developer, that is, a DAR coupler.

It is preferable that the development accelerator released from the DAR coupler has an adsorption group for silver halide.
It is described in No. 1.3F and Otter No. 770♂≠0. A sulfur or nitrogen atom separates from the coupling active site of a photographic coupler. Particularly preferred are DAR couplers that produce N-acyl-converted hydrazines having a monocyclic or condensed heterocycle as an adsorption group, and specific examples of such couplers are described in Japanese Patent Application No. 1-23770. ing.

JP-A-1999-1999 pO-37, which has a development accelerator moiety in the coupler residue! r31. The compounds described in the above-mentioned Japanese Patent Application No. Shoj♂-, 2/4j-♂0 which release a development accelerator or the like through an oxidation-reduction reaction with a developing agent may also be used as the light-sensitive material of the present invention. It can be used in

The DAR coupler is preferably introduced into the S-photosensitive silver halide emulsion layer of the light-sensitive material of the present invention, and
Tar/72 Otsu≠O issue or Tokuhan Showa jl? -,23710
As described in No. ≠, it is preferable to use substantially non-photosensitive silver halide grains in at least one of the photographic constituent layers.

Invention? The light-sensitive materials produced using the photosensitive materials contain hydroquinone derivatives, amine phenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamide phenol derivatives, etc. as color fogging inhibitors or color mixing inhibitors. May be contained.

Known anti-fading agents can be used in the light-sensitive material of the present invention. Known anti-fading agents include hydroquinones, O-hydroxychromans, and! -Hydroxycoumarans, spirochromans, p-alkoxyphenols,
Typical examples include hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, amine phenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Can be mentioned. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

In the photosensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer. For example, U.S. Patent No. 3
, ! ;! ;3, 7ri ≠ No. ≠ 2.23 O, O
/No. 3, Tokuko Akiyo/-otrIAo No. 3 and European Patent No. 3
7. IJ Azoles, U.S. Patent No. ≠, ≠Ta0,
No. 222 and the same No. ≠, /ri! , U.S. Patent No. 3.70, U.S. Pat. cinnamic acid esters described in US Pat. No. 3,2/2', 330 and British Patent No. 1. Benzophenones described in US Pat. No. 3.7AI, 272 and ≠.

A polymer compound having an ultraviolet absorbing residue such as that described in No. 1A3/, 721 can be used.

U.S. Patent No. 3. IA5P, No. 762 and IA5P No. 3゜7
The ultraviolet-absorbing optical brightener described in No. 00,≠Yo may be used. A typical example of a UV absorber is FLD2'
It is described in A23ri (/rig≠June), etc.

The photosensitive material of the present invention contains one or more surfactants for various purposes such as a coating aid, antistatic properties, improved slipperiness, emulsification and dispersion, prevention of adhesion, and improvement of photographic properties (for example, development acceleration, high contrast, and sensitization). But that's fine.

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

As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used, and in addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. be. An oil-soluble dye can also be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer.

In the photosensitive material of the present invention, the method for introducing a lipophilic compound such as a photographic coupler into the hydrophilic organic colloid layer is as follows:
Various methods can be used such as oil-in-water dispersion method, latex dispersion method, solid dispersion method, and alkali dispersion method, and the preferred method can be selected as appropriate depending on the chemical structure and physicochemical properties of the compound to be introduced. can.

The photographic coupler of the present invention can be added to two or more silver halide emulsion layers, preferably according to a latex dispersion method, more preferably an oil-in-water dispersion method. When following the oil-in-water dispersion method, the boiling point is /7j at normal pressure.
A water-based binder such as water or gelatin is dissolved in a high boiling point organic solvent (hereinafter referred to as "oil") having a temperature of 'C or higher or, if necessary, a low boiling point auxiliary solvent, preferably in the presence of a surfactant. Finely disperse in solution.

Representative examples of high boiling point organic solvents include U.S. Patent No. 21.272;
/ri No. 7, No. 2,322.027, Tokukai Sho! ≠-3/
72nd issue, and rlA-ii 21st issue, etc. (
above phthalate), JP-A-1973-/J20, same J! ;-
3, U.S. Patent No. 3,676.737, U.S. Patent No. 3,676.737
, 2/7. Kou No. 10, same No. ≠, 27g, 757, same No. ≠, 32 Otsu, 022, and same No. ≠, 3 yo 3. 79
(for phosphates or phosphonates), U.S. Pat. ! 33. ! ;/Hiroshi No., same No. ≠, iot.

tA0, and ≠, /27. t/3 etc. (amido), JP-A Showyu/-27722, JP-A-J3-/3
I1. /Hiroshi, same! 3-/3002♂, and U.S. Patent No. 2. ♂3. f, j7 number, etc. (alcohol or phenol), JP-A Showyu/-, 26037, same! /-2
7ri2/, same j/-/Hirori02♂, same! r/-/IAri02♂, same! ;2-31A7/j.

same! ;3-/jr2/, same 33-/3727, same Sahiro-
Yoto027, same! Otsu-Otsu≠333, same j Otsu-//lAri≠O1 U.S. Patent No. 3,7≠♂, /lA/ No.

3,777.76♂, ≠, 00≠, 72g, Gill, tAjO, lA21, and ≠,
Il, 30, 4122, etc. (all of which are aliphatic canebonic acid esters), JP-A-Sho! rf-10! /≠No. 7 (Ryo Nirin), Tokukai Sho! 0-Otsu 2 Otsu 3! , same j≠-Tata 1A32,
and U.S. Patent No. 3, 9/2.575, etc. (hydrocarbon), and others,
U.S. Patent No. 3. Otsu♂ri, No. 277, No. 3,700. ≠
Evening≠ issue, same No. 3, 76≠, 336, same No. 3, 7 Otsu! ,
♂ No. 77, No. ≠, 073.0, No. 12, No. ≠, 23
ri, Jj No. 1, West German Application Publication No. r, IAio, ri/II
Examples include those described in No. L. Two or more types of high boiling point organic solvents may be used in combination; for example, an example of a combination of phthalate and phosphate is US Patent No. 327.17.
It is stated in No. 3.

Tokukai Akira again! /-j Tata IA3, Special Publication Showa 51-37g
! No. 3, JLP-/2 Otsudo 30, U.S. Patent No. 2,77
2. /1, 3 and ≠, 20/.

It is also possible to use a dispersion method using a polymer described in J.R.

The binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention includes:

Although gelatin is advantageously used, other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; sodium alginate;
Sugar derivatives such as starch derivatives; single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylic pyrrolimide, polyvinylimidazole, polyvinylpyrazole, etc. A variety of synthetic hydrophilic polymeric materials can be used, such as.

As for gelatin, in addition to general-purpose lime-processed gelatin, acid-processed gelatin and the journal of the Japanese Society of Scientific Photography (Bull).

3oc, 3ci, photo, Japan), y16
Enzyme-treated gelatin 2 as described in /jp, page 30 (/ri6o) may be used, or a hydrolyzate of gelatin may be used.

In the photographic material of the present invention, an inorganic or organic hardening agent may be contained in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer. Specific examples include chromium salts, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), and N-methylol compounds (dimethylol urea, etc.). Active halogen compounds C2,4t-dichloro/Il-1,-hydroxy-/, 3°tertriazine, etc.) and active vinyl compounds (/, 3-bisvinylsulfonyl-2-propatur, /, 2-hisvinylsulfonyl) Acetamide ethane or a vinyl polymer having a vinylsulfonyl group in its side chain) is preferred because it quickly hardens hydrophilic colloids such as gelatin and provides stable photographic properties. N-carbamoylpyridinium salts and haloamidinium salts are also excellent in their fast curing speed.

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

Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The arrangement order of these layers can be arbitrarily selected as necessary. A preferred layer arrangement is in the order of red sensitivity, green sensitivity and blue sensitivity from the support side. Further, any emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the ultimate sensitivity, or a three-layer structure may be used to further improve graininess. Furthermore, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. A configuration may also be adopted in which emulsion layers of different color sensitivity are inserted between emulsion layers of the same color sensitivity.

Further, in a multilayer multicolor photographic material, a filter layer that absorbs light of a specific wavelength or a layer for preventing halation may be provided. The above-mentioned organic dyes can also be used in these light absorption layers.

Colloidal silver particles can also be used.

A non-light-sensitive fine-grain silver halide emulsion may be used in one or more non-light-sensitive layers of a multilayer, multicolor photographic material for the purpose of improving sensitivity by reflecting light or trapping development inhibitors.

A cyan-forming coupler in the red-sensitive emulsion layer and a magenta-forming coupler in the green-sensitive emulsion layer? Although it is common that each of the sensitive emulsion layers contains a yellow-forming coupler, a different combination χ may be used depending on the case. For example, it may be used in combination with an infrared-sensitive layer for pseudo-color photography or semiconductor laser exposure. Furthermore, as disclosed in Japanese Patent Publication No. 33-3≠♂/, unnatural color appearance can be removed by incorporating a coupler that develops a color other than a coupler that develops a color complementary to the color sensitivity wavelength of each layer. can.

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal that is commonly used in photographic materials. be done. Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (For example, paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer), etc.

The support may be colored using dyes or pigments.

It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion to photographic emulsion layers and the like. The support surface is coated before or after priming.
Glow discharge, corona discharge, ultraviolet irradiation, flame treatment, etc.2
It may be applied.

Various known coating methods such as dip coating, roller coating, curtain coating, and extrusion coating can be used to coat the photographic emulsion layer and other hydrophilic colloid layers. U.S. Patent No. 26112 as necessary≠
No., No. 27/77/, No. 33.21r, No. 2♂
Multiple layers may be applied simultaneously using coating methods such as those described in US Pat.

Various exposure means can be used for the photosensitive material of the present invention. Any light source that emits a radiation set corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination or writing light source. Natural light (sunlight), incandescent lamps, halogen-filled lamps, mercury vapor lamps, fluorescent lamps, and flash light sources such as strobes or metal-burning flashbulbs are common. Gaseous, dye solution or semiconductor lasers, light emitting diodes and plasma light sources emitting light in the wavelength range from ultraviolet to infrared can also be used as recording light sources. In addition, linear or planar microshutter arrays using phosphor screens (CRT, etc.), liquid crystals (LCD), and lanthanum-doped lead titanium zirconate (PLZT) emitted from phosphors excited by electron beams, etc. It is also possible to use an exposure means that combines a light source. If necessary, the spectral distribution used for exposure can be adjusted using color filters.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

Example/ On a trihedral acid cellulose film support with an undercoat,
Sample /16/, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is expressed in y/unit of silver for silver halide and colloidal silver, and for coupler.

For additives and gelatin, t is expressed in l/m, and for sensitizing dyes, t is expressed in moles per mole of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver...0. ≠gelatin
... 7.3 Colored coupler C-/
・ ・ 0.0 Otsu ultraviolet absorber UV-/
-0-0,/same as above UV-2...o8.2 Dispersion oil Qil-/...0.0/same as above
Qil-,! ...0.0/λth layer (intermediate layer) Fine grain silver bromide (average grain size 0.07μ) ...0. / Yoze “Lachin”
.../, 0 colored coupler C
-2... ・0.02 dispersion oil Qii-/
...0.7 3rd layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide emulsion, diameter 7/thickness ratio 2.
5 Average particle size 0.3μ)...Silver/,! gelatin
...0. Otsu sensitizing dye I ・
.../, 0x10"-'sensitizing dye II-
-・3.0X10-' Sensitizing dye I...
・/X/0-5 coupler C-J
...0.0 Otsu coupler C-Hiroshi ...0
．． 0 coupler C-f...0.0≠
Coupler C-Z...0.03 Dispersion oil Qil-/...0.03 Same as above Q
il-3...0, 072 Daiko II (second red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 6 molten, diameter/thickness ratio 3.5
Average particle size O0 μ) ・ ・ ・ / , Sensitizing dye ■ ... / × 10 ' Sensitizing dye ■ ... 3 X / 0-' Sensitizing dye ■ ... l × 10-5 power i-ra-
C-3・-・0.21A Coupler C-Hiroshi...0. ．． 21A Coupler C-K...0.0≠Coupler C-2・
・・o, oti− Dispersion oil Qil −/ ・・・0. /5 Same as above
Qil -3...0.0-Fifth layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 10 moles, diameter/thickness ratio/,
Evening average grain size 0.7μ) ...Silver! , 0 gelatin .../, 0 sensitizing dye ■
.../×10”-'sensitizing dye■
...3X10' sensitizing dye I
.../X10-5 coupler C-Otsu...
・0.0! Coupler C-7...0. / Dispersion oil Qi! -/...0.0/Same as above Qil-2...0.0! 2nd layer (middle layer) Gelatin...7.0 Compound c
pa-A...0.03 Dispersion oil Qi
L-/...O, OS 7th layer (first green-sensitive emulsion layer) Silver iodobromide emulsifier (silver iodide 2 molt, diameter/thickness ratio 2.
! Average particle size O63μ)...0.7 Sensitizing dye ■...! ×10' Sensitizing dye ■...0.3 x 10' Sensitizing dye V...2 X/0''-'Gelatin...7.0 Coupler C-
Ta...0.2 coupler C-Y
...0.03 coupler C-/
...0.03 dispersion oil 0il-/...
・Q, layer r-th layer (second green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide! Morch, diameter/thickness ratio 3. Average grain size 0.! μ) ・ ・ ・ /, 4' Sensitizing dye■ ...j X / 0-'
Sensitizing dye V...Co x 10-4 Sensitizing dye ■...0.3 x 10-' Coupler C-
Ta... 0.23 coupler C-/
...0.03 coupler C-10...
0.0/Ta coupler C-O...0.0/Dispersion oil Q i l-/...0.2 7th layer (third green-sensitive emulsion layer) Silver iodobromide emulsion (10 moles of silver iodide , diameter/thickness ratio/,
! r Average particle size 0.7μ) ...Silver/, tazelatin .../, 0 sensitized color accumulation■
...3. ! r×10' sensitizing dye ■
.../, lA×10' coupler C-/
/...0.0/Coupler C-72...
0.03 Coupler C-/3...0. ．． 20 coupler C-/...0.02 coupler C-
/l...0.02 Dispersion oil Q i
l-/...0.20 Same as above Qil-
,2...0.0! No. 70; Child (Yellow Filter M
) Gelatin...7.2 Yellow colloidal silver...O0/Otsu compound cpa-
B...0. /Dispersion oil Qil-/
...0.3 1st/layer (1F sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 6 molt, diameter/thickness ratio/, J' average grain size 0.3μ)... Silver 7.0 Gelatin.../, 0 Sensitizing dye ■...2 x 10' Coupler C-
/IA...0. ′? Coupler C-5...
・0.07 Dispersion oil Qil-/...0.1 12th layer (second blue-sensitive emulsion layer) Silver iodobromide (silver iodide 10 molt, diameter/thickness ratio/,!
Average particle size/, μ)...Silver 0.7 gelatin
...O0 Otsu sensitizing dye■ ・
・・・/×10' Coupler C-/≠ ・・・
0.2 to Labor Government Oil Qil-/...0.
07 No. 731 Excellent (first protective layer) Gelatin...O1♂ultraviolet absorber UV-/...0. / Same as above U
V-2...0.2 Dispersion oil Q i l-/...0.0/Dispersion oil Qil-2...0. O/ 1st≠14 (second protective layer) Fine grain silver bromide (average particle size 0.07μ) ・ ・ ・ 0.5 Gelatin ・・・0. ≠j polymethyl methacrylate particles (diameter/, jμ)...0.2 Hardener H-/...0. ≠Formaldehyde scavenger 8- /n・0. j Formaldehyde scavenger 8-,!・ ・
- 0.5 In addition to the above components, a surfactant was added to each layer as a coating aid.

Next, the chemical structural formulas or chemical names of the compounds used in this example are shown below: UV-/x/y-7/3 (weight ratio) UV-2 Qil-/tricresyl phosphate Qil-27 talic acid Dibutyl Q i I -371'keHis(,2-ethylhexyl)C-/C-co-j C-HiroIn+'6H13 -t C-/I CH3 -G C(CH3)3 0CH2Chi2SCH2COOH C-♂ C-ta CH3cooc4H9 α m'-=-, lj mol, wt, about, zo, oo.

C-/ / C-/2 α Sensitizing dye I Sensitizing dye ■ Sensitizing dye Sensitizing dye ■ Sensitizing dye ■ -j H-/ CH2-CH-3O2-CH2-CONH-CH2C)
(2-CH-3O2-CH2-CONH-C)i2S-
/ In addition, the compound described in the present invention (Table 2) was added to the first layer of the above sample.
) per /7rL',! , s x io-' moles were added according to Table 2-≠Table 2-Table 9-B, and other layers were the same as Sample /16/ to prepare sample plates 2 to ≠.

Further, sample waste O, A, 7 is the same as sample /16/.

The photographic element used a tungsten light source and the color temperature was adjusted to tA♂000K with a filter. After exposure to 2J-CMS, development was performed at 3rC according to the following processing steps.

(Processing process) Color development 3 minutes/even second bleaching So second bleach fixing
Washing with water for 7 minutes and 39 seconds Stable for 2 minutes and 30 seconds ≠ Q seconds The composition of the treatment liquid used in the process is as follows.

Color developer> Diethylenetriamine pentaB acid /, Oy/-hydroxyethylidene, z, oy-/, /-diphosphonic acid sodium sulfite ≠, oy potassium carbonate 30.0y potassium bromide i, ayy potassium chloride
/, 3-hydroxylamine sulfate 2. Hiroshi 1≠～(N-ethyl-N-β-≠, tough hydroxylethylamino)-2-methyl niline sulfate solution / 2pH 10
,00 (Bleach solution) Ethylenediaminetetraacetic acid 720 ferric ammonium salt Ethylenediaminetetraacetic acid 10. Op disonasodium salt ammonia water 7.0*1 ammonium nitrate 10. Ammonium oyyide ioo, oyy compound
j X / 0 = mol (compounds listed in Table-2,
Its addition follows the table-/) Add water / 2pH6,
0 Bleach-fix solution> Ethylenediaminetetraacetic acid so, oyy2
Iron ammonium salt ethylenediaminetetraacetic acid j, Oy dinasodium salt sodium sulfate /2. OP thiosulfate ammonium aqueous solution 2≠0-(70%) Ammonia water 10. Ow water? In addition / 2 pH 7, 3 stabilizer> * Lumari:y (37% W/V) 2,
Od Ho IJ Oxyethylene-P-mo/0.3P
Nonyl phenyl ether (average tOfio) water was added/2. The amount of residual silver was measured for each sample subjected to the above treatment. The results are shown in Table-/.

As is clear from the table, even in this short desilvering treatment time, the use of compound (1) or (9) or α mallet,
It can be seen that the amount of residual silver is smaller than that of the comparative example.

Table-/Table-2 Example-2 Seven of the bleaching accelerators shown in Table-3 were added to the bleaching bath at a rate of 72%. The treatment was carried out in the same manner as in Example-/, except that a bleaching solution containing 10 mol of silver was used and the bleaching time was 20 seconds, and residual silver was evaluated.

The results are shown in Table II-2.

In either case, it can be seen that more sufficient desilvering can be achieved by using the treatment method shown in the present invention.

Table-3 Table-≠-/(Using bleaching accelerator (II-3)) Table-4t-
, 2 (using bleach accelerator (rV-/)) Example-3 In Example-/, the diameter/thickness ratio of the emulsion and the amount of sensitizing dye were changed as follows.

5th layer (3rd red-sensitive emulsion layer) Diameter/thickness ratio7. j, sensitizing dye 1-1-,! times 7th layer (3rd green emulsion layer) Diameter/thickness ratio, ta, sensitizing dye ■, ■/.

6x 1st/layer (1st blue-sensitive emulsion layer) diameter/thickness ratio/layer, 3x sensitizing dye 72nd layer (2nd blue-sensitive emulsion layer)
Blue-sensitive emulsion layer) Diameter/thickness ratio: 20, sensitizing dye ■: 3. j times further embodiment-/coupler in /? Changed as below.

3rd layer (first red-sensitive emulsion layer) Using the same number of moles of C-/Yin instead of coupler C-Hiroshi. Addition table -! Example -≠ Example - except that the same emulsion as in Example 3 was used, a bleach solution containing the bleaching accelerator described in Example 2 was used, and the bleaching time was 20 seconds. The amount of residual silver after treatment was measured and the results are shown in Table B-/1 and Table B-2.

It can be seen that in any case, according to the present invention, more sufficient desilvering can be achieved.

Table-6-/(Using bleaching accelerator ([-j)) Table-Otsu-2(
Bleach accelerator (IT-/) used) Patent applicant: Fuji Photo Film Co., Ltd. Showa t/year] Mu/day Preservation Agency Director-General Palace 1゜Indication 1985 Patent Application No. 2744λ7
No. 2, Title of the invention Processing method for silver halide color photographic light-sensitive materials 3. Relationship with the case of the person making the amendment Patent applicant t Subject of the amendment ” Column 5, Contents of the amendment (“Silver halide” is inserted before “Processing method for color photosensitive materials” in “1. Title of invention column” of the 11EA specification.

(2) The "Detailed Description of the Invention" column of the specification is amended as follows.

“Patent applicant Fuji Photo Film Co., Ltd.” on page 726
Insert 6 in front of the following example.

Example to Example - Sample &l shown in / and the first layer of this sample,
Compounds described in the present invention (shown in Table 2)? As shown in Table 7, 2.1 x 10' mol per TrLz was added, and the other layers were the same as the sample &/ a% &/ b
, A/cf was created.

[Table 7] This photographic element was exposed to ICMS using a tungsten light source and the color temperature was adjusted by a filter, and then developed at 3r'C according to the processing steps below.

(Processing process/) Color development 3 minutes/j seconds bleach 30 seconds bleach fixing
Washing with water for 7 minutes and 30 seconds Stable for 2 minutes and 30 seconds ≠ Q seconds (processing step 2) Color development 3 minutes/J' seconds Bleaching 1 minute and 30 seconds Fixation Washing with water for 7 minutes and 30 seconds Stable for λ minutes and 30 seconds μO paper The composition of the treatment liquid used in the upper papermaking process was as follows.

<Color developer> Same as Example-/.

Bleach solution> Ammonium bromide /! 0.0? Compounds listed in Table-C Table-, rK Therefore, bleaching accelerators listed in Additive coating-3 Examples-/
same as.

(Bleach-fix solution) Same as Example 7 except that ethylenediaminetetraacetic acid or ferric ammonium salt was used.

Fixer> Ethylenediaminetetraacetic acid 1.0 and sodium salt Sodium sulfite ≠, ot Sodium bisulfite ≠, tf Ammonium thiosulfate water 171ml solution (7Q) Add water /1pH+,
+ <Stabilizing solution> Same as Example-7.

The amount of residual silver was measured for each sample subjected to the above treatment. The results are shown in Table-t.

As is clear from Table-r, A/(7 to 1
The improvement of desilvering by the treatment of the present invention is better than the improvement of desilvering by the treatment of the present invention with the bleach-bleach-fixing steps described in the present invention, using compounds and bleach accelerators for the process.
Alternatively, it can be seen that improvement in desilvering by treatment of /lμ to B shows better performance.

Example 6 Color photosensitive material containing the lithographic emulsion used in Example-3 @(
Sample &100) and the compound described in the present invention (shown in Table-λ) in the first layer of this sample, as shown in the entire table, /, 2
Add 4 mol of λ, J x 10 per layer, and sample &100 for other layers.
Sample shop 100a% & 100b, & 100c which is similar to
f was created.

[Table-2] Examples of these photographic elements! After processing in the same manner as above, the amount of residual silver was measured for each sample, and the results are shown in Table 10.

As is clear from Table 10, even when a lithographic emulsion is used, the bleach-bleach-fix process of the present invention is more effective when used with a bleach accelerator than the conventional bleach-fix desilvering process. It is clear that it is possible to make full use of its characteristics.

+ 17' foot 11 food 1 da - fΣ door discharge 〃 田 1. Indication of the case: Japanese Patent Application No. 276627 of 1982 2, Title of the invention: Processing method for silver halide color photographic light-sensitive materials 3, Person making the amendment 4, Date of amendment order: Sunset, February 2, 1988 (shipment date) 5 , Subject of amendment Specification 6, Contents of amendment Purification of the specification: 1 [F (no change in content)] will be submitted.

Claims (4)

[Claims] (1) In a processing method of desilvering in the presence of a compound represented by the following general formula [1] after color development, the desilvering step consists of a bath having a bleaching ability and a bath having a bleach-fixing ability provided afterwards. A processing method characterized by: General formula [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, A is an n-valent aliphatic linking group or an aromatic linking group (
When n=1, A represents a monovalent aliphatic group, aromatic group, heterocyclic group, or hydrogen atom; X is -O-, -S-
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R^1
, R^2 represents a substituted or unsubstituted lower alkyl group,
R^3 represents a lower alkylene group, and R^4 represents a lower alkyl group. Here R^1 and R^2, R^1 and A,
R^1 and R^3, R^2 and A, or R^2 and R^3 may be connected to form a ring. Y represents an anion, l represents 0 or 1, m represents 0 or 1, n represents 1, 2 or 3, p represents 0 or 1, and q represents 0, 1, 2 or 3; Selected to maintain sex. (2) Claim No. (1) characterized in that the bath having bleaching ability contains at least one bleach accelerator selected from compounds having a mercapto group or disulfide bond, isothiourea derivatives, and thiazolidine derivatives.
Treatment method described in Section. (3) The processing method according to claims (1) and (2), characterized in that an overflow liquid from the bath having bleach-fixing ability is introduced into the bath having bleach-fixing ability. (4) The silver halide color photographic light-sensitive material is characterized in that it has at least one layer on a support of a silver halide emulsion containing tabular silver halide grains with a grain size of 5 times or more the grain thickness. Claims (1) and (2)
and (3).