JPH03174152A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent edge staining due to permeation of a color developing solution from the ends of a support by incorporating at least one of epoxydated higher fatty acid amide, alkylketene dimer, higher fatty acid salt, and alkenylsuccinic anhydride in a paper base and a specified compound in the color developing solution. CONSTITUTION:The silver halide photographic sensitive material is obtained by forming a photosensitive silver halide emulsion layer on the paper base coated on both sides with polyolefin and it is processed with the color developing solution containing an aromatic primary amine color developing agent, and the paper base contains at least one of epoxydated higher fatty acid amide, alkylketene dimer, higher fatty acid salt, and alkenylsuccinic anhydride. The color developing solution contains the compound or its salt represented by formula I in which L is alkylene; A is carboxy, sulfo, or the like; and R is H or alkyl, thus permitting edge staining due to permeation from the ends of the photographic paper base coated with a resin on both sides.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for processing silver halide color photographic materials. The present invention relates to a development processing method that prevents etching stains caused by penetration.

(Prior Art) Conventionally, so-called baryta paper, in which one side of the paper is coated with a baryta layer mainly composed of barium sulfate, has been used as a reflective support for photography. In order to speed up the process, waterproof supports in which both sides of base paper are coated with resin have come to be used. however,
Even when the above-mentioned waterproof support is used, it is not possible to prevent the developer from permeating through the cut surface of the end of the support. The developer that permeates through the cut edges cannot be removed in a short period of time, and will turn brown due to heat or over time, staining the etched areas of the photograph, and significantly reducing the value of the photograph. In order to prevent this edge staining, attempts have been made to provide a high size property to the base paper layer.

Fatty acid soap type sizing agents as shown in Japanese Patent Publication No. 47-26961 and alkyl ketene dimers as shown in Japanese Patent Application Laid-open No. 51-132822 have been used as sizing agents for photographic paper, but each has its drawbacks. And it's not enough.

That is, the sizing agent for fatty acid soap tamps has the disadvantage that it has a low sizing effect on the alkali in the developer, and that the strength of the paper decreases significantly as the amount added increases, and the stiffness of the paper decreases. On the other hand, alkyl ketene dimers have good sizing properties in water, but have poor sizing properties in alkaline water and water containing organic solvents such as alcohol, and are known as boria ξ topolia ξ as a fixing agent.
Both sizing agents have the disadvantage of requiring the use of a relatively large amount of chlorohydrin resin, and none of the sizing agents are fully satisfactory for use in photographic base paper. Therefore, there was a strong desire to develop a technology that would prevent edge staining even when using a small amount of sizing agent and a small amount of polyamide polyamine epichlorohydrin resin.

In recent years, in the photographic processing of color photosensitive materials, there has been a desire to shorten the processing time, reduce the amount of replenishment of processing liquid, and reduce the amount of waste liquid due to the shortening of finishing delivery times and the reduction of laboratory work. It has been put into practical use in minilabs, etc., and is spreading to the market. Increase in temperature of processing solution due to rapid processing, shortening of washout time, deterioration of processing solution (coloring and tarring of developer) due to reduction in replenishment amount, and accumulated I concentration of eluates from photosensitive materials. As processing conditions become more severe, there is a strong desire to solve the problem of edge stains.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to prevent the developer from seeping into the edges of a photographic support whose base paper is coated with resin on both sides, and to significantly suppress edge staining. It is an object of the present invention to provide a developing processing method.

(Means for Solving the Problems) The object of the present invention is to coat at least one aromatic silver halide color photographic light-sensitive material having a light-sensitive silver halide emulsion layer on a paper support coated on both sides with polyolefin. In a method of processing with a color developer containing a primary amine color developing agent, at least l [I Contains
The present invention has been achieved by a method for processing a silver halide color photographic material, wherein the color developer contains a compound represented by the following general formula (I) or a salt thereof.

General formula (1) In the formula, L represents an alkylene group that may be substituted, and A is a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group that may be substituted with alkyl,
Represents an alkyl-substituted ammonio group, an alkyl-substituted carbamoyl group, an alkyl-substituted sulfamoyl group, an optionally substituted alkylsulfonyl group, and R is a hydrogen atom, which may be substituted. Represents an alkyl group.

The -format (I) will be explained in detail below.

In the formula, L represents a linear or branched alkylene group having 1 to 10 carbon atoms, which may be substituted, and preferably has 1 to 5 carbon atoms. Specifically, methylene, ethylene, trimethylene,
Propylene is mentioned as a preferred example. Examples of substituents include carboxy groups, sulfo groups, phosphono groups, phosphinic acid residues, hydroxy groups, and alkyl (preferably 1 to 5 carbon atoms) optionally substituted ammonio groups; Preferred examples include a group and a hydroxy group. A is a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an alkyl (preferably 1 to 5 carbon atoms) optionally substituted amino group, an alkyl group (preferably 1 to 5 carbon atoms); ) optionally substituted ammonio group, alkyl (preferably 1 carbon number)
~5) represents an optionally substituted carbamoyl group, an optionally substituted alkyl (preferably 1 to 5 carbon atoms) sulfamoyl group, an optionally substituted alkylsulfonyl group,
Carboxy group, sulfo group, hydroxy group, phosphono group,
Preferred examples include carbamoyl groups which may be substituted with alkyl. Preferred examples of -LA include carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, and hydroxyethyl group. Particularly preferred examples include a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group.

R represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, which may be substituted, and preferably has 1 to 5 carbon atoms. Examples of substituents include a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be substituted with alkyl, an ammonio group which may be substituted with alkyl, a carbamoyl group which may be substituted with alkyl, and an alkyl group. An optionally substituted sulfamoyl group, an optionally substituted alkylsulfonyl group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonyl group, an optionally substituted amino group with an alkyl group,
Represents an arylsulfonyl group, a nitro group, a cyan group, or a halogen atom. There may be two or more substituents.

R is a hydrogen atom, a methyl group, an ethyl group, a propyl group,
Preferable examples include carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, and hydroxyethyl group, and hydrogen atom, carboxymethyl group, and carboxyethyl group , sulfoethyl group, sulfopropyl group, phosphonomethyl group, and phosphonoethyl group are particularly preferred examples. L and R may be connected to form a ring.

Furthermore, when A and R have dissociated protons, A and R
can also be used as alkali metal salts such as sodium salts and potassium salts.

The above-mentioned sizing agents have the disadvantage that they do not completely prevent edge staining and have insufficient sizing effects. Furthermore, disadvantages such as a decrease in paper strength occur as the amount added increases.

As a result of various studies conducted by the present inventors for the purpose of preventing edge staining, the present inventors have found that at least one sizing agent selected from epoxidized higher fatty acid amide, alkyl ketene dimer, higher fatty acid salt, or alkenyl succinic anhydride, It has been found that edge staining can be significantly prevented by combined use with a color developer containing the compound represented by formula (I).

- Compounds of the form (, 1) are known as preservatives for developing solutions, but although they show almost no size effect when used alone, when used in combination with the above-mentioned sizing agents, they specifically exhibit size effects. What it showed was a completely unexpected and truly surprising effect.

Conventionally, when an alkyl ketene dimer is used as a sizing agent, it is known that the sizing effect is low against alcohols such as benzyl alcohol in the developer, but certain amine compounds shown in the general formula (+) The fact that the sizing agent increases the effect of the sizing agent has not been known until now, and has been made clear for the first time by the present invention.

The compound represented by the -S formula ([) has almost no size effect when used alone, so the size effect due to this combination is as follows:
The compound of general formula (I) has the size effect of the above sizing agent!
Although it is thought that this phenomenon is caused by a large amount of carbon dioxide, the details are unknown and will be clarified through future research.

Further, by using the compound of general formula (I) in combination with the above-mentioned sizing agent, the amount of the sizing agent added can be reduced, and drawbacks such as a decrease in paper strength due to an increase in the amount added can also be improved.

The processing liquid used in the present invention will be explained in detail below.

Specific examples of the compound of general formula (1) in the present invention are listed below, but the present invention is not limited thereto.

In addition, the amount of the following compounds added to the color developing solution is 0.00
5 mol/11 to 0.5 mol/l, preferably 0.03
Mol/It-0.1 mol/i! (It is desirable to add so as to achieve the D concentration.

(1) (4) (5) (6) CH.

C2H- C.Hr. Hs Hr (8) (9) H H (13) CH.

CH.

H H (19) HO-NH-CH,CO,H ω HO-NH-CHICHaCO,H (21) 0 NH-CH-CO,H CHi (22) HO-NH-CH-CO,H 2H1 (23) HO-NH-CH-Co, H C,H.

(24) HO-NH-CH-CH, -CO,H CH.

(25) HO-NHCH2CHCH2 CH2 (26) H.O. NH-CH, CH, 5OIH (27〉 HO-NHCHtCHCH2S○,H OH (28) (29) (30) (31) HO-NH-(CHt)+SO+H H○-NH-(CH2), 5OIH HO-NH-CH! P.O., H.

HONHCH-POsHt H5 (32) (33) (34) (35) HO-N HCH, CH2P Os H2H〇-NHC
H2CH20H HONH(CHri'-0H HONHCH+ PO□H2 (36> HO-NH-CH2CH2N(CHi)s(37) HONHCH2CH2H2N(CHs)sH (42) (46> HONHCH2CH(PO3Hri1 (48) HO -N N -CHICH2C0IH\” (49) (50) (53) (54> HON HCH2CH2CN HC(CH3) 2 C
H2S Os HO (55) Among the above-mentioned exemplified compounds, compounds (1), (2), (3),
(7), (8), (11), (12), (14), (1
9), (22), (23), (26), (27), (3
0), (31), (40), (43), (44), (5
2) and (53) are more preferred.

Among these, compounds (2) and (7) are particularly preferred in terms of preventing edge staining.

The compound represented by the general formula (1) can be obtained by converting commercially available hydroxylamines into alkylation reactions (nucleophilic substitution reactions,
addition reaction, Mannich reaction). West German Patent No. 1159634, "Inorganic force, chemical force, acta J"
ica Chimica Acta), 93,
(1984) 101-108, etc., and a specific method is described below.

Synthesis Example Synthesis of Exemplified Compound (7) 11.5 g of sodium hydroxide and 96 g of sodium chloroethanesulfonate were added to 200 g of an aqueous solution of 20 g of hydroxylamine hydrochloride, and the mixture was kept at 60°C and mixed with an aqueous solution of 23 g of sodium hydroxide (40 g) for 1 hour. I added it slowly.

Further, the temperature was maintained at 600C for 3 hours, the reaction solution was concentrated under reduced pressure, 200% of concentrated hydrochloric acid was added, and the mixture was heated to 50C. Insoluble materials were filtered, and 500 d of methanol was added to the filtrate to obtain the desired product (exemplified compound (7)) as crystals of monosodium salt 641
g (yield 53%) Synthesis of exemplified compound CIt) Hydroxylamine hydrochloride 7.2 g and phosphorous acid 18,0 g
32.6 g of formalin was added to the aqueous hydrochloric acid solution and heated under reflux for 2 hours. The resulting crystals were recrystallized from water and methanol to obtain 9.2 g (42%) of Exemplified Compound (11).

The color developer used in the present invention contains a known aromatic primary amine color developing agent.

Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylamine toluene D-32-amino-3-(N-ethyl-N-laurylamino)toluene D-44-[N-ethyl- N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-64-amino-3-methyl-N-ethyl-N -Cβ
-(methanesulfonamido)ethyl]-aniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D8N,N-dimethyl-
p-phenylenediamine 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 Among the above p-phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl-N-[β-(
methanesulfonamido)ethylcoaniline (exemplified compound D-6) and 2-methyl-4-[N-ethyl-N-(
β-hydroxyethyl)aminocoaniline (exemplified compound D-5).

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates. The amount of the aromatic-grade amine developing agent used is preferably about 0.1 g to about 20 g per 11 of the developer solution.
More preferably a concentration of about 0.5g to about 15g.

In the present invention, the compound represented by the general formula (A) is preferably used from the viewpoint of improving the storage stability during one night of development (prevention of deterioration of the developing agent and the compound of form (I) and prevention of tar). In addition, in terms of preventing the etch mark, (A-3)
is preferably used.

- Format (A) (wherein R1 is a hydroxyalkyl group having 2 to 6 carbon atoms,
R1□ and R1 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group, or formulas X and X' are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, Alternatively, it represents a hydroxyalkyl group having 2 to 6 carbon atoms. ) Preferred specific examples of the compound represented by the above-mentioned form [A] are as follows.

(A-1) Ethanolamine, (A-2) Jetanolamine, (A-3)
) reethanolamine, (A-4) di-isopropanolamine, (A-5) 2-methylaminoethanol, (A-6) 2-dithylaminoethanol, (A-7) 2-dimethylaminoethanol ,
(A-8) 2-diethylaminoethanol, (A
-9) 1-diethylamino-2-propatool, (A-10) 3-diethylamino-1-propatool, (A-11) 3-dimethylamino-1-propatool, (A-12) Isopropylaminoethanol, (A
-13) 3-amino-1-propatol, (A-1
4) 2-amino-2-methyl-1,3-propanediol, (A-15) ethylenediaminetetraisopropanol, (A-16) benzyljetanolamine, (A-
17) 2-amino-2-(hydroxymethyl)-1,3
-propanediol, (A-18) l,3-diaminopropanol, (
A-19) 1.3-bis(2-hydroxyethylmethylamino)-propatol.

These compounds represented by the above-mentioned form (A) have an effect of 3 to 10 g per color developer Iff.
It is preferably used in the range of 0g, more preferably 6g~
It is used in a range of 50g.

In the color developer according to the present invention, compounds represented by the following formats [B-1] and [B■] are more preferably used from the viewpoint of suppressing deterioration of the developer.

General formula General formula CB-II) R1 In the formula, Rl 1, R4, R1, and R1: hydrogen atom, halogen atom, sulfonic acid group, number of carbon atoms, respectively
~7 alkyl group, -0R4, represents a group. Also, R11, R11, Rzo and R11
each represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. However, when R1 represents -OH or a hydrogen atom, R+4 represents a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, or a -0R4 group.

The alkyl groups represented by R4, R1, R1, and R17 include those having substituents, such as methyl group, ethyl group, 1so-propyl group, n-propyl group, t-butyl group, n-butyl group, Examples include a hydroquine methyl group, a hydroxyethyl group, a methylcarboxylic acid group, a benzyl group, etc., and the alkyl group represented by R1°, R1, R2° and R11 has the same meaning as above, and further examples include an octyl group, etc. Can be done.

Furthermore, the phenyl groups represented by R11, RIB, R4 and R17 include phenyl group, 2-hydroxyphenyl group, 4
-aminophenyl group and the like.

Typical specific examples of the chelating agent of the present invention are listed below, but the invention is not limited thereto.

(B-I-1) 4-isopropyl-1,2-dihydroxybenzene (B-1-2) 1.2-dihydroxybenzene-3,5-disulfonic acid (B-I-3) 1.2.3- Trihydroxybenzene-5-carboxylic acid (B-I-4) 1.2.3-trihydroxybenzene-5-carboxymethyl ester (B-I-5) 1.2.3-trihydroxybenzene-5-carboxy -n-butyl ester (B-I-6) 5-t-butyl-1,2,3-trihydroxybenzene (B-I-7) 1,2-dihydroxybenzene-3,4,6-trisulfonic acid ( B-n-1) 2.3-dihydroxynaphthalene-6-sulfonic acid (B-If-2) 2.3.8-) Lihydroxynaphthalene-6-sulfonic acid (B-n-3) 2.3- Dihydroxynaphthalene-6-carboxylic acid (B-n-4) 2.3-dihydroquine-8-isopropyl-naphthalene (B-n-5) 2.3-dihydroxy-8-chloro-naphthalene-6-
Among the above-mentioned sulfonic acid compounds, compounds particularly preferably used in the present invention include 1,2-dihydroxybenzene-3,
Examples include 5-disulfonic acid, which can also be used as alkali metal salts such as sodium salt and potassium salt. (Specific exemplary compound (B-I-2)).

In the present invention, the above-mentioned -format CB-I) and CB-[
] The compound represented by
It can be used in the range of 15 to 1 g, preferably 15 to 1
It is desirable to use the amount in the range of 0g/1, more preferably 25~7g.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate,
Sodium tetraborate (borax), potassium tetraborate, 0
-Sodium hydroxybenzoate (sodium satylylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

The amount of the buffer added to the color developer is 0. 1 mole/
It is preferably 1 or more, particularly 0. 1 mol/l-
Particularly preferred is 0.4 mol/1.

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

Specific examples are shown below, but the invention is not limited to these. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid,
N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N-N'-tetramethylenephosphonic acid, 1,3-diamino-2-propatoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid , l,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, hydroxyethylenediamine triacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene -1,1-diphosphonic acid, N,N--bis(2-hydroxybenzyl)ethylenediamine-N,N-diacetic acid, catechol-3,4,6-trisulfonic acid, catechol-3,5-disulfonic acid , 5-sulfosalicylic acid,
4-Sulfosalicylic acid.

Among these chelating agents, preferred are ethylenediaminepentaacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminoprobanoltetraacetic acid, ethylenediamine-N, N, N-, N-
-Tetrakis (methylenephosphonic acid, hydroxyethyliminodiacetic acid are good)

Two or more of these chelating agents may be used in combination, if necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example 11
It is about 0.1g to 10g per serving.

Any development accelerator can be added to the color developer if necessary.

As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, No. 38-7826, No. 44-123
No. 80, No. 45-9019 and U.S. Patent No. 3,813
, 247, p-phinidine diamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-Sho 5
Quaternary ammonium salts shown in Japanese Patent Publication No. 0-137726, Japanese Patent Publication No. 44-30074, Japanese Patent Application Publication No. 56-156826 and Japanese Patent Publication No. 52-43429, etc., U.S. Patent No. 2.6
No. 10.122 and p described in No. 4,119゜462
-Aminophenols, U.S. Patent No. 2,494,903
No. 3. 128. No. 182, 4,230,79
No. 6, No. 3,253゜919, Special Publication No. 41-1143
No. 1, U.S. Pat. No. 2,482. ．． No. 546, 2,59
6,926 and 3,582,346, etc., Japanese Patent Publication No. 37-16088, 42-
25201, U.S. Patent No. 3,128,183, Japanese Patent Publication No. 41-11431, Japanese Patent Publication No. 42-23883, and U.S. Patent No. 3,532.501, and other l-phenyl-3-pyrazolidones. hydrazines, mesoionic compounds, ionic compounds, imidazoles, etc. can be added as necessary.

The color developer preferably does not substantially contain benzyl alcohol from the viewpoint of preventing edge stains. Substantially means 2.0 or less per 11 color developing solutions, and more preferably no content at all.

It is particularly preferable that it not be substantially contained in terms of preventing etch stains.

For the purpose of preventing fog, especially when processing a photosensitive material with a high silver chloride content of 80 mol % or more, it is preferable that chlorine ions and bromine ions be present in the color developer. Preferably as chlorine ion, 1. 0XIO-”~1.5X10
-' mol/1 more preferably 4XlO-2 to lXl0-
' Contains mol/l. Chlorine ion concentration is 1.5X10-
If the amount is more than 'mol/i, it has the disadvantage of delaying development. Further, if the amount is less than 3.5xlO''mol/1, fogging cannot be prevented.

Bromine ions are preferably added to the color developer at 3°0XIO.
Contains -S mol/12-1.0XIO-' mol/l.

More preferably 5.0×10-' to 5×10-' mol/l, still more preferably 1. .

Xl0-' to 3XlO-' mol/1. If the bromide ion concentration is more than 1X10-'' mol/i, the development will be delayed and the maximum density and sensitivity will be reduced, and if it is less than 3.0 x 10-j mol/1, fog cannot be prevented.

Here, chloride ions and bromine ions may be added directly to the developer, or may be eluted from the photosensitive material during development.

When added directly to a color developer, chloride ion supplying substances include sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride.
Among them, preferred are sodium chloride and potassium chloride.

It may also be supplied in the form of a sealed ring of fluorescent brightener added to the developer. As a supply material for bromide ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, cadmium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide,
Examples include thallium bromide, of which potassium bromide and sodium bromide are preferred.

When eluted from the light-sensitive material during development, both chlorine ions and bromine ions may be supplied from the emulsion, or may be supplied from a source other than the emulsion.

In the present invention, in addition to chlorine ions and bromide ions, any antifoggant can be added as necessary. As antifoggants, alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-
Nidropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention preferably contains a fluorescent brightener. As a fluorescent brightener, 4,4'-
Diamino-2,2'-disulfostilbene compounds are preferred. The amount added is 0 to 10g/(1, preferably 0.1
~6g/l.

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

The processing time of the color developer of the present invention is 10 seconds to 120 seconds,
Preferably, the effect of the present invention is significant in 20 seconds to 60 seconds. Further, the effects of the present invention are particularly remarkable when the treatment temperature is 33 to 45°C, preferably 36 to 40'C.

The replenishment amount of the color developer during continuous processing is preferably 20 to 220 J per 1.7 of the photosensitive material, preferably 25 to 160 J, particularly preferably 307 to 110 J, in that the effects of the present invention can be effectively exhibited. .

In addition, the color developer of the present invention has relatively superior performance in its liquid aperture ratio (air contact area (cr1)/liquid volume (cr1)) than combinations other than those of the present invention under any conditions. From the viewpoint of the stability of the developer, the opening ratio of the solution should be 0 to 0. 1 cm −1 is preferred. In continuous processing, practically 0. 001cm-'~0.05cm-'
The range is preferably 0.002 cm-', more preferably 0.002 cm-'
~0.03 cm.

Generally, when hydroxylamine etc. are used as a preservative, even if the aperture ratio of the color developer is reduced,
It is widely known that decomposition occurs due to heat or trace metals. However, in the color developer of the present invention,
These decompositions are extremely small, and the color developer can be sufficiently put to practical use even when the color developer is stored or used for a long period of time. Therefore, in this case, the smaller the liquid aperture ratio is, the more preferable it is, and the most preferable is 0 to 0.002 cm-'.

On the other hand, there are cases where processing is performed with a wide aperture ratio under the condition that a certain amount of processing is processed and then discarded, but in such a processing method, if the structure of the present invention is followed, excellent performance can be achieved. Can be done.

In the present invention, desilvering treatment is performed after color development. The desilvering step generally consists of a bleaching step and a fixing step, but it is particularly preferable that they are carried out simultaneously.

The bleach or bleach-fix solutions used in the present invention may contain bromides (e.g., sodium bromide, sodium bromide, ammonium bromide), or chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride), or iodides. (eg, ammonium iodide).

If necessary, one or more inorganic substances having pH buffering ability 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. Acids, organic acids and alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate, guanidine, etc. can be added.

The fixing agent used in the bleach-fixing solution or fixing solution according to the present invention is a known fixing agent, namely sodium thiosulfate,
Thiosulfates such as ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; thioether compounds such as ethylene bisthioglycolic acid and 3,6-cythia-1,8-octanediol, and water-soluble thioureas. These silver halide solubilizers can be used alone or in combination of two or more. It is also possible to use a special bleach-fix solution made 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. In the present invention, thiosulfate,
Particularly preferred is ammonium thiosulfate. The amount of fixing agent per 11 moles is preferably 0.3 to 2 moles, more preferably 0.5 to 1 mole. It is in the range of 0 mol.

The pH range of the bleach-fix solution or fixer solution in the present invention is as follows:
3 to 8 are preferred, and 4 to 7 are particularly preferred. p
If H is lower than this, the desilvering property will be improved, but the deterioration of the solution and the leucoization of the cyan dye will be promoted. On the other hand, if the pH is higher than this, desilvering is delayed and staining is more likely to occur.

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

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

The bleach-fix solution and fixer solution used in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite,
ammonium sulfite, etc.), bisulfites (e.g. ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfites (e.g. potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) ) and other sulfite ion-releasing compounds. These compounds are approximately 0.0 in terms of sulfite ion.
The content is preferably 2 to 0.50 mol/l, more preferably 0.04 to 0.40 mol/l. Particularly preferred is the addition of ammonium sulfite.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Sulfinic acids, carbonyl compounds, sulfinic acids, etc. may be added.

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

The bleach-fix solution of the present invention has a processing time of 10 seconds to 120 seconds, preferably 20 seconds to 60 seconds. Also, the replenishment amount is 1r of photosensitive material.
30-250-1 preferably 40-150-1 per d
It is. Generally, an increase in staining and poor desilvering tend to occur as the amount of replenishment is reduced, but according to the present invention, the amount of replenishment of the bleach-fix solution can be reduced without causing such problems. Can be done.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to a water washing and/or stabilization process after fixing or desilvering treatment such as bleach-fixing.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (the number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. this house,
The relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion.
Picture and Television Engineers (
Journal of the Society of
Motion Picture and Television
ion Engineers) Volume 64, 9.248~
253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium and magnesium described in Japanese Patent Application No. 61-131632 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds and thiabendazoles, chlorinated sodium incyanurate, and other benzotriazoles described in JP-A No. 57-8542, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, It is also possible to use the disinfectants described in the Sanitation Technique Complete Volume ``Sterilization of Microorganisms, Disinfection, and Anti-Mildew Techniques'' and the Japan Antibacterial and Antifungal Society Line ``Encyclopedia of Antibacterial and Antifungal Agents.''

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 9.
and preferably 5 to 8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 2 minutes at 15 to 45°C, preferably 25 to 45°C.
A range of 30 seconds to 1 minute and 30 seconds at 0°C is selected.

Even in such short-time water washing, according to the present invention, there is no increase in staining and good photographic characteristics can be obtained.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-open Nos. 57-8543 and 58-1
No. 4834, No. 59-184343, No. 60-22.
No. 0345, No. 6o-238832, No. 60-239
No. 784, No. 6゜-239749, No. 61-4054
The known method described in No. 61-118749, etc.
All can be used. In particular, a stabilizing bath containing 1-hydroxyethylidene-1,1-diphosphonic acid, 5-chloro-2-methyl-4-isothiazolin-3-one, a bismuth compound, an ammonium compound, etc. is preferably used.

Further, following the water washing process, a further stabilization process may be performed, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

The processing time of the present invention is defined as the time from when the photosensitive material comes into contact with the color developer until it exits the final bath (generally water washing or stabilization bath).
The effects of the present invention can be significantly exhibited in a rapid treatment process in which the processing time is 30 seconds or less, preferably 3 minutes or less.

Next, a silver halide photosensitive material using a support in which both sides of a base paper are coated with polyolefin will be described.

In the present invention, in the base paper of this support, 0.01% by weight or more, preferably o, oi to 1% by weight, based on the absolute dry weight of the pulp in the paper,
Particularly preferably 0.1-0.7% by weight of epoxidized higher fatty acid amide, 0.05% by weight or more, preferably 0.05-2% by weight,
Particularly preferably 0. 3-1. 5% by weight of alkyl ketene dimer 0.1% by weight or more, preferably from 0.1 to 3% by weight, particularly preferably 0.5% by weight. 5-2% by weight of higher fatty acid salts or 0.1% by weight or more, preferably 0.1% by weight or more. 1-2% by weight,
Particularly preferably, by containing at least one kind of alkenyl succinic anhydride in an amount of 0.3 to 1.5% by weight or more, prevention of edge staining when processed with the developer is achieved.

These base paper additives may be used in combination of two or more types or all four types.

Any compound known in this field can be used as the epoxidized higher fatty acid amide. Especially RI-CoNH-
A compound having a structure represented by (CHri, -long-(CH2).-NHCO-RI (where R' represents a substituent such as an alkyl group, n represents a positive integer, and X represents an anion) is preferable.An example thereof is NS-715 (modernized character type).

As the alkyl ketene dimer, any compound known in this field can be used, but in particular R''-CH=C
A compound having a structure represented by -CH-RL O-C=O (where R1 is an alkyl group, such as hexadecyl, octadecyl, eicosyl, tocosyl, etc.) is preferred. Examples include Accobel 12, Barcon W1 Bar Stove 02 (manufactured by Dick Vercules), Cysone H20 (manufactured by Kao), 5PK-9.
03 (manufactured by Arayo Kagaku) and the like.

As the higher fatty acid salt, any compound known in this field can be used. Especially the alkali metal salts of saturated fatty acids (
sodium or potassium salts of hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, tocosanoic acid, etc.).

As the alkenyl succinic anhydride, any compound known in this field can be used, but in particular, the compound represented by (where R1 represents a substituent such as an alkyl group, and R4 represents a divalent group such as an alkynyl group) is used. preferable. Examples include Size Pine 5A-850, Size Pine 5A-81.
0 (manufactured by Arayo Kagaku), R5-168E (manufactured by Sanyo Kagaku), and the like.

These additives can be added by such means as being mixed into the pulp during the making of the base paper.

The base paper used in the present invention is NBKP and LBKP.

Paper is mainly made using wood pulp such as NBSP and LBSP, but the ratio of wood pulp such as vinylon to 1:5. It is also possible to mix fibers or synthetic pulp such as polyethylene. Considering the formation and paper-making suitability of the pulp-filtered charcoal, 20
0 to 350C3F is preferred.

In addition to the above additives, the present invention also uses fillers such as clay talc, calcium carbonate, and urea resin fine particles, sizing agents such as rosin and paraffin wax, paper strength agents such as polyacrylamide, fixing agents such as sulfuric acid, and cationic polymers. Agents may be added as necessary.

Furthermore, it is preferable to subject film-forming polymers such as gelatin, starch, carboxymethyl cellulose, polyacrylamide, polyvinyl alcohol, and polyvinyl alcohol modified products to surface size treatment, and polyvinyl alcohol or polyvinyl alcohol modified products are particularly preferred. Examples of polyvinyl alcohol modified products include carboxyl modified products, silanol modified products, and copolymers with acrylamide. The coating amount of the coating polymer is 0.1 to 5.0 g/bo, preferably 0.1 to 5.0 g/bo. It is 5 to 3.0 g/m'. If necessary, it is also possible to use an antistatic agent, a fluorescent whitening agent, a pigment, an antifoaming agent, a compound having a cation, etc. in combination with the coating forming polymer for surface size treatment.

As the equipment for making the paper used in the present invention, a normal Fourdrinier paper machine can be used, and it is preferable that the paper machine is equipped with a calender before winding and before surface size.

The weight and thickness of the paper in the waterproof support of the present invention are each 60
g/rtr ~230 g/ffl, 55 t, t
~230μ.

Examples of the polyolefin resin used to coat both sides of the base paper include homopolymers of α-olefins such as polyethylene and polypropylene, and mixtures of these various polymers. Particularly preferred polyolefins are high density polyethylene, low density polyethylene and mixtures thereof. These polyolefins are usually coated on both sides of the base paper by an extrusion coating method, and therefore there is no particular restriction on their molecular weight as long as they can be extrusion coated, but usually the molecular weight is in the range of 10' to 10@. Certain polyolefins are used.

The thickness of the polyolefin coating layer is not particularly limited and can be determined according to the thickness of the polyolefin coating layer of a conventional photographic paper support, but it is usually preferably 10 to 50 .mu.m.

It is preferable that the polyolefin coating layer on the front side, that is, the side to which the photographic emulsion is coated, contains a white pigment.
The type, amount, etc. of this white pigment can be appropriately selected from known ones. Furthermore, a fluorescent whitening agent,
It is also possible to add known additives such as antioxidants.

Further, the facing polyolefin coating layer may be composed only of the polyolefin resin, but it may also be composed of colored pigments,
A white pigment or the like may be added, and the same additives as those for the polyolefin coating layer on the front surface may also be added.

Incidentally, as the extrusion coating equipment for extrusion coating polyolefin, a usual polyolefin extruder and laminator are used.

In order to provide a silver halide emulsion layer on the polyolefin coating layer, the surface of the polyolefin coating layer is preferably subjected to corona discharge treatment, glow discharge treatment, flame treatment, etc., and if necessary, an undercoat layer or antihalation layer is provided. A silver halide emulsion may be applied thereon.

Next, the color photographic material used in the present invention will be explained in detail.

The color photographic light-sensitive material of the present invention can be constructed by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer on a support. In general color photographic paper, the layers are usually coated on the support in the above order, but they may be applied in a different order. Furthermore, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. These photosensitive emulsion layers contain a silver halide emulsion sensitive to each wavelength range, and dyes that are complementary colors to the sensitizing light - yellow for blue, magenta for green, and cyan for red.
By containing a so-called color coupler that forms a color, subtractive color reproduction can be performed. However, the coloring hues of the photosensitive layer and the coupler may not correspond as described above.

As the silver halide emulsion used in the present invention, one consisting of silver chlorobromide or silver chloride that does not substantially contain silver iodide can be preferably used. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same among the grains, but if an emulsion having the same halogen composition among the grains is used, it is easy to make the properties of each grain uniform. In addition, regarding the halogen composition distribution inside silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in every part of the silver halide grain, and grains with a core inside the silver halide grain and a shell surrounding it. (Shell) [-layer or multiple layers] Particles with a so-called laminated structure in which the halogen composition is different, or
Appropriately select and use particles with a structure that has parts with different halogen compositions in a non-layered manner inside or on the particle surface (if it is on the particle surface, parts of different compositions are joined to the edges, corners, or faces of the particle). be able to. In order to obtain high sensitivity, it is more advantageous to use one of the latter than particles with a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When silver halide grains have the above-mentioned structure, even if the boundaries between different parts of the silver halide composition are clear, the boundaries may be unclear due to the formation of mixed crystals due to compositional differences. It is also possible to have continuous structural changes.

Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide/silver chloride ratio can be used. Although this ratio can vary widely depending on the purpose, a silver chloride ratio of 2% or more is preferably used.

Furthermore, so-called high-silver chloride emulsions having a high silver chloride content are preferably used in light-sensitive materials suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more,
More preferably 95 mol% or more.

Such a high silver chloride emulsion preferably has a structure in which the localized silver bromide layer is provided inside and/or on the surface of the silver halide grains in a layered or non-layered manner as described above. The halogen composition of the localized layer preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%. These localized layers can be located inside the grains or on the edges, corners, or surfaces of the grain surfaces, and one preferred example is one in which they are epitaxially grown on a part of the corner of the grains.

On the other hand, in order to minimize the decrease in sensitivity when a photosensitive material is subjected to pressure, even in high silver chloride emulsions with a silver chloride content of 90 mol% or more, grains with a uniform structure with a small distribution of halogen composition within the grains are used. It is also preferable to use

Furthermore, it is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the amount of replenishment of the development processing solution.

In such cases, the silver chloride content is 98 mol% to 10
Emulsions of almost pure silver chloride, such as 0 mol %, are also preferably used.

Average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is taken)
is 0. It is preferably lμ to 2μ.

In addition, their particle size distribution has a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20%.
Hereinafter, a so-called monodisperse material having a content of 15% or less is preferable. At this time, in order to obtain a wide latitude, it is preferable to blend the above-mentioned Sato-dispersed emulsions in the same layer or to apply multilayer coating.

The shape of silver halide grains contained in photographic emulsions is regular (cubic, tetradecahedral, or octahedral).
lar) those with crystal shapes, those with irregular crystal shapes such as spherical, plate-like, etc.
Alternatively, a composite form of these can be used. Moreover, it may be made of a mixture of crystals having various crystal forms. In the present invention, among these particles, it is preferable to contain particles having the above-mentioned regular crystal shape in an amount of 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition to these, the average aspect ratio (yen equivalent diameter/
An emulsion in which tabular grains with a projected area of 5 or more, preferably 8 or more (thickness) exceeds 50% of the total grains can also be preferably used.

The silver chlorobromide emulsion used in the present invention is P, Glafkid
Chimie et Ph1sique Pho by es
tographique (Paul!+!onte1, 1967), by G.F. Duffin, Ph.
otographic Emulsion Chemi
try (Focal Press, 1966)
, V.L., 2elikman et al.Maki
ngand Coating Photography
c Emulsion (published by Focal Press,
(1964) and others. 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 method such as one-sided mixing method, simultaneous mixing method, or a combination thereof. May be used.

A method in which particles are formed in an atmosphere containing excess silver ions (so-called back mixing method) can also be used.

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, the so-called Chondrald 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.

Various polyvalent metal ion impurities can be introduced into the silver halide emulsion used in the present invention during the process of emulsion grain formation or physical ripening.

Examples of compounds used include cadmium, zinc, lead,
Salts such as copper and thallium, or iron, which is a group II element,
Examples include salts or complex salts of ruthenium, rhodium, palladium, osmium, iridium, platinum, and the like. In particular, the above-mentioned Group Ⅰ elements can be preferably used. The amount of these compounds added varies over a wide range depending on the purpose, but is preferably from 10@-9 to 10@-1 mol relative to silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

Regarding the chemical sensitization method, sulfur sensitization typified by the addition of unstable sulfur compounds, noble metal sensitization typified by gold sensitization, or reduction sensitization can be used alone or in combination. Regarding compounds used for chemical sensitization, see the lower right column on page 18 of the specification of JP-A-62-215272.
Those described in the upper right column of page 22 are preferably used.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye-spectral sensitizing dye that absorbs light in a wavelength range corresponding to the desired spectral sensitization. Spectral sensitizing dyes used at this time include, for example, Het.
erocyclic compoundsCyanin
e dies and related compou
nds (John Wiley & 5ons [Ne
W York, London 1, 1964).

Specific examples of compounds and spectral sensitization methods can be found in the upper right column of page 22 of the specification of JP-A-62-215272 mentioned above.
The one described on page 38 is preferably used.

The silver halide emulsion used in the present invention has the following properties:
Alternatively, various compounds or their precursors can be added for the purpose of stabilizing photographic performance. As specific examples of these compounds, those described on pages 39 to 72 of the specification of JP-A-62-215272 mentioned above are preferably used.

The emulsion used in the present invention may be either a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface or a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Also good.

When the present invention is applied to a color photosensitive material, the color photosensitive material includes a yellow coupler, a magenta coupler, and a cyan coupler that form yellow, magenta, and cyan colors respectively by coupling with an oxidized product of an aromatic amine color developer. is usually used.

Cyan couplers, magenta couplers and yellow couplers preferably used in the present invention are represented by the following general formulas (C-I), (C-II), (M-■), (M-n) and (Y). It is something.

General formula (C-I) General formula (C-11) Y.

One form CM-I) General formula (M-〇) Zc=2b General formula (Y) In general formulas (C-I) and (C-If), R1,
Rt and R4 represent a substituted or unsubstituted aliphatic, aromatic or heterocyclic group, Rs, Rs and R1 represent a hydrogen atom, halogen atom, aliphatic group, aromatic group or acylamino group, R, is R2 It may also represent a group of nonmetallic atoms that together form a nitrogen-containing 5- or 6-membered ring. Yl
, Y represents a hydrogen atom or a vine group that is separated during a coupling reaction with an oxidized product of a developing agent. n represents 0 or l.

R3 in general formula (C-n) is preferably an aliphatic group, such as methyl group, ethyl group, propyl group, butyl group, pentadecyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, phenyl group. Examples include thiomethyl group, dodecyloxyphenylthiomethyl group, butanamidomethyl group, and methoxymethyl group.

Preferred examples of the cyan coupler represented by the general formula (C-I) or (C-II) are as follows.

In general formula (C-I), preferable R1 is an aryl group,
A heterocyclic group, such as a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group,
More preferably, it is an aryl group substituted with a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group.

In general formula (C-I), when R3 and R2 do not form a ring, R2 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R3 is preferably a hydrogen atom.

In general formula (C-11), R4 is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In the general formula (C-I[), R6 preferably has 2 to 2 carbon atoms.
It is a methyl group having 15 alkyl groups and a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In general formula (C-11), R3 is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

In general formula (C-11), preferred R6 is a hydrogen atom,
A halogen atom, with chlorine and fluorine atoms being particularly preferred. Preferred Y and Y2 in general formulas (C-I) and (C-n) are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

In the general formula (M-I), R7 and R represent an aryl group, R8 represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group,
Y represents a hydrogen atom or a leaving group. The substituents allowed for the aryl group (preferably the phenyl group) of R7 and R1 are the same as the substituents allowed for the substituent R3, and when there are two or more substituents, they may be the same or different. You can. R1 is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, particularly preferably a hydrogen atom. Preferred Y is of the type that leaves off with either sulfur, oxygen or nitrogen atoms, for example as described in US Pat. No. 4,351,897 and International Publication WO 3810479.
The sulfur atom detachment type as described in No. 5 is particularly preferred.

In the general formula (M-IF), R1 represents a hydrogen atom or a substituent. Y represents a hydrogen atom or a leaving group, and particularly preferably a halogen atom or an arylthio group. Za, Zb
and Zc is methine, substituted methine, =N- or -NH-
, one of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. The case where the Zb-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. This includes the case where a dimer or more multimer is formed with RID or Y, and when Za, Zb or Zc is a substituted methine, the case where a dimer or more multimer is formed with the substituted methine.

Among the pyrazoloazole couplers represented by the general formula (M-It), the imidazo(1,2 -bl pyrazoles are preferred;
Pyrazolo [1] described in US Pat. No. 4,540°654
, 5-b) (1°2.4) Riazole is particularly preferred.

In addition, a branched alkyl group as described in JP-A No. 61-65245 is directly connected to the 2.3 or 6-position of the pyrazolotriazole ring to create a pyrazolotriazole coupler, which is described in JP-A No. 61-65246. pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, European Patent Publication No. 226, It is preferred to use pyrazolotriazole couplers having an alkoxy or aryloxy group in the 6-position, such as those described in No. 849 and No. 294.785.

In the general formula (Y), Rl represents a halogen atom, an alkoxy group, a trifluoromethyl group, or an aryl group, and Rl represents a hydrogen atom, a halogen atom, or an alkoxy group. A is -NHCOR, J, NHS Ot R
4, SO2N HR+ s, -COOR,, -SO
,NR,,. However, R8 R1 and R14 each represent an alkyl group, an aryl group or an acyl group. Y represents a leaving group. R11 and R4,
The substituents for R+4 are the same as those allowed for R4, and the leaving group Y is preferably of the type that leaves at either an oxygen atom or a nitrogen atom;
Particularly preferred is the nitrogen atom detachment type.

General formulas (C-I), (C-11), (M-I), (M-
Specific examples of couplers represented by n) and (Y) are listed below.

(C-1) ShiL (C-4) 0)1 (C-5) (1 (C-6) tHs 1 (C-7) (C-8) tHs (C-9) (C-10) (C-12) H (C-13) (C-14) (C-15) (C-16) Js (C-17) (C-18) (C-19) (C-20) (C-21) (C-22) (M-1) I 1 (M-2) I Shil (M-3) t (M-4) CM-6) Shil (M-7) CM-8) CH.

Hz (Y-1) (Y-2) (Y-3) i (Y-4) (Y-5) (Y-6) (Y-7) (Y-8) (Y-9) Above - Couplers of the form (C-I) to (Y) are:
The silver halide emulsion layer constituting the photosensitive layer usually contains 0.1 to 1.0 mol per mol of silver halide, preferably 0.
．． It is contained in an amount of 1 to 0.5 mol.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by the oil-in-water dispersion method known as the oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in an aqueous gelatin solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water droplet dispersion with phase inversion.

Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method. From the coupler dispersion,
The low-boiling organic solvent may be removed by distillation, noodle washing, ultrafiltration, or the like, and then mixed with the photographic emulsion.

As a dispersion medium for such couplers, the dielectric constant (25°C
) It is preferable to use a high boiling point organic solvent and/or a water-insoluble polymer compound having a refractive index (25° C.) of 1.5 to 1.7.

As the high boiling point organic solvent, preferably the following general formula (A) ~
A high boiling point organic solvent represented by (E) is used.

General formula (A) General formula (B) -coo-w2 General formula (C) General formula (D) W, W.

\/ General formula (E) Wl-0-Wt (wherein Wl, W2 and W are each substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group,
represents an aryl group or a heterocyclic group, W, is Wl,
represents OWI or S −W +, n is l to 5
is an integer of , and when n is 2 or more, W may be the same or different from each other; - In the general formula (E), Wl and W
, may form a fused ring).

The high boiling point organic solvent that can be used in the present invention also has a melting point of 100'C or less and a boiling point of 140'
It can be used as long as it is a compound that is immiscible with water at temperatures above °C and is a good solvent for the coupler. The melting point of the high-boiling organic solvent is preferably 80°C or lower. The boiling point of the high boiling point organic solvent is preferably 160°C or higher, more preferably 170°C or higher.

For details on these high boiling point organic solvents, please refer to JP-A-62
-215272 Publication Specification, page 137, lower right column ~ 14
It is written in the upper right column of page 4.

These couplers can also be synthesized with rhodapul latex polymers (
For example, U.S. Patent No. 4. 203. No. 716) or dissolved in a water-insoluble but organic solvent-soluble polymer to emulsify and disperse in an aqueous hydrophilic colloid solution.

Homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO 38100723 are preferably used, and acrylamide polymers are particularly preferred from the viewpoint of color image stabilization.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

Various anti-fading agents can be used in the photosensitive material of the present invention. That is, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and silylation of the phenolic hydroxyl groups of each of these compounds. Representative examples include alkylated ether or ester derivatives. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiorubamato)nickel complex can also be used.

Specific examples of organic antifade agents are described in the following patent specifications:

Hydroquinones are disclosed in U.S. Patent No. 2,360,290;
Same 2nd. 418. No. 613, s2,700.45
No. 3, No. 2,701,197, No. 2,728,6
No. 59, same No. 2. 732. No. 300, No. 2.73
No. 5,765, No. 3,982.944, No. 4,4
30.425, British Patent No. 1,363.921, U.S. Patent No. 2,710.801, U.S. Patent No. 2.816,02
No. 8, etc., 6-hydroxychromans, 5-hydroxycoumarans, and spirochromans are disclosed in U.S. Patent No. 3゜43.
2.300, 3,573.050, 3,5
No. 74,627, same No. 3. 698. No. 909, No. 3,764,337, and JP-A-52-152225, spiroindanes are disclosed in U.S. Patent No. 4,360,58.
No. 9, p-alkoxyphenols are disclosed in U.S. Patent No. 2,
No. 735,765, British Patent No. 2.066.975;
Hindered phenols are disclosed in U.S. Pat.
No. 0.455, JP-A-52-72224, U.S. Patent No. 4
, No. 228.235, Special Publication No. 52-6623, etc.
Gallic acid derivatives, methylenedioxybenzenes, and amine phenols are each disclosed in U.S. Patent No. 3,457,079.
No. 4,332,886, Special Publication No. 56-2114
No. 4, etc., and hindered amines are disclosed in U.S. Patent No. 3. 3
36. 135, British Patent No. 4,268,593, British Patent No. 1,326,889, British Patent No. 1,354,313, British Patent No. 1,410,846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. No. 58-114036, No. 59-53846
Metal complexes are described in U.S. Patent Nos. 4,050,938 and 4,241,155, and British Patent No. 2,027.731(A), etc. ing. The purpose of these compounds can be achieved by co-emulsifying them with a coupler and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight based on the corresponding color coupler. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to it.

As ultraviolet absorbers, benzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533.L
94), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3,314°794, U.S. Pat. No. 3,352,
681), benzophenone compounds (e.g., those described in JP-A No. 46-2784), Keihi Shunnistil compounds (e.g., those described in U.S. Pat. Nos. 3,705,805 and 3,707,395), ), butadiene compounds (as described in U.S. Pat. No. 4,045,229), or benzoxidole compounds (e.g., U.S. Pat. No. 3,406,070; 271,307) can be used. An ultraviolet-absorbing coupler (for example, an α-naphthol-based cyan colorant), an ultraviolet-absorbing polymer, or the like may be used. These ultraviolet absorbers may be mordanted in specific layers.

Among these, benzotriazole compounds substituted with the above-mentioned aryl group are preferred; in addition, it is particularly preferable to use the following compounds together with the above-mentioned couplers. Particularly preferred is the combination with a pyrazoloazole coupler.

That is, a compound (F) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. For example, in storage after processing, the compound (G) that chemically bonds with the oxidized form of a group amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly. This is preferable in order to prevent staining and other side effects caused by the formation of coloring dyes due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler.

A preferred compound (F) has a second-order reaction rate constant with p-aningine of * (in trioctyl phosphate at 80°C) of 1.01/mol sec.
It is a compound that reacts in the range of ~1×10-S1/mol-8eC. Note that the second-order reaction rate constant is based on JP-A-63-1.
It can be measured by the method described in No. 58545.

When kl is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if k is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, side effects of the remaining aromatic amine developing agent may not be prevented.

A more preferable compound (F) can be represented by the following formula (FI) or (Fn).

General formula (F1) R+-(A), -X General formula (Fn) R, -C=Y In the formula, R+ and Rt each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group that reacts with the aromatic amine developer to form a chemical bond, and X represents a group that reacts with the aromatic amine developer and leaves. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents the addition of an aromatic amine developing agent to the compound of general formula (F n). Represents a promoting group. Here R2 and X1Y
and R2 or B may be bonded to each other to form a cyclic structure.

Among the methods of chemically bonding with the residual aromatic amine developing agent, the typical ones are substitution reaction and addition reaction.

For specific examples of compounds represented by general formulas (FI) and (F, I[), see JP-A-63-158545 and JP-A-63-158545;
-283338, European Patent Publication No. 298321, 2
Those described in specifications such as No. 77589 are preferred.

On the other hand, a more preferable compound (G) that chemically bonds with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inert and colorless compound is the following general formula (GI ).

General formula (GI) R'Z In the formula, R5 represents an aliphatic group, an aromatic group or a heterocyclic group. Z represents a nucleophilic group or a group that decomposes in the photosensitive material to release a nucleophilic group. In the compound represented by the general formula (GI), Z is Pearson's nucleophilic 'CH,I value (R,G, Pearson, et al., J
, Am.

Chem, Soc, 9th edition, 319 (1968
)) is preferably 5 or more, or a group derived therefrom.

For specific examples of compounds represented by the general formula (GI), see European Patent Publication No. 255722, Japanese Patent Application Laid-Open No. 1430-1980
No. 48, No. 62-229145, patent application No. 63-136
No. 724, No. 62-214681, European Patent Publication 29
Those described in No. 8321, No. 277589, etc. are preferred.

Further, details of the combination with the above-mentioned compound (G) and compound (F) are described in European Patent Publication No. 277589.

The photosensitive material produced using the present invention contains a water-soluble dye or a dye that becomes water-soluble through photographic processing as a filter dye in the hydrophilic colloid layer or for various purposes such as preventing irradiation or halation. You can leave it there. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin, written by Arthur Vuis (Academic Press, published in 1964).

As the support used in the present invention, transparent films such as cellulose nitrace film and polyethylene terephthalate, which are usually used in photographic materials, and reflective supports can be used. For purposes of the present invention, the use of reflective supports is more preferred.

The "reflective support" used in the present invention is one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Examples include those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, and reflective layers were added. Alternatively, a transparent support using a reflective substance, such as a glass plate, a polyester film such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, a polyamide film, a polycarbonate film,
Examples include polystyrene film and vinyl chloride resin.

As other reflective supports, supports having a specular reflective or second type diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.0 in the visible wavelength range.
The number is preferably 5 or more, and the metal surface is preferably roughened or metal powder is used to make it diffusely reflective. The metal may be aluminum, tin, silver, magnesium, or an alloy thereof, and the surface may be a surface of a metal plate, metal foil, or thin metal layer obtained by rolling, vapor deposition, plating, or the like.

Among these, it is preferable to obtain the metal by vapor-depositing the metal onto another substrate. Preferably, a layer of water-resistant resin, particularly thermoplastic resin, is provided on the metal surface. It is preferable to provide an antistatic layer on the side of the support of the present invention opposite to the side having the metal surface. For details of such a support, see, for example, JP-A-61-210
No. 346, No. 63-24247, No. 63-24251
No. 63-24255, etc.

These supports can be appropriately selected depending on the purpose of use.

For the light-reflecting substance ζ, it is best to thoroughly knead a white pigment in the presence of a surfactant, and also coat the surface of the pigment particles with
It is preferable to use one treated with ~tetrahydric alcohol.

The occupied area ratio (%) of white pigment fine particles per defined unit area is calculated by dividing the observed area into adjoining unit areas of 6 μm x 6 μm, and dividing the area of fine particles projected onto that unit area. It can be determined by measuring the occupied area ratio (%) (R,). The coefficient of variation of the occupied area ratio (%) can be determined by the ratio s/R of the standard generic difference S of R+ to the average value of R. The number (n) of target unit areas is preferably 6 or more. Therefore, the coefficient of variation S/trap can be determined.

In the present invention, the coefficient of variation of the occupied area ratio (%) of the pigment fine particles is preferably 0.15 or less, particularly 0.12 or less. When it is 0.0a or less, it can be said that the dispersibility of the particles is substantially "uniform".

Example 1 Photographic paper samples (1) to (1'') were prepared by coating a photosensitive silver halide emulsion layer on a photographic paper support as follows.

Canadian Freeness 280C3F-
It was refined.

To this paper stock, the internal sizing agents and paper strength agents shown in Table 1,
A fixing agent and a pH adjuster were added in specified amounts.

Paper was made using the paper stock, and 1.0 g/rrr of carboxyl-modified polyvinyl alcohol was added using a size press.

Calcium chloride was applied at 1.0 g/rd. Adjust the thickness with a calender, weighing 150g/rri thickness 150
I made μ paper.

Next, use a laminator to apply 1 layer of titanium oxide to the front surface.
Polyethylene containing 0% by weight was laminated with 28g/% of polyethylene alone on the back side, and the surface of the polyethylene containing titanium oxide of the support was subjected to corona discharge treatment, and then the following silver 10 genide emulsion layer was applied.

1st layer coating solution preparation Yellow coupler (ExY) 60. Og and 28.0 g of anti-fading agent (Cpd-1), 150 cc of ethyl acetate, 1.0 cc of solvent (Solv-3), and 28.0 g of anti-fading agent (Cpd-1).
-4) Add and dissolve 3.0 cc, add this solution to 450 cc of a 10% gelatin aqueous solution containing sodium dodecylbenzenesulfonate, and then disperse with an ultrasonic homogenizer. A first layer coating solution was prepared by mixing and dissolving this in 420 g of a silver chlorobromide emulsion (silver bromide 0.7 mol %) containing a sensitive dye.

Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. The gelatin hardening agent for each layer is 1.2-
Bis(vinylsulfonyl)ethane was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer; anhydro-5,5'-dichloro-3,
3"-disulfoethyl thiacyanine hydroxide green-sensitive emulsion layer; anhydro-9-ethyl-5,5"-diphenyl-3,3'-disulfoethyl oxacarbocyanine hydroxide red-sensitive emulsion layer; L3--diethyl -5-methoxy-9,
11-Neopentylthiazidylupocyanine iodide The following was used as a stabilizer for each emulsion layer.

1-(2-acetaminophenyl) The following was also used as an irradiation-preventing dye.

[3-carboxy-5-hydroxy-4-(5-(3-
Carboxy-5-oxo-1-(2,5-bisulfonatophenyl)-2-pyrazolin-4-ylidene)-1-propenyl)-1-pyrazolyl]benzene-2,5-disulfonate-disodium salt N,N- -(4,8-dihydroxy-9,10-dioxo-3,7-cissulfonatoanthracene-1,5-diyl)bis(aminomethanesulfonate)-tetrasodium salt [3-cyano-5-hydroxy-4- (3-(3-cyano-5-okine-1-(4-sulfonatophenyl)-
2-pyrazolin-4-ylidene)-1-pentanyl)-
1-pyrazolyl]benzene-4-sulfonate-sodium salt (layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/d). The silver halide emulsion represents the coated amount in terms of silver.

Support Paper support laminated on both sides with polyethylene, the surface of which was subjected to corona discharge treatment Layer (blue-sensitive layer) Silver chlorobromide emulsion (AgBr 0.7 mol%, cubic,
Average particle size: 069μm) 0.29 Gelatin 1.80 Yellow coupler (ExY) 0.60 Anti-fade agent (Cp
d-1) 0.28 solvent (Solv-3)
0.01 solvent (Solv-4)
0.03 Second layer (color mixing prevention layer) Ceratin 0.80 Color mixing prevention agent (Cpd-2) 0. 055 Solvent (Solv
-1) 0.03 solvent (Solv-2)
0.15 Third layer (green-sensitive layer) The above-mentioned silver chlorobromide emulsion (AgBr0.7 mol%, cubic,
Average particle size: 0.45 μm) 0.18 Gelatin magenta coupler (ExM) Anti-fading agent (Cpd-3) Anti-fading agent (Cpd-4) Solvent (Solv-1) Solvent (Solv-2) Fourth layer (color mixing prevention Layer) Gelatin color mixing inhibitor (Cpd-2) Ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2) Solvent (Solv-1) Solvent (Solv-2) Fifth layer (red sensitive layer) Above-mentioned salt Silver bromide emulsion (AgBr average grain size 0.5 μm) Gelatin cyan coupler (ExC-1) Cyan coupler (ExC-2) Antifading agent (Cpd-1) 4 mol%, cubic, 0.21 1.80 0. 26 0.12 0.20 Solvent (Solv-1) 0.16 Solvent (
Solv-2) 0.09 color accelerator (
Cpd-5) 0.15 6th layer (ultraviolet absorption layer) Ceratin 0.70 ultraviolet absorber (UV-1) 0.26 ultraviolet absorber (U
V-2) 0.07 solvent (Solv-])
0.30 Soluv & (Sol v-2)
0. 09 Seventh layer (protective layer) Gelatin 1.07 (ExY)
Yellow coupler α-pivalyl α-(3-benzyl-1-hydantoinyl)-2-chloro-5-[β-(dodecylsulfonyl)
butyramide] acetanilide (ExM) magenta coupler 7-chloro-6-ituprobyl-3- +3-[(2-
Butoxy-5-tert-octyl)benzenesulfonyl]propyl]-18-pyrazolo[5,1-dan]-1,
2,4-) lyazole (ExC-1) cyan coupler 2-pentafluorobenzamide-4-chloro-5[2
-(2,4-di-tert-amylphenoxy)-3-
Methylbutyramidephenol (ExC-2) Cyan coupler 2,4-dichloro-3-methyl-6-[α(2,4-di-tert-amylphenoxy)butyramide]phenol (Cpd-1) Anti-fade agent -(- CH2-CH+.

CON　HC=Ha(n) Average molecular weight so, oo.

(Cpd-2) Color mixing inhibitor 2.5-di-tert-octylhydroquinone (Cp
d-3) Anti-fade agent 7.7'-dihydroxy-4,4,4-,4-mono-tetramethyl-2,2'-spirochroman (Cpd-4) Anti-fade agent N-(4-dodecyloxyphenyl)-morpholine (Cpd-5) Color development accelerator p-(p-toluenesulfonamide)-phenyl-dodecane (Solv-1) Solvent di(2-ethylhexyl) phthalate (Solv-2) Solvent dibutyl phthalate (Solv-3) Solvent di( i-nonyl)phthalate (Solv-4) solvent N,N-diethylcarbonamido-methoxy-2,4-
Di-t-amylbenzene (UV-1) UV absorber 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole (UV-2) UV absorber 2-(2-hydroxy-3, 5-tert-butylphenyl) benzotriazole The above coated samples (1) to (13) were processed using a continuous automatic processor (Fuji Film Mini Lapo Paper Processor f-FA140).
It was developed by The treatment steps, treatment time, and composition of the treatment liquid are as follows.

Processing process Eishin Tusei color development 38℃ 45 seconds bleach fixing 35℃ 45 seconds rinse ■ 35℃ 30 seconds rinse ■ 35℃ 30 seconds rinse ■ 35℃ 30 seconds drying 80℃ 60 seconds Color developer Water 60〇 -ethylenediamine-N,N.

N-,N=-tetramethylenephosphonic acid 2.0g Potassium bromide 0.015g Potassium chloride
3.1g triethanolamine
10.0g Potassium carbonate optical brightener (W) IITEX, 4B Sumitomo Chemical) Additive (preservative) N-ethyl-N-(β-methanesulfonamidoethyl) -3-methyl-4-amino 7g 1.0g See Table 2 Add water to pH (25°C) Bleach-fix solution Water Ammonium thiosulfate (70%) Sodium sulfite Iron (In) ethylenediaminetetraacetic acid Ammonium ethylenediaminetetraacetic acid Di-1000% 10°400-10 〇- 7g 5g Add thorium water to 1007 PH (25°C) 6.0 unit ≦ (trace ion exchange water (calcium, magnesium 3pp each)
m or less) Change the preservative in the developer as shown in Table 2, and apply sample (1)
- (13) were processed and the degree of edge staining was examined.

After the treatment, a 1 m arbitrary section of the cut surface of the end of the support of the sample was examined, and edge staining was evaluated based on the ratio of the soiled area to the cut surface.The results are shown in Table 2.

According to the results in Table 2, it can be seen that when the support of the present invention is treated with a developer using the compound represented by the general formula (I) of the present invention, the etch stain is significantly improved.

Example-2 Photographic paper samples (101) to (101) in which a photosensitive silver halide emulsion layer was coated on a photographic paper support in the same manner as in Example-1.
113) was created.

Canadian Freeness 280C3Fd is prepared by mixing 50% by weight of kraft hardwood valve (LBKP) and 50% by weight of sulfide hardwood valve (LBSP).
It was refined.

Specified amounts of internal sizing agents, paper strength agents, fixing agents, and pH adjusters shown in Table 3-1 were added to this paper stock. Using the paper stock, paper was made using a size press with 1.0 g/d of carboxyl-modified polyvinyl alcohol and 1.0 g/d of calcium chloride.
g/% was applied.

Adjust the thickness with a calender and weigh 150 g/m1
Paper with a thickness of 150μ was made.

Next, use a laminator to apply 1 layer of titanium oxide to the front surface.
Polyethylene containing 0% by weight was laminated with 28 g/m of polyethylene alone on the back side, and after the surface of the polyethylene containing titanium oxide of the support was subjected to corona discharge treatment, the following silver halide emulsion layer was coated.

A multilayer color photographic paper having the layer structure shown below was prepared on a paper support coated with polyethylene on both sides. The coating solution was prepared as follows.

No.-N Coating Solution Preparation Yellow coupler (ExY) 19.1 g, color image stabilizer (Cpd-1) 4.4 g and color image stabilizer (Cp
d-7) Add and dissolve 27.2 cc of ethyl acetate and 8.2 g of solvent (Solv-1) to 0.7 g, and dissolve this solution in 8 cc of 10% sodium dodecylbenzenesulfonate.
The mixture was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution. On the other hand, a compacted silver bromide emulsion (cubic, average grain size 0.8
B, 3 = 7 mixture of later and 0.70 - (silver molar ratio) 0 coefficient of variation of particle size distribution is 0.08 and 0.1
0, each emulsion contains 2 mol % of iI O bromide locally on the grain surface) and the blue-sensitive sensitizing dye shown below is added to s! 2.0X10-' for large size emulsions per mole, respectively.
molar addition, and for small size emulsions, 2.
Sulfur sensitization was prepared after addition of 5×10 −′ moles.

The above emulsified drink and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below.

□Heavy liquid for the second to seventh layers is also applied in the same way as the heavy liquid for layer 1! ! ! Manufactured. The gelatin hardening agent for each layer is 1
-oxy-3,5-dichloro-8-triazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue sensitive emulsion layer (2.0 X 10'' mole each for large size emulsions and 2.5 X 10'' mole each for small size emulsion per mole of halogenation) Green sensitive emulsion layer (per mole of silver halide, 4.0 x 10-' moles for large size emulsions, 5.6 moles for small size emulsions)
x 10° 4 mol) and (per mol of silver halide, ?, 0 x 10-' mol for large size emulsions, and 1
．． 0x10-' mol) Red-sensitive emulsion layer (per mole of halide s!, 0.9x10-' mol for large size emulsions and 1.1x10-' mol for small-sized emulsions) Red-sensitive emulsion For the layer, the following compounds are halogenated i
! 3 moles of 2.6X10 were added per mole.

In addition, for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to each mole of halogenated S, B, 5 x 10'' mmole, ?, 7X10-'mol, 2.
Added 4 moles of 5X10°.

Furthermore, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene was added at 1×10° per mole of silver chloride, respectively.
4 moles and 2X10'' moles were added.

The following dyes were added to the emulsion layer to prevent irradiation.

and (N configuration) The composition of each layer is shown below.

The number is the coating amount (g/rrf) The silver halide emulsion that represents S! Represents the converted coating amount.

Support polyethylene laminate (the polyethylene on the first layer side contains a white pigment (TiOi) and a bluish dye (ulmarine)) No.-N (blue-sensitive layer) Said silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow Coupler, (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.3
Five-color image stabilizer (Cpd-7) 0
．． 06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08)
Container (Solv-1)
0.16 solvent (Solv-4)
0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (cubic, 1=3 mixture of one with an average grain size of 0.554 and one with an average grain size of 0.39- (Ag molar ratio) 0 grain size distribution The coefficient of variation is 0.10 and 0.08,
(Each emulsion contained 8 mol% of AgBrO locally on the grain surface) 0.12 Gelatin
1.24 Mazenk Cobra (EX C) 0.20 Color Image Stabilizer (Cpd-2
) 0.03 color image stabilizer (Cpd
-3) 0.15 color image stabilizer (C
pd-4) 0.02 color image stabilizer (Cpd, 9) 0.02 solvent (
Solv-2) 0.40 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixture prevention agent (Cpd-5) 0.05
Container (Solv-5)
0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (cubic, l:41 compound of average grain size 0.58μ and 0.45μ (Ag molar ratio) 0 grain size distribution The coefficient of variation is 0.09 and 0.11.
Each emulsion contained 6 gBrO, 6 mol% locally on a part of the grain surface') 0.23 gelatin
1.34 cyan coupler (Ex
C) 0.32 color image stabilizer (Cp
d-6) 0.17 color image stabilizer (
Cpd-7) 0.40 Color image stabilizer (Cpd-8) 0.04 Solvent (SOIV-6) 0.15
Sixth layer (ultraviolet absorption layer) Gelatin 0.53 ultraviolet,
J absorber (UV-1) 0.16
Color mixing inhibitor (Cpd-5) 0.
02 Solv W (Solv-5)
0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 17)
%) O,LT liquid paraffin 0.03 (ExY) 1:1 mixture (molar ratio) with yellow coupler (ExM) 1: ■ mixture (molar ratio) of Mazenk coupler (EXC) Cyan coupler R-CtHs and Ca A mixture of 2=4:4 by weight of 'd* and H (Cpd-1) Color image stabilizer (Cpd-2) Color image stabilizer C00CtHS (Cpd-3) Color image stabilizer (Cpd-4) Color Image stabilizer (Cpd-5) Color mixture inhibitor H (Cpd-6) 2=4=4 mixture of color image stabilizers (weight ratio) (Cpd-7) Color image stabilizer 1+CI1. -C11)r- CONHC4H4(t) Average molecular weight 6Q, 0OO (Cpd-8) Color image stabilizer R (Cpd-9) Color image stabilizer (UV-1) 4:2:4 mixture of ultraviolet absorber (by weight 2:l mixture (volume ratio) of (Solv-1) solvent (Solsee 2) solvent (Solv-4) solvent (Solsee 5) solvent C00Cdl+t (CH□).

C00CJ + Tsu (Solv-6) Solvent After imagewise exposure of the above samples (101) to (113), using an automatic paper processor, the following processing steps and processing compositions were used to process twice the tank capacity of the color developer. Continuous processing (running test) was carried out until replenishment.

The composition of the color developer was changed as shown in Table 3-2.

Processing process Toyo Seishin 0 tank capacity Color development 38°C 45 seconds 109d 41 Bleach fixing 30-36°C 45 seconds 215mA' 4A stable 3
0~37°C 20 seconds -21 Stable ■ 30~37°C 20 seconds -21 Stable ■ 30~37°C 20 seconds 364m1 21 Dry
Drying 70-85°0 60 seconds Replenishment amount per 1 d of light-sensitive material (3-tank countercurrent system from stable ■ to ■ and 1.) The composition of each processing stage is as follows.

Water 800 mj 800 d Ethylenediaminetetraacetic acid 5.0 g 5.0 g 5.6-hydroxybenzene-1+ 2゜4-trisulfonic acid Triethanolamine Potassium chloride Potassium bromide Potassium carbonate N-ethyl-N-(β Methanesulfonamidoethyl )-3- Methyl-4-aminoaniline sulfate organic preservative (see Table 3-2) Sodium sulfite fluorescent brightener (Sumitomo Chemical rWtllTEX-4J diaminostilbene series) Add water to give 0.3 g 8 .0g 3.2g 0.015g 5g 5.0g 0.03mol 0.1g 0.3g 8.0g 5g 9.5g 0.05mol 0.2g 1, Og 2.5g 100 (W 1000.v4 pH (25° C) 10.05 10.
60 bleach-fix solution (tank solution and replenisher are the same) water
400d Ammonium thiosulfate (70%) 100J Sodium sulfite 17g Iron(II[) ammonium ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 5g Glacial acetic acid
Add 9g water
l OUOatpH (25°C)
5.40 stable e (tank solution and replenisher are the same) Formalin (37%) 0.1g formalin-sulfite adduct 0.7g 5-chloro-2-
Methyl-4 Isothiazolin-3-one 0゜2g 2-Methyl-4-isothiazolin-3-one O, 01g Copper sulfate
0.005g ammonia water (28%)
Add 2.0n flood water
1000 ml pH (25°C) 40
In addition, the replenishment night concentrations were set so that the current (!&l night's chloride ion centrality and bromide ion concentration) would maintain the tank liquid centrality from the start to the end of the running process.

In order to examine the edge stains of these coated samples, after the running was completed, the above coating sample 1 was processed, and the edge stains were determined as Af 1lIliL, according to the ratio of the stained area to the cut surface of sample 1 in the same manner as in Example-1. , the mucus is shown in Table 3-2.

As is clear from Table 3-2, when the support of the present invention and the compound of general formula (+) of the present invention are used in combination, edge staining is significantly improved.

Furthermore, among the sizing agents of the present invention, when Al-1;luketene dimer is used, it is found that the effect of preventing edge tl slippage is particularly excellent.

Table 3 2 Table 3 2 (Continued) 3f 1IIli) 1 tli o%: No edge stains 1 to 5%: Some edge stains have occurred, but they are hardly noticeable and are not suitable for practical use. Level 6 to 20% without any problem; level 20% or higher where conspicuous machining and nozzle stains are a practical problem: level where edge stains are noticeable and the product price decreases Example-3 Treated water j#13 of Example-2 In the same manner as above, except that the preservative (2) of the color developer was changed to the Na salts of (1) and (7), the Na salts of (8) and (8), and the Na salts of (11) and (11). , (12), (14), (19), (20), (23)
, (26), (27), (31), (40), (42)
, (43), (44), (52), and (53), similarly good results were obtained.

(Effect of light) When a compound represented by -C (+) or a salt thereof is used as in the present invention, edge stains that still occur even if a specific sizing agent such as nil is used can be greatly improved. You can do it.

Claims (1)

[Scope of Claims] 1) A silver halide color photographic light-sensitive material having a light-sensitive silver halide emulsion layer on a paper support coated with polyolefin on both sides and at least one aromatic primary amine color developing agent. In the method of processing with a color developer containing, the paper support contains at least one of an epoxidized higher fatty acid amide, an alkyl ketene dimer, a higher fatty acid salt, or an alkenyl succinic anhydride, and the color developer A method for processing a silver halide color photographic material, which comprises a compound represented by the following general formula (I) or a salt thereof. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, L represents an alkylene group that may be substituted, and A
is a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be substituted with alkyl, an ammonio group which may be substituted with alkyl, a carbamoyl group which may be substituted with alkyl, a carbamoyl group which may be substituted with alkyl, R represents a hydrogen atom or an optionally substituted alkyl group. )