JPS6330845A - Color photographic developing solution composition and method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance the stability of a color developing solution, to reduce its change at the time of successive recessing or the like, and to prevent the rise of fog by incorporating an aromatic primary amine color developing agent and a specified compound. CONSTITUTION:The color photographic developing solution composition contains the aromatic primary amine color developing agent and the specified compound represented by the formula shown on the right in which R<1> is >=7 C alkyl or hydroxyalkyl; each of R<2> and R<3> is H, alkyl, or hydroxyalkyl; and at least one of each of R<1>-R<3> is hydroxyalkyl. This compound is added in an amount of 0.01-50g/l, preferably, 0.1-20g/l. This developing solution composition is superior in stability and color development performance and it can remarkably reduce the rise of the fog at the time of successive recessing or the like.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a color photographic developer composition and a method for processing silver halide color photographic light-sensitive materials using the same, and particularly relates to the stability of color developers. and improved color development,
The present invention also relates to a color photographic developer composition in which an increase in fog during continuous processing is significantly reduced, and a processing method using the same.

(Prior Art) Color photographic developers using aromatic primary amine color developing agents (hereinafter simply referred to as color developers) have long been used in color image forming methods, and are currently used in color photographic image formation. It plays a central role in the method. However, the color developer mentioned above is highly susceptible to oxidation due to the presence of air and metals, and if a color image is formed using a developer that has deteriorated over time, fog may increase and sensitivity and gradation may change. It is well known that the photographic characteristics may be different from what is desired.

Therefore, various methods of improving the preservation properties of color developing solutions have been investigated, and among them, the most common method is to use hydroxylamine and sulfite ions in combination. However, when hydroxylamine is decomposed, ammonia is generated, which causes fog, and sulfite ions act as competing compounds for developing agents, impeding color development. It's hard to call it a drug.

In addition, various preservatives and chelating agents have been investigated in order to improve the stability of color developers. For example, as a preservative, JP-A-52-49828,
Aromatic polyhydroxy compounds described in No. 9-160142, No. 56-47038, and U.S. Patent No. 3,746.544, etc., U.S. Patent No. 3,615,503 and British Patent No. 1,306,176 Hydroxycarbonyl compounds described in JP-A-52-143020 and JP-A-53-8
Examples thereof include α-aminocarbonyl compounds described in JP-A No. 9425, alkanolamines described in JP-A-54-3532, metal salts described in JP-A-57-44148 and JP-A-57-53749, and the like. In addition, as a chelating agent, Japanese Patent Publication No. 48-30496 and No. 44-3023
Aminopolycarboxylic acids described in No. 2, JP-A-56-97
No. 347, Special Publication No. 56-39359 and West German Patent No. 2
, 227,639, JP-A-5
No. 2-102726, No. 53-42730, No. 54-
121J27, 55-126241 and 55-
Examples include phosphonocarboxylic acids described in Japanese Patent Publication No. 65956, etc., and other compounds described in Japanese Patent Application Laid-open No. 58-195845, Japanese Patent Publication No. 58-203440, and Japanese Patent Publication No. 53-40900.

(Problem to be solved by the invention) However, even if these conventional techniques are used, satisfactory results have not been obtained, with both advantages and disadvantages, such as insufficient storage performance and adverse effects on photographic properties. do not have.

In particular, in color developing solutions from which benzyl alcohol, which is problematic in terms of pollution prevention and solution preparation, is removed, it is inevitable that the source of color development will deteriorate, and in such systems, preservatives that act as competing compounds are In order to significantly inhibit color development,
The conventional techniques described above are often unsatisfactory.

Furthermore, color photographic materials containing silver chlorobromide emulsions with a high chlorine content tend to cause fogging during color development, as disclosed in Japanese Patent Application Laid-open Nos. 58-95345 and 59-232344.
As stated in the issue. When using such emulsions, it is essential to develop a preservative that reduces the solubility of the emulsion and has better preservative performance.In this sense, there is also a demand for the development of a new developing solution. .

Therefore, an object of the present invention is to provide a developer composition for a silver halide color photographic light-sensitive material, which has excellent stability and color development properties and significantly reduces the increase in fog during continuous processing.

A further object of the present invention is to provide a color developer composition that does not substantially contain benzyl alcohol but does not reduce color density and has excellent stability.

Furthermore, the present invention improves the stability of the color developer,
An object of the present invention is to provide a method for processing a silver halide color photographic material, which significantly reduces changes over time during continuous processing and prevents an increase in cuff.

(Means for Solving the Problems) The above object of the present invention is to provide a silver halide color photographic photosensitive material containing an aromatic primary amine color developing agent and a compound represented by the following general formula (1). The developer composition of the material and the silver halide color photographic light-sensitive material are substantially free of pencil alcohol and contain the developer composition described above. This was achieved by a method for processing silver halide color photographic materials, which is characterized by processing with a developer.

General formula (I) In the formula, R1 is an alkyl group (7 or more carbon atoms, e.g. heptyl group, isooctyl group, t-octyl group, etc.), a hydroxyalkyl group (7 or more carbon atoms, e.g. 7-hydroxyethyl group, 7, 8-dihydroxyoctyl group, 4,4-
dihydroxy-1-methylhexyl group, etc.),
R2 and R3 each represent a hydrogen atom, an alkyl group (e.g. methyl group, isopropyl group, t-butyl group, etc.), or a hydroxyalkyl group (e.g. hydroxyethyl group, 3,3-dihydroxypropyl group, 2,3-dihydroxy -1-methylpropyl group, etc.).

The term "hydroxyalkyl group" as used herein refers to a straight or branched alkyl group substituted with one or more hydroxy groups.

In general formula (I), preferred substituents for R1, R2, and R3 are hydroxyalkyl groups. R1, R2
The total number of hydroxy groups introduced on R3 and R3 is preferably 2 or more, more preferably 2 to 6.

Further, the total number of carbon atoms of R 1 , R2, and R3 in general formula (I) is preferably 30 or less, more preferably 20 or less.

In the present invention, the amount of the compound of general formula (I) added is 0.0
The amount is 1 to 50 g, preferably 0.1 to 20 g.

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

I-(1) C7H15N(CH2(:II□0H)2I-(2) r-(3) (HOC)12)3CN(C7815)2I-(4) I-(5) r-(6) HO( (:+12) 7-NH2 I-(7) HO(OH) -N(CIl3)2 l-(8) HO-CIl -CI-((:I2)6-N(CH2C
l(20H)2I -(10) [HO-(C)I2)7+28CH3 I-(11) OH [+1o-cH-CIl-(Cll) +5-co(
CH3)2I-(12) C; H3 to H3 I-(1:1) C7H15N((:H□Cll2CH2011) 2l
-(14) I-(is) HO-(:H-C11-((:I2)6-Ni+2I-
(17) CHN[C(II:820+1)3]2I-(18) OH HO-(:H-CH-(CH) -N[(:(CH□0
11) 312I-(19) I-(20) The compounds according to the present invention can generally be synthesized according to the following synthesis examples or according to the method described in Japanese Patent Publication No. 57-8096.

Synthesis Example 1 (Exemplary Compound I-(1)) 115 g of n-hebutylamine, 300 g of 2-bromoethanol, and 330 g of potassium carbonate were placed in 2 volumes of dimethylformamide, and the temperature was raised to 120°C with stirring for 3 hours. Ho9ta.

After cooling, inorganic salts (potassium carbonate, potassium bromide) were filtered off from the reaction solution, and the solvent was distilled off from the filtrate. The obtained oil was distilled off under reduced pressure, and a pale yellow liquid bis(2
-hydroxyethyl) -n-hebutylamine to 160
I got g.

Actual measurement value as C11H25N02 C; 55.10 H, 12,45N, 6.
77 Calculated value C; 64.98 H: 1219 N
, 6.89 Synthesis Example 2 (Synthesis of Exemplified Compound I-(3)) 115 g of n-hebutylamine in Synthesis Example 1 was added to Tris(
450 g of pale yellow liquid tris(hydroxymethyl)-N,N-diheptylaminomethane was obtained in exactly the same manner except that 121 g of hydroxymethyl)aminomethane and 300 g of 2-bromoethanol were replaced with 430 g of 1-bromoheptane.

Actual value as 038H39N03 C, 81, 65H; 7.01 N, 2.6
:1 calculated value C, 81, 83H, 7, 05N, 2.5
The color developer of the present invention will be explained below.

The color developer used in the present invention contains a known aromatic primary amine color developing agent. Preferred examples are p-phenylenecyamine derivatives, and representative examples are shown below, but the invention is not limited to these.

D-I N,N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-[N-ethyl -N-(β-hydroxyethyl)aminocoaniline D-52-Methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-6N-ethyl-N-(β-methanesulfonamide ethyl)-3-methyl-4-aminoaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenecyamine D-94-amino-3- Methyl-N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline These p-phenylenecyamine derivatives may also be salts such as sulfate, hydrochloride, sulfite, and p-toluenesulfonate. The amount of the aromatic-grade amine developing agent used is 1 in the developing solution! ; the concentration is about 0.1 g to about 20 g per liter, more preferably about 0.5 g to about log.

The color developer of the present invention preferably contains a hydroxylamine represented by the following general formula (II).

General formula (II) R4-N-R''H In the formula, R4 and R5 represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, or an unsubstituted or substituted aryl group.

It is preferable that R, R'' is an alkyl group or an alkenyl group, and it is more preferable that at least one of them has a substituent. Furthermore, R4 and R5 may be connected together with a nitrogen atom to form a heterocycle.

Alkyl groups and alkenyl groups may be linear, branched, or cyclic, and substituents include halogen atoms (F, 0,
Br, etc.), aryl group (phenyl group, P-chlorophenyl group, etc.), alkoxy group (methoxy group, ethoxy group, methoxyethoxy group, etc.), aryloxy group (phenoxy group, etc.), sulfonyl group (methanesulfonyl group,
p-toluenesulfonyl group, etc.), sulfonamide group (
methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (diethylsulfamoyl group,
(unsubstituted sulfamoyl group, etc.), carbamoyl group (unsubstituted carbamoyl group, diethylcarbamoyl group, etc.), amide group (fuhythamide group, benzamide group, etc.), ureido group (methylureido group, phenylureido group, etc.)
, alkoxycarbonylamino group (such as methoxycarbonylamino group), aryloxycarbonylamino group (such as phenoxycarbonylamino group), alkoxycarbonyl group (such as methoxycarbonyl group), aryloxycarbonyl group (such as phenoxycarbonyl group), cyano group , hydroxy group, carboxy group, sulfo group, nitro group,
Amino group (unsubstituted amino group, diethylamino group, etc.),
Examples include alkylthio groups (such as methylthio groups), arylthio groups (such as phenylthio groups), and heterocyclic groups (such as morpholyl groups and pyridyl groups). Kotete R
and R5 may be the same or different from each other, and R4
, the substituents of R5 may also be rotated or different.

Further, the number of carbon atoms in R4 and R5 is preferably 1 to 10, particularly preferably 1 to 5. Examples of the nitrogen-containing heterocycle formed by linking R4 and R5 include a piperidyl group, pyrrolysilyl group, N-alkylpiperazyl group, morpholyl group, intolinyl group, and benztriazole group.

Preferred substituents for R4 and R5 are a hydroxy group, an alkoxy group, an alkyl or arylsulfonyl group, an amide group, a carboxy group, a cyano group, a sulfo group, a nitro group and an amino group.

Specific examples of the compound represented by the general formula (II) used in the present invention are shown below, but the scope of the present invention is not limited to these compounds.

H "C,, H5-N-C2H40CH3 n -(F) H CH3-N-C2H4QC2H5 n -(4) II-(5) H CH30(, H4-N-C2H40CH3II -(6
) H C2Hs OC2H4-N C2H40C2Hsn
-(7) H CH3QC2H,QC2)14-N-C2H4(XI:
2840CH3n -(a) H C2H3oC2H4N-C2H5 H HibikiC2H3QC2H4NCH2-CH2CH2II-(1
0) II-(11) n-(1z) ○H CH3-N-C2H4C0NH2 n-(13) II-(14) U-(Is) II-(16) ? 0 n - (17) H ■ 02H5302C2)1. -N-C2H4SO2C2H
5II-(18) ■-(19) ff-(20) U-(22) ■-(23) II-(24) II-(25) H "HOOC-CH2-N-CH2-Co○HII-( 27
) H HOCH2CH2NCH2CH,,0HII -(28
) n-(29) II-(30) 113-M, tag 112 and 1″2 digits +12 and +12 u-kun 3II-(31) II-(32) H II-(3:l) n- (:14) H20H The compound represented by the general formula (■) can be synthesized by the known method shown below.

U.S. Patent No. 3,661,996, U.S. Patent No. 3,362.96
No. 1, No. 3,293,034, Special Publication No. 42-2794
No. 3,491.151, U.S. Patent No. 3,655
, No. 764, No. 3.467.711, No. 3,45
No. 5,916, No. 3.287, 125, No. 3.28
No. 7,124 These compounds may form salts with various acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, and acetic acid.

The amount of the compound represented by the general formula (n) added to the color developer is 1 g to 20 g, preferably 0.5 g to Log o per 12 of the color developer.

The color developer of the present invention preferably does not substantially contain benzyl alcohol in terms of pollution prevention, liquid formulation properties, and prevention of cuffing. Substantially not containing T4 means that one color developer contains no more than two units of benzyl alcohol, preferably not at all.

Further, as a preservative, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts may be added as necessary. The amount of these additions is Og~20g/or preferably Og~5g/
If the stability of the color developer can be maintained, a smaller amount is preferable.

Other preservatives include hydroxyacetones described in U.S. Patent No. 3,615,503 and British Patent No. 1,306,176;
α-aminocarbonyl compound described in No. 425, JP-A No. 1973
Various metals described in JP-A-7-44148 and JP-A-57-53749, various saccharides as described in JP-A-52-102727, hydroxamic acids as described in JP-A-52-27638, α as described in JP-A-59-160141, α'-dicarbonyl compounds, salicylic acids described in No. 59-180588, alkanolamines described in No. 54-3532, No. 56
The poly(alkylene imine) described in No.-94349, the gluconic acid derivative described in No. 56-75647, etc. may be contained as necessary, and two or more of these preservatives may be used in combination as necessary. Good too.

Further, it is preferable to add an aromatic polyhydroxy compound.

The color developer of the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0, and may contain other known developer components.

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

Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt, N,N dimethylglycine salt, leucine salt, norleucine salt, quanine salt, 3,4-dihydroxy Phenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,
3-propanediol salt, Hasson's salt, Farosone's salt, trishydrodiaminomethane salt, lysine salt, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates are excellent buffer sources in the high pH range of 9.0 and above, and have excellent photographic properties even when added to color developers. It is particularly preferable to use these buffering agents because they have the advantages of having no adverse effect on surfaces (fogging, etc.) and being inexpensive.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, and boric acid. Potassium, sodium tetraborate (boric acid), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicyl), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (5- Examples include sodium sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is preferably 0.1 mole/or more, particularly 0.1 mole/or more. 1 mole/also ~0
．． Particularly preferred is 4 mol/liter.

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

The chelating agent is preferably an organic acid compound.

For example, Special Publication No. 48-30496 and No. 44-3023
Aminopolycarboxylic acids described in No. 2, JP-A-56-97
No. 347, Special Publication No. 56-39359 and West German Patent No. 2,
Organic phosphonic acids described in No. 227,639, JP-A-52
-102726, 53-42730, 54-1
No. 21127, No. 55-126241 and No. 55-6
Phosphonocarboxylic acids described in JP-A-58-195845, JP-A-58-203440, and JP-B-53-40900 can be mentioned. Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid diethylenetriamine pentaacetic acid ugly ethylenecyamine tetraacetic acid triethylenetetramine hexaacetic acid N,N,N-)-rimethylenephosphonic acid ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid 1,3-diamino -2-Propano-tetraacetic acid transcyclohexanecyaminetetraacetic acid nitrilotrifluoropionic acid 1.2-diaminopropanetetraacetic acid hydroxyethyl Phosphonobutane-1,2,4-tricarboxylic acid l-hydroxyethylidene-1,1-diphosphonic acid N,N'-bis(2-hydroxybenzyl)ethylenecyamine-N,N'-diacetic acid These chelating agents are necessary Two or more types may be used in combination depending on the situation.

These chelating agents may be added in an amount sufficient to sequester all conjugated ions in the color developer. For example, it is about 0.1 g to 10 g per sentence.

An optional development accelerator may be added to the color developer, if necessary. As a development accelerator,
No. 16088, No. 37-5987, No. 38-7826
No. 44-12380, No. 45-9019, and U.S. Pat. No. 3,813.247, etc.;
p-phenylenecyamine compound represented by No. 15554, JP-A-50-137726, equity 1 44-3
No. 0074, JP-A-56-156826 and JP-A No. 52-
Quaternary ammonium salts represented by No. 43429 etc., U.S. Patent Nos. 2,610,122 and 4,119,462
p-Aminophenols described in US Pat. No. 2,494
, No. 903, No. 3,128,182, No. 4,230,
No. 796, No. 3,253,919, Special Publication No. 41-11
No. 431, U.S. Pat. No. 2,482,546, U.S. Patent No. 2,59
Amine compounds described in Japanese Patent Publications No. 6,926 and No. 3.5s2,346, etc., Japanese Patent Publication No. 37-16088, No. 42-2
No. 5201, U.S. Patent No. 3,128,183, Special Publication No. 4
1-11431, 42-23883, and U.S. Pat. No. 3,532.501, and other l-phenyl-3-pyrazolidones,
hydrazines, mesoionic compounds, ionic compounds,
Imidazole and the like may be added as necessary.

In the present invention, any antifoggant may be added as necessary. Antifoggants include sodium chloride,
Alkaline total halides such as potassium bromide, potassium iodide, and organic anti-cuffing agents may be used. Examples of the organic anti-cuff agent include pentrienol, 6-nidropenzimitazole, 5-nitroinintasol,
Such as 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-henzimitazole, 2-thiazolylmethyl-benzimitazole, intasoles, hydroxyazaindolizine adenine Nitrogen-containing heterocyclic compounds can be cited as a representative example.

It is preferable that the color developer of Kippatsu 11 contains an optical brightener. As the fluorescent brightener, 4°4'-cyamitsu-2,2'-disulfostilbene compounds are preferred.

The amount added is O to 5 g/l, preferably 0.1 g to 4 g/l.

Furthermore, various surfactants such as alkylsulfonic acids, arylphosphonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 40°C. Processing time is 20 seconds ~ 5
Preferably 30 seconds to 2 minutes. The amount of replenishment is preferably small, or 1 rrr'' of photosensitive material + 20 to 600 rubs, preferably 50 to 300 rubs.More preferably 1 o
The print is od~200.

Next, the bleach solution, bleach-fix solution, and fix solution used in the processing method of the present invention will be explained.

As the bleaching agent used in the bleaching solution or bleach-fixing solution used in the present invention, any bleaching agent can be used, especially organic complex salts of iron(III) (e.g., ethylenecyaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc.). Complex salts of aminopolycarboxylic acids, aminopolyphosphonic acids, phosphonocarboxylic acids, and organic phosphonic acids) or organic acids such as citric acid, tartaric acid, and malic acid; n-sulfur atom: hydrogen peroxide, and the like are preferred. Among these, iron (II
The organic complex salts [) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. aminopolycarboxylic acids, aminopolyphosphonic acids useful for forming organic complexes of iron(III);
Or organic phosphonic acids or their salts are listed as ethylenecyaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β-oxyethyl)-N
, N”.

N'-triacetic acid, 1,3-diaminopropanetetraacetic acid, triethylenetetraminehexaacetic acid, propylenecyaminetetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, cyclohexanecyaminetetraacetic acid, 1,3-diamino-2-propanacetic acid Tools tetraacetic acid, methyliminodiacetic acid, iminodiacetic acid,
Hydroxyliminoniacetic acid, dihydroxyethylchrysine ethyl ether cyamisotetraacetic acid, glycol ethercyaminetetraacetic acid, ethylenecyaminetetrapropionic acid, ethylenediaminenipropionic acid, phenylenecyaminetetraacetic acid, 2-phosphonophthane-1°2. 4-triacetic acid, 1
,3-diaminopropanol-N,N,N',N'-
Tetramethylenephosphonic acid, ethylenediamine-N, N
, N-,N'-tetramethylenephosphonic acid, ■,3-propylenediamine-N,N,N',N''-tetramethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, etc. can.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 3-diaminopropanetetraacetic acid, iron ([[) complex salts of methyliminodiacetic acid, or bleaching blades are preferred because of their high cost.

These ferric ion complex salts may be used in the form of complex salts, and ferric salts 1 such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate A ferric ion rust salt may be formed in a solution using iron or the like and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid. When used in the form of a complex salt, one type of complex salt 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 a chelating agent, one or more types of ferric salts may be used.

Furthermore, one or more types of chelating agents may be used. In any case, the chelating agent is
It may be used in excess to form a diiron ion complex salt.

Among the iron complexes, aminopolycarboxylic acid iron rust is preferred, and the amount added is 0.01-L, Omol/u, preferably 0.05-0°5011oL/layer.

Further, a bleach accelerator may be used in the bleaching solution or the bleach-fixing solution, if necessary. Specific examples of useful bleach accelerators include U.S. Pat. No. 3,893,858, German Pat.
No. 53-32736, 53-57831, 53-37418, 53-65732, 5
No. 3-72623, No. 53-95630, No. 53-9
No. 5631, No. 53-1413, No. 53-12442
No. 4, No. 53-141623, No. 53-28426, Research Disclosure No. 17129 (July 1978), etc. Compounds having a mercapto group or disulfide group 2 JP-A-14012-1982
Thiazolidine derivatives as described in No. 9: Japanese Patent Publication Nos. 45-8506, 20832-1983, 53
-32735, thiourea derivatives described in U.S. Patent No. 3,706,561; Iodides described in West German Patent No. 1゜127.715 and JP-A-58-16235: West German Patent No. 966.410 , polyethylene oxides described in JP-A No. 2,748,430; polyamine compounds described in JP-A-45-8836; and other JP-A-49-424.
No. 34, No. 49-59644, No. 53-94927, No. 54-35727, No. 55-26506 and No. 58-163940, as well as iodine and bromide ions.

Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and in particular, US Pat. No. 3,893,858 and West German Patent No. 1,290,81
No. 2 and JP-A-53-95630 are preferred.

Additionally, the bleach or bleach-fix solutions of the invention may contain bromides (e.g. potassium bromide, thorium chloride, ammonium bromide) or chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride) or iodides (e.g. iodine). (ammonium chloride) rehalogenating agents. Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, as required
Adding one or more inorganic acids or organic acids with pH buffers such as sodium phosphate, citric acid, sodium citrate, and tartaric acid, and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine. I can do it.

The fixing agent used in the bleach-fixing solution or fixing solution in the present invention is a known fixing agent, namely sodium thiosulfate,
Thiosulfates such as ammonium thiosulfate: Thiocyanates such as sodium thiocyanate and ammonium thiocyanate: Water-soluble thioether compounds such as ethylenebisthiochricholic acid, 3.6-cythia 1.8=octanediol, and thioureas. These silver halide solubilizers can be used alone or in combination of two or more. In addition, a special bleach-fixing solution consisting of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354 can also be used.In the present invention, thiosulfate Particularly preferred is the use of ammonium thiosulfate.

The amount of fixing agent per sentence is preferably in the range of 0.3 to 2 moles, more preferably in the range of 0.5 to 1.0 moles.

The pH range of the bleach-fix solution or fixer solution in the present invention is as follows:
3 to 10 is preferred, and 5 to 9 is particularly preferred.

When the pH is lower than this, the desilvering property is improved or the deterioration of the solution and the leucoization of the cyan dye are promoted. On the other hand, if the pH is higher than this, desilvering is delayed and staining is likely to occur.

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

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

In the present invention, the bleach-fixing solution and the fixing solution are used as preservatives such as sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), methane, etc. Contains sulfite ion releasing compounds such as bisulfites (eg potassium metabisulfite, sodium metabisulfite, metabisulfite tj, ammonium acid, etc.). These compounds are approximately 0.02 to 0 in terms of sulfite ion.
．． It is preferable to contain 50 mol/metal, more preferably 0.04 to 0.40 mol/state.

As a preservative, a sulfite salt may be generally added, or ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, etc. may be added.

Furthermore, buffering agents, optical brighteners, chelating agents, antifungal agents, etc. may be added as necessary.

Next, the water washing step of the present invention will be explained. In the present invention, instead of the usual "water washing treatment", a simple treatment method may be used, such as performing only a so-called "stabilization treatment" without providing a substantial water washing step. In this way, in the present invention, “
"Water washing treatment" is used in the broad sense mentioned above.

The amount of washing water in the present invention varies depending on the number of baths in multistage countercurrent washing and the amount of pre-bath components of the photosensitive material brought in, so it is difficult to specify, or in the present invention, bleaching and fixing solution components in the final washing bath are It is sufficient if it is less than or equal to 1×1O−4. For example, in the case of 3-tank countercurrent water washing, approximately 1
It is preferable to use 000ri or more, more preferably 5
000d or more. In addition, in the case of water-saving treatment, 1 rrl of photosensitive material can be used for 100 to 1000 m! Is it okay to use it?

Water washing temperature is 15°C to 45°C1, preferably 20°C
~35°C.

In the washing process, for the purpose of preventing precipitation and stabilizing the washing water,
Various known compounds may be added. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphonic acid, bactericidal agents and antihyperglycants that prevent the growth of various bacteria, algae, and molds (for example, ``Journal of Antibacterial and Antibiotics'') J, AnLibact, Antifung
, Agents) Vol, 1 1, N01
5, p. 207-223 (1983) and the compounds described in "The Chemistry of Antibacterial and Antibacterial Kubo" by Hiroshi Horiguchi, gold Tjj, salts, alkali metals and ammonium salts represented by magnesium salts and aluminum salts, or A surfactant or the like may be added as necessary to prevent dry smoke load and unevenness. Or West's ``Photographic Science and Engineering Magazine (Phot).

A compound described in Sci.

Furthermore, the present invention is particularly effective in cases where a chelating agent, a bactericide, or an anti-piping agent is added to the washing water, and the amount of washing water is greatly reduced by multi-stage white wave washing using two or more tanks. It is also particularly effective when carrying out a multistage countercurrent stabilization process (so-called stabilization process) as described in JP-A-57-8543 instead of the usual water washing process. In these cases, the bleaching and fixing components in the final bath may be at most 5xlO', preferably at most 1x10-2.

Various compounds are added to this stabilizing bath for the purpose of stabilizing the image. For example, adjusting the membrane pH (for example, pH 3 to
8) various buffering agents (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) Typical examples include aldehydes such as (used in combination) and formalin. In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarbonate), fungicides (thiazole series, isothiazole series, halogenated phenols, sulfanilamide, penzo) Triazole, etc.), surfactants, optical brighteners, hardeners, and other various additives 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 types of ammonium such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate to improve image preservation.

When the amount of washing water is significantly reduced as described above, it is preferable to allow some or all of the overflow liquid of washing water to flow into the bleach-fixing bath or fixing bath, which is a pre-bath, for the purpose of reducing the amount of drainage liquid. .

In this treatment step, during continuous treatment, a constant finish can be obtained by using a replenisher for each treatment solution to prevent fluctuations in the liquid 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, nitrogen stirring, air stirring, etc., as necessary.

If the method of the present invention uses a color developer,
It can be applied to any processing process. For example, it can be applied to processing color vapor, color reversal vapor, color positive film, color negative film, color reversal film, etc.

/'/'7.' The silver halide emulsion of the light-sensitive material to which the processing method of the present invention is applied does not contain any halogen such as silver iodobromide, silver bromide, silver chlorobromide, silver chloride, etc. Although a silver chloride emulsion or a silver chloride emulsion containing 60 mol% or more of silver chloride is preferable when performing rapid processing or low replenishment processing, it is preferable to use a silver chloride emulsion containing 60 mol% or more of silver chloride. Particularly preferred is 80 to 100 mol%.

In addition, high sensitivity is required, and during manufacturing, storage, and/or
Alternatively, if it is necessary to particularly suppress fog during processing, a silver chlorobromide emulsion or a silver bromide emulsion containing 50 mol % or more of silver bromide is preferred.

More preferably, it is 70 mol% or more. If the silver bromide content exceeds 90 mol%, rapid processing becomes difficult or means for accelerating development, such as using a development accelerator such as a silver halide solvent, a cuffing agent, or a developer as described below during processing. In some cases, it may be preferable to use the method, since development can be accelerated to some extent without being limited by the content of silver bromide. In either case, it is not preferable to contain a large amount of silver iodide, and it is sufficient if the content is 3 mol % or less.

In the present invention, the silver halide grains of the silver halide emulsion may have different phases in the interior and surface layers, may have a multiphase structure such as a bonded structure, or may have a uniform phase throughout the grains.

Also, they may be mixed.

The average grain size of the silver halide grains (in the case of spherical or near-spherical grains, the grain diameter is the grain size, and in the case of cubic grains, the grain size is the ridge length, and is expressed as the average based on the projected area. In the case of tabular grains, it is also spherical. Expressed by calculation) is
It is preferable to have a value of 0.1μ or more, particularly preferably 1.5μ or less. tsJL or higher. The grain size distribution may be narrow or wide, and is preferably within 20% of the standard deviation of the grain size distribution curve of the silver halide emulsion divided by the average grain size (variation rate). 1
It is preferred to use so-called monodisperse silver halide emulsions of up to 5% in the present invention. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are used in an emulsion layer having substantially the same color sensitivity (monodispersity is defined as the above-mentioned type). (preferably those having a variable rate) may be mixed in the same layer or coated in separate layers. Furthermore, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or in a layered manner.

The silver halide grains used in the present invention have a regular shape such as a cube, octahedron, rhombidodecahedron, and dodecahedron.
It may have an ar) crystalline structure or a coexistence of these crystals, or it may have an irregular shape such as a spherical shape.
It may have a crystalline form (gular), or it may have a composite form of these crystalline forms. Tabular grains may also be used, especially when the length/thickness ratio is 5 or more, especially 8.
The above tabular grains or an emulsion occupying 50% or more of the total projected area of the grains may be used. An emulsion consisting of a mixture of these various crystal forms may also be used. These various emulsions may be of either a surface latent image type in which a latent image is formed on the surface as a seed, or an internal latent image type in which a latent image is formed inside the grains.

The photographic emulsion used in the present invention is described in "Chemistry and Physics of Photography J" by Glafkides [P., Glafkides, Chi.
mieet Physique Phbtograph
ique (published by Paul Monte 1, September 1967, "Photographic Emulsion Chemistry" by Duffin [G, F, D
uffin, Photographic Emulsi
on (:hemistry(Focal Pres.
V, L, Zelikman et al., "Production and Coating of Photographic Emulsions J"
l, “Making and Cocting Ph.
oLogr'aphic Emulsion (Foca
It can be prepared using the method described in J. Press, 1964). i.e. acid method,
Any of the 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.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). Simultaneous mixing method 1
PAg in the liquid phase formed by silver halide as two forms
The method of keeping constant is the so-called chondral
A double jet method can also be used. According to this method, a silver halide emulsion with crystalline or regular grain size and nearly uniform grain size can be obtained.

Furthermore, emulsions prepared by the so-called conversion method, which involves a process of converting silver halide already formed during the silver halide grain formation process to silver halide with a smaller solubility, and Emulsions which have undergone similar halogen conversion after the silver grain formation process can also be used.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, lead salt, copper salt, thallium salt, iridium salt or its v1it! , a rhodium salt or a complex salt thereof, an iron salt or an iron rust salt, etc. may be present together.

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

Known silver halide solvents (e.g. ammonia, Rodanka or U.S. Pat. No. 3,271,157, JP
1-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717, JP-A-54-155828, etc.) by precipitation, physical It can be used by aging or chemical ripening. In order to remove soluble silver salts from the emulsion after physical ripening, a Nupur water washing method, a flocculation sedimentation method, an ultrafiltration method, etc. are used.

The silver halide emulsion used in the present invention contains active gelatin and sulfur-containing compounds that can react with silver (for example, thiosulfate,
Sulfur sensitization method using reducing substances (such as stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds): Metals Compounds (e.g., total complex salts, Pt, Ir, Pd, Rh, Fe
A noble metal sensitization method using complex salts of metals of group 1 of the periodic table) can be used alone or in combination.

The blue-sensitive, green-sensitive and red-sensitive emulsions of the present invention are spectrally sensitized with methine dyes and other dyes so as to have their respective color sensitization properties. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. Namely, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, virol 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 Nuclei, quinoline nuclei, etc. can be applied. These nuclei may be replaced on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohytantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, etc.
It is possible to apply a ring 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. Typical examples are U.S. Patent Nos. 2,688,545, 2,977.229, 3,397,060, 3,522,052,
Same No. 3,527.64-. No. 1, No. 3,617,29
No. 3, No. 3.628,964, No. 3,666.4
No. 80, No. 3,672,898, No. 3.679.
No. 428, No. 3.703, 377, No. 3.769
, No. 301, No. 3,814,609, No. 3,83
No. 7,862, iR4,026,707, British Patent No. 1,344,281, British Patent No. 1,507,803, Japanese Patent Publication No. 43-4936, Japanese Patent Publication No. 53-12375, Japanese Patent Publication No. 110618-1983 No. 52-109925.

Along with sensitizing dyes, dyes that do not themselves have spectral sensitizing effects or substances that do not substantially absorb visible light, 1
Substances exhibiting supersensitization may also be included in the emulsion.

These sensitizing dyes may be added at any stage during particle formation, before or after chemical sensitization, during chemical sensitization, or during coating. Addition during particle formation not only enhances adsorption, but is also effective in controlling crystal shape and intraparticle structure. Furthermore, addition during chemical sensitization does not strengthen adsorption, and is effective in controlling chemical sensitization sites and preventing crystal deformation. These addition methods are particularly effective in the case of emulsions containing a high content of KM silver, and it is also particularly useful to apply them to grains with a high content of silver bromide or silver iodide on the grain surface. It is.

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized, and whose coupling active position is t-substituted with a leaving group rather than a four-equivalent color coupler with a hydrogen atom. 2-equivalent color couplers, 0 color-forming dyes that can reduce the amount of silver coated, couplers with appropriate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor upon coupling reaction, or developable couplers. Couplers that release promoters may 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 U.S. Patent No. 2,40
No. 7,210, No. 2゜875.057 and No. 3
, No. 265, 506, etc. The use of two-equivalent yellow couplers is preferred for the present invention; U.S. Pat.
No. 3,933,501 and No. 4゜022.62
0, etc., or Japanese Patent Publication No. 58-10739, U.S. Patent No. 4,
No. 401,752, No. 4,326,024, RD1
8053 (April 1979), British Patent No. 1,425,
020, West German Application No. 2.219,917, West German Application No. 2,261,361, West German Application No. 2,329,587 and West German Application No. 2,433,812, etc. Yellow coupler is a typical example. 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 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and typical examples thereof include U.S. Pat. Same 2nd and 3rd
No. 43,703, No. 2,600,788, No. 2,
No. 908,573, No. 3,062.653, No. 3
, No. 152,896 and No. 3,936,015. As a leaving group for a two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or U.S. Pat.
．． 5-pyrazolone couplers, preferably having an arylthio group as described in European Patent No. 897, and a ballast group as described in European Patent No. 73,636, provide high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
369,879, preferably the pyrazolo[5,1-c][1,2,4] triazoles described in U.S. Pat. No. 3,725,067, Research Disclosure 24220
(June 1984) and Research Disclosure 24230 (19
In terms of the low yellow side absorption and light fastness of color-forming dyes, the imidazo [
1,2-b]pyrazoles are preferred, as described in European Patent No. 11
Pyrazolo [1,5-bl [1,
2°4] triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenolic couplers, preferably the naphthol-based couplers described in U.S. Pat. No. 2,474,293, and preferably U.S. Pat.
, No. 212, No. 4.146,396, No. 4,22
Typical examples include f$, an atom dissociative type two-equivalent naphthol coupler described in No. 8,233 and No. 4,296,200. Further, specific examples of phenolic couplers are given in U.S. Patent Nos. 2,369,929 and 2
, No. 801,171, No. 2,772.162, No. 2,895,826, etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention and are typically described in U.S. Pat.
72,002, a phenolic cyan coupler having an alkyl group of ethyl or higher in the meta-position of the phenol nucleus, U.S. Pat. No. 2,772,162, U.S. Pat. No. 3,
No. 758,308, No. 4,126.396, No. 4
, No. 334,011, No. 4.327,173, West German Patent Publication No. 3,329.729 and Japanese Patent Application No. 1983-4
2,5-diacylamino-substituted phenolic couplers described in U.S. Pat. No. 2671, etc. and U.S. Pat.
．． 559 and No. 4,427,767, etc., which have a phenylureido group at the 2-position and have a 5-
These include phenolic couplers having an acylamino group in the position.

Graininess can be improved by using a coloring dye or a coupler with appropriate diffusivity. Such dye-diffusive couplers are described as examples of magenta couplers in U.S. Pat. No. 533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,451,82.
No. 0 and No. 4,080.211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102.173 and US Pat. No. 4,367.2.
It is described in No. 82.

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 the same compound can be used in two different layers. It is also possible to introduce more than the above.

The coupler used in the present invention can be introduced into the light-sensitive material by the oil droplet dispersion method in ice. In the oil droplet dispersion method, the boiling point or 1
After dissolving in either a high boiling point organic solvent of 75°C or higher and a low boiling point so-called auxiliary solvent, either alone or in a mixture of both, finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. do. Examples of high boiling point organic solvents include those described in U.S. Pat. It may be used for coating after being removed or reduced by a filtration method or the like.

Specific examples of high-boiling organic solvents include phthalate esters (dibutyl phthalate, dicyclohexyl phthalate,
(di-2-ethylhexyl phthalate, decyl phthalate, etc.), esters of phosphoric or phosphonic acids (triphenyl phosphate, tricresyl phosphate, 2-
ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.), benzoic acid esters (2-ethyl hexylbennoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyldodecane amide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4- tert-amylphenol, etc.),
Aliphatic carboxylic acid esters (dioctyl azelate,
glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (
N,N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or above, preferably 50°C or above and about 160°C or below, can be used, and typical examples include ethyl acetate, butyl acetate,
Examples include ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of latex dispersion processes, effects, and latex for impregnation include U.S. Pat. It is described in.

Typical amounts of color couplers used range from 0.001 to 1 mole per mole of photosensitive silver halide, preferably from 0.01 to 0.1 mole for yellow couplers.
5 mole, 0.003 to 0.3 for magenta coupler
moles, and 0.002 to 0.3 for cyan couplers
It is a mole.

The photosensitive materials to which the method of the present invention can be applied include hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, and sulfonamide phenols as color antifogging agents or color mixing inhibitors. It may also contain derivatives and the like.

A known antifading agent may be used in the photosensitive material to which the method of the present invention is applied. Organic antifading agents include hydroquinones, 6-hydroxycoumaras, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, and methylenedioxybenzene. Typical examples include aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Further, a total bending complex represented by a (bissalicylaldoximate) nickel complex and a (bis-N,N-dialkyldithiocarbamate) nickel complex can also be used.

To prevent yellow dye images from deteriorating due to heat, humidity and light.
As described in U.S. Pat. No. 4,268,593,
Compounds having the blue moiety structures of hindered amine and hindered phenol in the same molecule give good results. In addition, in order to prevent deterioration of magenta dye images, especially deterioration due to light, substitution of spiroindanes as described in JP-A-56-159644 and pytroquinone diether or monoether as described in JP-A-55-89835 is recommended. chromans give favorable results.

In order to improve the storage stability of the cyan image, particularly the light fastness, it is preferable to use a benzotriazole ultraviolet absorber in combination, and this ultraviolet absorber may be co-emulsified with the cyan coupler.

The amount of ultraviolet absorber applied should be sufficient to impart photostability to the cyan dye image; however, if too much is used, it may cause yellowing of the unexposed areas (white areas) of the color photographic light-sensitive material. It is usually preferably set in the range of 1X10-' mol/ba to 2X10-3 mol/ml, particularly 5X10-' mol/ga 1.5X10-3 mol/ml.

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

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

The photosensitive material to which the present invention is applied includes, as a filter dye,
Alternatively, a water-soluble dye may be contained in the wood-philic colloid layer for various purposes such as preventing irradiation or halation. Oxonol-based, anthraquinone-based, or azo-based dyes are preferred. Oxonol dyes that absorb green and red light are particularly preferred.

The photographic emulsion layer or other wood-philic colloid layer of the light-sensitive material to which the present invention is applied may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener. Water-soluble brighteners may be used, and water-insoluble brighteners may be used in the form of dispersions.

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

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

In addition to the silver halide emulsion layer, the light-sensitive material to which the present invention is applied is preferably provided with auxiliary layers such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, and a back layer.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material to which the present invention is applied, it is advantageous to use gelatin, or other wood-philic colloids can also be used.

For example, gelatin derivatives, craft polymers of gelatin and other macromolecules, proteins such as albumin and casein:
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate esters, sodium alginate, Ha derivatives such as tenbun derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, bot-N-vinylpyrrolidone, bot acrylic acid, polymethacrylic acid, A wide variety of synthetic wood-philic polymeric materials can be used, such as single or copolymers of polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. The use of acrylic bobbinyl alcohol as a protective layer is particularly useful, and becomes even more useful when rapidly processed with high silver chloride emulsions.

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

Enzyme-treated gelatin as described in No. 16, p. 30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

In addition to the above-mentioned additives, the photosensitive material to which the present invention is applied includes:
Furthermore, various stabilizers, antifouling agents, developing agents or their precursors, development accelerators or their precursors as mentioned above, lubricants, mordants, matting agents, antistatic agents, plasticizers, and other materials useful for photographic materials. Various additives may be added; representative examples of these additives include Research Disclosure No. 17643 (December 1978) and Research Disclosure No. 17643 (December 1978)
8716 (November 1979).

These additives are of great importance in rapid printing, rapid processing, and also in relation to compound (I) of the present invention. In addition, especially when the halogen composition of the emulsion used contains a high content of silver chloride, the combined use of mercaptoazole, mercaptothiadiazole, and mercaptobenzazole compounds is useful for the present invention in terms of color development and fogging. It is.

“Reflective support” that can be used in photosensitive materials to which the present invention is applied
This type of reflective support enhances the reflectance and sharpens the dye image formed in the silver halide emulsion layer.Such reflective supports include titanium oxide, zinc oxide, calcium carbonate, calcium sulfate, Examples include baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, etc. Paper, transparent supports with a reflective layer or reflective materials, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide films, polycarbonate films, polystyrene films, etc.
These supports can be appropriately selected depending on the purpose of use.

□-1 (Effects of the Invention) The developer composition for the silver halide color photographic light-sensitive material of the present invention has excellent stability and color development, and provides a color developer in which an increase in fog during continuous processing is significantly reduced.

Also, the developer of the present invention! The above effects are further enhanced by using a system that does not substantially contain pencil alcohol.

By using the developer composition of the present invention, stability can be increased and deterioration of color development can be prevented without using substances such as sulfite ions that act as competing compounds for the developing agent.

(Example) The present invention will be explained in more detail based on examples.

Example 1 A multilayer color photographic paper was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

-th layer coating liquid 23! 19.1 g of ltA yellow coupler (a) and color image stabilizer (b)
) 4.4 g to 27.2 g of ethyl acetate and solvent (c) 7.
9fi was added and dissolved, and this solution was emulsified and dispersed in a 10% gelatin aqueous solution 185 ml containing 8 ml of 10% sodium dodecylbenzenesulfonate. On the other hand, the following blue-sensitive sensitizing dyes were added to a silver chlorobromide emulsion (containing 1.0% silver bromide, 70 g/kg Ag) in silver chlorobromide 1@o, &
A blue-sensitive emulsion containing s, oxio-' + mol was prepared at 90gyJ. The emulsified dispersion and the emulsion were mixed and dissolved, and the gelatin concentration was adjusted to have the composition shown in Table B to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. As the gelatin hardening agent for each layer, 1-oxy-3,5-cyclo-5-)-lyazine sodium salt was used.

The following spectral sensitizers were used as spectral sensitizers for each emulsion, and the blue-sensitive emulsion layer and green-sensitive emulsion layer (4.OX 10-
' mol addition) (7 per 1 mol of halogenated tlu
．． (Addition of OXlO-+mol) Red-sensitive emulsion layer The following dyes were used to prevent irradiation of each emulsion layer.

The structural formulas of the compounds used in the green-sensitive emulsion layer, red-sensitive emulsion layer, coupler, etc., are as follows.

(8) Yellow coupler CH3 (C1 solvent tdl color mixing inhibitor H (e) solvent (fl color image stabilizer fgl 2+1 mixture (weighted) of solvent) UV absorber I:5:3 mixture?1 (molar ratio ) (kl 1:1 mixture of cyan coupler (MoJ ratio) (1) 1:3:3 mixture of color image stabilizer (molar ratio) (m) Magenta coupler Ca H+ y(t) As above The resulting color photographic paper was wedge-shaped exposed and then processed through the following processing steps.

Processing process Temperature Time Color development 35°C 45 seconds bleach-fixing 35°C 45 seconds rinse 1 35°C 20 seconds rinse 2 35°C 20 seconds rinse 3 35°C 20 seconds drying 80'C 60 seconds The solutions used are as follows. .

Color developer N, N-diethylhydroxylamine 4g Potassium carbonate 30g E D T A
・2 N a ・2 H202g Sodium chloride
1.0g 4-amino-3-methyl-N
- Ethyl-N-(β-(methanesulfonamido)ethyl]-p-phenylenecyamine sulfate 4 s, 0 g Fluorescent brightener (4,4'-diamino-stilbene type) 3.0 g General formula (
Compound I) Table 1 Add water
1000 lessons pH 10,10 Bleach-fix solution E D T A Fe (m) N H・2 H2
060gE D T A ・2 N a ・2 H20
4g ammonium thiosulfate (70%) 120d
Sodium sulfite 16g ice vinegar #
Add 7g water and rub for 1000pH5,
5 Rinsing liquid 1-hydroxyethylidene-1,1'-diphosphonic acid (60%>1.6d Bismuth chloride 0.35g Polyvinylpyrrolidone 0.25g Aqueous ammonia (26%)
2.5d nitrilotriacetic acid/3Na
1. OgEDTA 4H0.5g Sodium sulfite 1.0g5-chloro-2-methyl-4-inthiazolin-3-one 50*g Formalin (37%) 0. l Add standing water
A portion of the color developer obtained in the above manner was stirred at 40° C. for 20 days in an open system under a single beer force, and then treated again in the above treatment steps.

The treatment using the color developer that had been left in the stirrup for 20 days was the aged solution test, and the treatment using the color developer before stirring was the fresh solution test.

The photographic properties of the obtained fresh solution and the photographic properties of the aged solution test are shown in Table 1.

Photographic properties were expressed in three points: Dmin at yellow density, sensitivity, and gradation.

The sensitivity point is expressed as the density value of a constant exposure l (toocMs), and since one gradation represents a density of 0.5, iogE
It is expressed as the density change up to the density point on the high exposure side of 0.3.

According to the present invention, there is almost no change in photographic properties even when the developer is stored in an open system for a long period of time, and a stable photographic material can be obtained.

On the other hand, when sodium sulfite or triethanolamine is used, it changes over time, and the photographic image may become foggy or the gradation may change. 1st layer (@lower layer) to 7th layer (@lower layer) on laminated paper
(top layer) was applied to prepare a sample.

The coating liquid for the first layer was prepared as follows. That is, after heating and dissolving a mixture of 200 g of the yellow coupler shown in the table, 93.3 g of the antifading agent, and 5 g of high boiling point solvents (p) Log and (q) to which 600 rubs of ethyl acetate was added as an auxiliary solvent at 60°C, 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) 33
Mixed with 3,300 d of 5% gelatin aqueous solution containing 0.
A coupler dispersion was prepared by emulsifying using a colloid mill. Ethyl acetate was distilled off under reduced pressure from this dispersion, and the sensitizing dye for the blue-sensitive emulsion layer and 1-methyl-2-mercapto-5 were added.
-Acetylamino-1°3.4-)-lyazole was added to 1,400 g of emulsion (96.7 g as Ag, including 170 g of gelatin), and 2,600 g of a 10% aqueous gelatin solution was further added to prepare a coating solution. . 2nd layer to 7th layer
The coating liquid for the layer was prepared in the same manner as for the first layer.

n2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole o2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole p di(2-ethylhexyl) phthalate q dibutyl phthalate r 2,5-di-tert-amylphenyl-3,5-
di-tert-butylhydroxybenzoate s 2,5-di-tert-octylhydroquinone t 1,4-di-tert-amyl-2,5-dioctyloxybenzene u2,2”-methylenebis(4-methyl-6-tert
-Methylphenol) The following were used as sensitizing dyes for each emulsion layer.

Blue-sensitive emulsion layer: anhydro-5-methoxy-5'-methyl-3,3'-disul7obrovir selenacyanine hydroxyto green-sensitive emulsion layer, anhydro-9-ethyl-5,5'-diphenyl- 3,3'-disulfoethyloxacarbocyanine hydroxide red-sensitive emulsion layer; 3,3'-diethyl-5-methoxy-9
,9=-(2,2-dimethyl-1,3-propano)thiadicarbocyanine iosito The following were used as stabilizers for each emulsion layer. 1-methyl-2-mercapto-5-acetylamino-1,3,
4-Triazole and the following were used as anti-irradiation dyes.

4-(3-carboxy-5-hydroxy-4-(3-(
3-Carboxy-5-oxo-1-(4-sulfonatophenyl)-2-pyrazoline-4-isodene)-1-propenyl)-1-pyrazolyl)benzenesulfonate di-potassium salt N,N'-( 4,8-dihydroxy-9,10-dioxo-3,7-cisulfonatoanthracene-1,5-diyl)bis(aminomethanesulfonate)-tetrasodium salt and 1,2-bis(vinyl sulfonyl)ethane was used.

The couplers used are as follows.

Yellow coupler Magenta coupler α Cyan coupler (C-1; C-2-50: Mixture of 50 (molar ratio)) The multilayer color photographic paper obtained as follows was exposed to wedge-shaped light and then processed in the following processing steps. did.

Processing process Time Temperature color development
3 minutes 30 seconds 33℃ bleach fixing
1 minute 30 seconds 33°C rinse (3 tank cascade-1) 3 minutes 30°C dry
Drying 1 minute
The processing solution used at 80°C is as follows.

Color developer water 8
00d Pencil alcohol Table 2 Diethylene glycol Table 2 Diethylenetriaminepentaacetic acid 1.0gN,N''-bis(2
-hydroxypencil) ethylenediamine- N,N'-cyaacetic acid 0.1g nitrilo-
N,N,N-)-rimethylenephosphonic acid (40%) 1.0g Potassium bromide 1.0g General formula (I)
Compounds Table 2 Hydroxylamines Table 2 Charcoal Potassium
30g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.5g optical brightener (4,4”-diaminostilbene type) 1. Add Og wood 1000w100O pH 10,10 bleach-fixing axillary ammonium thiosulfate (70%) 150d sodium sulfite 15g ethylenecyamine iron(III) ammonium 60g ethylenecyaminetetraacetic acid 10g optical brightener (4,4
--Diaminostilbene type) 1.0g 2-Mercapto-5-amino-3,4-thiadiazole Add 1.0g water 1000 ml with ammonium water pH 7.0 Rinse liquid 5-chloro-2-methyl-4-isothiazowan -3-one 40 mg 2-methyl-4-inthiazolin-3-one 10 m g 2-methyl-4-isothiazolin-3-one 10 mg bismuth chloride (40%) o, 5 g nitrilo-N,N
, N-)-limethylenephosphonic acid (40%) 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid (60%) 2.5 g Optical brightener (4,4'-diaminostilbene type) 1. Og ammonium wood (26%) 2.0mf! Add water and use 1000119KOH to pH 7.5 In the same manner as in Example 1, determine the magenta Dmin, sensitivity, and gradation in the fresh solution and the preserved solution, and take each photo based on the photographic properties in the fresh solution. Table 2 shows the change values of the sexual sources.

From the results in the table above, it can be seen that the developing solution Mir& of the present invention shows excellent effects in systems containing pencil alcohol, and in particular, the photographic performance is significantly stabilized when used in systems not containing benzyl alcohol. Experiment No. 12.13.14.15.18.19.20.2
1.22).

On the other hand, when using hydroxylamines alone,
The storage solution changes over time, and the photographic quality changes greatly.

Example 3 The silver halide emulsion composition of the third layer of the sample photographic paper was changed to silver bromide 8.
Photographic paper was prepared in the same manner as in Example 2, except that the concentration was 0 mol%, and it was stored and tested for changes in photographic properties in the same manner as in Experiment No. 9 to 22. As in Example 2, hydroxylamines alone In contrast, the developer composition of the present invention showed remarkable stability, especially in a system that did not contain benzyl alcohol, whereas the photographic properties changed significantly due to changes in the storage solution over time.

Claims (2)

[Claims] (1) A developer composition for a silver halide color photographic light-sensitive material, comprising an aromatic primary amine color developing agent and a compound represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 is an alkyl group or hydroxyalkyl group having 7 or more carbon atoms, and R^2 and R^3 are a hydrogen atom or an alkyl group, respectively. or represents a hydroxyalkyl group, and at least one of R^1, R^2, and R^3 is a hydroxyalkyl group.) (2) A silver halide color photographic light-sensitive material is processed with a developer that does not substantially contain benzyl alcohol and contains an aromatic primary amine color developing agent and a compound represented by the following general formula (I). A method for processing a silver halide color photographic light-sensitive material. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 is an alkyl group or hydroxyalkyl group having 7 or more carbon atoms, and R^2 and R^3 are a hydrogen atom or an alkyl group, respectively. or represents a hydroxyalkyl group, and at least one of R^1, R^2, and R^3 is a hydroxyalkyl group.)