JPH03102344A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the increase in stain in continuous processing and to decrease the contamination by suspended matter as well as to enhance the image preservable property of the processed photosensitive material by processing the photosensitive material contg. a slipping agent in the outermost layer with a color developing soln. contg. specific compds. CONSTITUTION:After the color photographic sensitive material contg. the slipping agent (e.g. the compd. expressed by formula I) in the outermost layer is exposed, the material is processed with the color developing soln. contg. an arom. primary amine color developing agent and the compd. expressed by formula II. In the formula II, L denotes (substd.) alkylene; A denotes carboxy, sulfo, etc.; R denotes H, (substd.) alkyl. The compd. expressed by formula III, etc., are usable as the component of the formula II.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for processing silver halide color photographic light-sensitive materials. The present invention relates to a treatment method that prevents this.

(Prior Art) Silver halide color photographic light-sensitive materials (hereinafter abbreviated as color light-sensitive materials) generally consist of a support such as various plastic films or paper coated with plastic, and a light-sensitive emulsion layer, an intermediate layer, and a protective layer. , a back layer, an antihalation layer, a yellow filter layer, and other structural layers are applied in combination as necessary.

Hydrophilic colloids, mainly gelatin, are usually used as the binder for the structural layers of this color sensitive material. However, coating films made of gelatin have a high coefficient of friction and have the disadvantage that they are easily scratched when they come into contact with other metal surfaces, plastic surfaces, or gelatin film surfaces. In particular, silver halide in photographic materials is sensitive to pressure, which causes pressure blur and desensitization, which has a fatal effect on images. This problem has become particularly serious in recent years as sensitivity has increased.

For this reason, in photographic materials, a non-photosensitive protective layer is usually provided on the photosensitive silver halide emulsion layer, or a back layer is provided on the other side of the support provided with the photosensitive layer. Measures have been taken to reduce the coefficient of friction.

One such means is the use of compounds called slip agents.

Regarding such lubricants, Japanese Patent Publication No. 50-40664
No., JP-A-51-115j92, JP-A No. 55-12613
No. 8, etc., describes a method of dispersing fine powders such as silica and glass, polymers, etc. in the protective layer or back layer of a photosensitive material. Also, U.S. Patent Nos. 2,976.148, 3,121,060, 3,933.516, and British Patent No. 1,320. No. 757, 1,321,
No. 994, No. 1,430,997, West German Patent Nos. 1 and 3
No. 00,015, No. 2,347,301, JP-A-51
No. 37217, No. 58-86540, etc., describe methods using high-boiling organic solvents, higher fatty acid salts or esters thereof, and polymers.

However, the above-mentioned slipping agents have problems such as insufficient reduction of the coefficient of sliding friction and the tendency for photosensitive materials to adhere to each other. Several methods have been proposed for improving the slipperiness of the surface of a photosensitive material by including it in the back layer. Some examples of these include, for example, U.S. Pat. No. 3,042,522, U.S. Pat.
No. 2, No. 55-49294, JP-A-60-14034
No. 1, No. 60-140342, No. 60-191240
No. 62-203152, No. 82-203154, No. 62-203155, and stipulates the storage conditions for sensitive materials using these compounds and the amount of coating on the layer containing them. 3-
6 5 No. 46, 6 3-8 6 4 2, 64
No.-77052, JP-A-1-107'25
5 etc.

However, a small amount of these lubricants are eluted into the processing solution and adhere to the photosensitive material as scum (floating matter), causing stains or causing tar and tar produced by oxidative deterioration of the developing agent in the processing solution. It has become clear that adsorption of so-called colored substances leads to an increase in staining and reduces processing stability in continuous processing. Furthermore, when the above-mentioned organosiloxane compounds are used, a new problem has arisen in that stains slightly increase when the photographic material after processing is allowed to age.

In recent years, in the processing of color photographic materials, there has been a demand for reduction of photographic waste liquid from the viewpoint of preventing environmental pollution, and for this purpose efforts have been made to reduce the amount of processing liquid replenishment. As a result, the above-mentioned problems are becoming more serious, and urgent solutions are required.

(Problems to be Solved by the Invention) Accordingly, a first object of the present invention is to provide a processing method for silver halide color photographic materials in which contamination by suspended matter is reduced. A second object of the present invention is to provide a processing method that prevents an increase in stain during continuous processing and has excellent processing stability. A third object of the present invention is to provide a processing method that provides excellent image storage stability of photographic materials after processing.

(Means for Solving the Problems) As a result of intensive research to solve the above problems, the present inventors have found that the purpose can be achieved by the method described below. That is, in a method in which a silver halide color photographic light-sensitive material is exposed and then treated with a color developer containing an aromatic primary amine color developing agent, the color developer contains at least one of the compounds represented by the following general formula (I). and at least one of the outermost layers of the silver halide color photographic light-sensitive material contains at least one slip agent. I was able to violate the commandment.

General formula (I) K (wherein L represents an optionally substituted alkylene group, A
is a carpoxy 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: R represents a hydrogen atom or an optionally substituted alkyl group. ) General formula (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 the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, and an alkyl (preferably carbon number 1 to 5) optionally substituted ammonio group; , hydroxy group is mentioned as a preferable example. A is a carpoxy group, a sulfo group,
Phosphono group, phosphinic acid residue, hydroxy group, alkyl (preferably 1 to 5 carbon atoms) optionally substituted amino group, alkyl (preferably 1 to 5 carbon atoms) optionally substituted ammonio group, alkyl (preferably represents a carbamoyl group which may be substituted with 1 to 5 carbon atoms, a sulfamoyl group which may be substituted with alkyl (preferably 1 to 5 carbon atoms), and represents a carboxy group, a sulfo group, a hydroxy group, a phosphono group, an alkyl-substituted group. A preferred example is a carbamoyl group which may be optional. -As examples of L-A, carboxymethyl group, carboxyethyl group, carboxyprobyl group,
Sulfoethyl group, sulfopyl group, sulfobutyl group,
Preferred examples include a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group, and particularly preferred examples include a carboxymethyl group, a carpoxyethyl group, a sulfoethyl group, a sulfobrobyl 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 the substituent 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 ammonia group which may be substituted with alkyl, a carbamoyl group which may be substituted with alkyl, Represents a sulfamoyl group which may be substituted with alkyl. There may be two or more substituents. Preferred examples of R include a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a carboxyprobyl group, a sulfoethyl group, a sulfopyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group. Carboxymethyl group, carboxyethyl group, sulfoethyl group,
Particularly preferred examples include a sulfobrobyl group, a phosphonomethyl group, and a phosphonoethyl group. L and R
may be connected to form a ring.

Specific examples of the compounds of the present invention are listed below, but the present invention is not limited thereto.

(3) CHI (4) C. H. C2 Hi (5) (6) CH. 1 1 CH. (8) 0H OH (19) HO-NH-CH. CO, (20) HO-NH-CH2CH. CO2 (2l) HO-NH-CH-Co! CH. (l2) CH. CH. (22) H O N H - C H - C O gH H, (23) HO-NH-CH-Co. H H, (24) HO-NH-CH-CH2 1 CH. C O 2 H (25) HO-NH-CH. -CH-Co. 1 CH. H (26) HO-NH-CH! CH. S08 H (27) HO-NH-CH. CHCHI SO, OH (28) HO-NH1 (CH!). SO3 H (29) HO-NH- (CH,), So, H (30) HO NH CH2 P○, HO-NH-CH-PO. tCH. (32) HO-NH-CH! CH2 PO, (33) HO-NH-CH! CH. OH (34) HO-NH- (CH!)1 OH (35) HO-NH-CH2 POz (46) HONHCHt CH (PO. H,), (53) (54) HO-NHCH. CHI C-NHC (CHs)
2CH! -SO3HII O The content of these compounds in the color developer is preferably 0.5 g to 50 g, more preferably 1.0 g to 30 g, particularly preferably 1.
It is 5g to 20g.

These compounds may be present in the photosensitive material. In addition, color developing agents present in each solution (such as brought in from a color developing device), not only in color developing solutions, but also in bleaching and bleach-fixing solutions, washing or washing substitute stabilizing solutions, etc. It can act on the oxidant to give good performance.

The compound represented by the general formula (I) can be prepared by alkylation reaction (nucleophilic substitution reaction) of commercially available hydroxylamines.
addition reaction, Mannitz reaction). West German Patent No. 1159634 "Inorganica Acta"
Chimica Acta), 9 3, (I9
84) No. 101-108, etc., and the 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 ml of an aqueous solution of 20 g of hydroxylamine hydrochloride, and the mixture was kept at 60°C and 40 ml of an aqueous solution of 23 g of sodium hydroxide was added over 1 hour. I added it slowly. Further, the temperature was maintained at 60°C for 3 hours, the reaction solution was concentrated under reduced pressure, 200 ml of concentrated hydrochloric acid was added, and the mixture was heated to 50°C. Insoluble materials were filtered, and 500 ml of methanol was added to the filtrate to obtain the desired product (exemplified compound (7)) as monosodium salt crystals. 41 g (yield 53%) Synthesis of Exemplary Compound (I1) Hydroxylamine hydrochloride 7.2 g and phosphorous acid 18. Og
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 Exemplary Compound (I 1).

Next, the slip agent used in the present invention will be explained in detail.

The slip agent used in the present invention may be any compound as long as it reduces the coefficient of static friction of the material surface when it is present on the material surface compared to when it is not present.

Typical examples of such slip agents include, for example, U.S. Pat. Nos. 3,042,522 and 3,080,317
No. 3,489,567, No. 4,004,92
No. 7, No. 4, 047, 958, No. 4, 4
No. 73,676 (reissue 32514), British Patent No. 9
No. 55,061, No. 1,313,384, Japanese Unexamined Patent Publication No. 6
No. 0-1403'41, No. 60-140342, No. 6
No. 0-191240, No. 62-203152, No. 62
-203154, 6 2-2 0 3 1 5 5
Silicone-based slip agent described in US Patent No. 2,45, etc.
No. 4,043, No. 2,588,765, No. 2,7
No. 32,305, No. 2,976,148, No. 3,
No. 121,060, No. 3,206,311, No. 3
, 933,516, British Patent No. 1,198.387, British Patent No. L, 263,722, British Patent No. 1,320,564.
No. 1,320,565, No. 1,320,75
No. 7, No. 1,321,994, West German Patent No. 1,28
No. 4,294, No. 1,284,295, No. 1,
No. 300, 015, No. 2,347,301,
Special Publication No. 57-9057, No. 58-33541, No. 5
No. 8-34820, No. 5B-34821, Japanese Unexamined Patent Publication No. 1973
-37217, No. 58-86540, No. 58-90633, No. 63-19647, etc., higher alcohols, higher fatty acids, and salts thereof;
Suitable lubricants include esters of various acids including higher fatty acids, acid amides, ethers, and various polymers. These can be used alone or in combination of two or more kinds by a known method.

In the present invention, at least one organopolysiloxane is preferably used in at least one outermost layer of the color sensitive material.

In the present invention, at least one organopolysiloxane represented by the following general formulas (II-1), (U-2) and (Il-3) is used in at least one outermost layer of a color sensitive material. It is more preferable that

General formula (n-1) In the formula, R is an aliphatic group {for example, an alkyl group (preferably one having 1 to 18 carbon atoms), a substituted alkyl group (for example, an aralkyl group, an alkoxyalkyl group, an aryloxyalkyl group, etc.), etc. 1 or an aryl group (eg, phenyl group). R' is a hydrogen atom, an aliphatic group {for example, an alkyl group (preferably one having 1 to 12 carbon atoms), a substituted alkyl group, etc., or an aryl group (for example, a phenyl group)
represents. R' is an alkyl group (such as a methyl group),
Or it represents an alkoxyalkyl group (for example, a methoxymethyl group). A represents a divalent residue of an aliphatic hydrocarbon. n is O or an integer from 1 to 12, p is a number from 0 to 50,
q is a number from 2 to 50 (preferably 2 to 30), X is O to 1
00, y is a number from 5 to 50, 2 is a number from O-100, and X+y+z is from 5 to 250 (preferably lO to 50).
) is the number of

Specific examples of R include methyl, ethyl, proyl, pentyl, cyclobentyl, cyclohexyl, dimethylpentyl, heptyl, methylhexyl, octyl, dodecyl, octadecyl, phenylethyl, methylphenylethyl, phenylpropyl, cyclohexylpropyl, Includes penzyloxyprovir, phenoxyprovir, ethyloxybupil, butyloxyethyl, phenyl, etc.

The group represented by A is methylene, l-on-trimethylene,
Examples include 2-methyl-l-on-trimethylene. The alkyl group represented by R' is methyl, ethyl,
Examples include proyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl groups.

General formula (n-2) General formula (II-2) is a cyclic siloxane having a siloxane unit represented by the following general formula (II-2-1) and a siloxane unit represented by the general formula (n-2-1). and a terminal group represented by the following general formula [:II-2-2].

General formula (II-2-1) CH. -Si-0- R General formula (n-2-2) CHs R. -Si-0- CH. In the formula, R1 represents an alkyl group having 5 to 20 carbon atoms, a chloroalkyl group, an alkoxyalkyl group, an arylalkyl group, an aryloxyalkyl group, or a glycidyloxyalkyl group.

R2 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxyalkyl group, an arylalkyl group, an aryloxyalkyl group, and a glycidyloxyalkyl group.

l represents 0 or a number greater than or equal to 1, m represents a number greater than or equal to 1, and 1+m represents a number from 1 to 1000. Preferably 1+m is 2-5
It is 00.

Specific examples of R in the compound represented by formula (Il-2) include pentyl, methylpentyl, cyclobentyl,
Cyclohexyl, methylpentyl, heptyl, methylhexyl, octyl, eicosyl, phenylethyl, methylphenylethyl, phenylpipil, cyclohexylpipil, penzyloxyprovil, phenoxyprovir, tolyloxyprovir, naphthyl These include brovil, ethyloxypipil, butyloxyethyl, octadecyloxypipil, glycidyloxypipil, and glycidyloxybutyl.

General formula (n-3) In the formula, R. , R4, R, and R6 represent a hydrogen atom, a hydroxy group, an unsubstituted or substituted alkyl group, a cycloalkyl group, an unsubstituted or substituted aryl group. m is 0 to 10
．． Represents an integer of 000. R,,R. , R. and R,
may be the same or different. However, R3,
R. , Rl and R6 are never hydrogen atoms at the same time, and R, and R5 and R are never simultaneously hydroquine groups.

In formula (II-3), R. , R. , R5 and R,
The alkyl and cycloalkyl groups have 1 to 18 carbon atoms.
For example, methyl, ethyl, iSO-propyl, t-butyl, bentyl, methylbentyl, cyclobentyl, hexyl, cyclohexyl, dimethylpentyl, methylhexyl, octyl, t-octyl, decyl, dodecyl, tetradecyl, hexadecyl, Such as octadecyl group. Substituents for substituted alkyl and cycloalkyl groups include halogen atoms (fluorine, chlorine, bromine), hydroxyl groups, cyano groups, aryl groups, -OR,0 I1 -SR1-So. R, -COOR, -OCR, -NHC
OR, -CONHR, -COR, -So. NHR, -N
HSO. They are an R group and a substituted aryl group. R represents the above-mentioned alkyl, cycloalkyl, or aryl group, and may be similarly substituted. The substituents of the substituted aryl group are the same as those just mentioned. Substituted cycloalkyl groups are the same as those described for the substituents of substituted alkyl groups, including the alkyl groups described above. The aryl group represents a phenyl group or a naphthyl group, and the substituents for the substituted aryl group are the same as those described for the substituted alkyl group in addition to the above-mentioned alkyl group.

Next, representative examples of compounds represented by the general formula (II-1) will be shown.

(n-1-1) (n-1-4) (n-1=2) x+y+z=30 1 (OCR.CH!). OH (n-1-5) x+y+z=so (QC}ItC}I)s(OCHtCHt)s-OHC
H. (n-1-3) x+y+z=4o (OCR=CH!)1. O.C. H. (II-1-6
) (00bCHt)+.戊4}19 x+y+z=100 (O CR! CH) +. (OCHtCH!)1.

QCsHtx+y+z=35 CHx (n-1-7) (n-1-9) CB2011CO (001.CI!). ．． (IIx+
y+z=2 0 0 z+y+z=10 (n-1-10) (■ 1-8) OCR. -C}IcHIOcH. 0(CH5xO)tel show.

(II-2-1) (II-2-5) (II-2-2) (n-2-6) (n-2-3) (II-2-7) (n-2-8) (n-2-9) (IF-2-12) CH. 0 n-C<　He (II-2-13) CH2 CH2 O n-CuHst (II-2-10) (■-2-1!) (■-2 14) (n-2-15) 1 CH. ■ (n-2-17) (n-2-18) (n-3-1) (n-3-2) (n-3-3) (II-2-19) (n-2-20) CHs　-Si-CL CH. general formula (n-3) Among the compounds represented by Examples of typical compounds are shown below.

(II-3-4) n! =+100 (■-3-5) (II-3-6) n#100 n''=.300 (n-3-7) (■-3-10) (II-3-8) (n-3- 11) (n-3-12) (n-3-9) n#500 (n-3-13) Including the aforementioned organosiloxane compounds, they can be used alone or in combination of two or more.

(Example of compound) L-1 ■ e C. ,H. ．． COOCH2CH2N (CH!)l
・ClL-2? ．． H■COOCl6Hhs (■ 3-14) L-3 L-5 (C+yHssCOO) 2 Ca L-6 C. ．． H. ．． COOK L-7? C. ■HzaO) sp=o In addition to the above-mentioned organopolysiloxane compounds, it is also preferable to use compounds such as those exemplified below, but the slip agent used in the present invention is not limited to these. . These slip agents are L-8 CH. -OCOC,. H2, CH-OCOC. ,H2. CH. -OCOC. 2H2, L-9 C (CH. OCOC. H,.) 4L-2 1 L-22 L-11 L-12 L-1S L-16 L-17 L-18 L-19 L-20? CH! CH! C O O C lo H■
)! Go CH* CH! OCOC. H■), Ct. H.
．． CONHC. H. Cl, H4. CONH. C,. Hx. oH HO's CHxiOH Paraffin Chlorinated Paraffin L-24 L-25 L-26 L-27 ffo C F ! C F sfi'=? ．． ,H■
CONHC. H. C. H-+CONHCt Hs CH2 0H I C,,H. sCOOCH. -C-CH. OCOC,,}
13.1 CH. OH L-28 L-29 L-30 CH. OCOC. ．． H. $1 C. ,H. sCOOCH! -C-CH20COC. ．． H
2. C}{2 0COC=Hu The amount of the slip agent used in the present invention is not particularly limited, but I
5 to 1,000 cm per square meter is preferable, especially l
It is preferable that it is 0 to 100 cm. If the amount is less than this lower limit, the effect will be small, and if it exceeds the upper limit, the physical properties of the film will be affected (decrease in scratch strength, decrease in reticulation temperature, stability of the slip agent in the film (coagulation, damage to other contact surfaces). transfer, etc.), viscoelasticity, etc.).

The slip agent used in the present invention can be emulsified and dispersed using a known method and then applied as is or mixed with a suitable binder. Organic solvents used for dispersion include low boiling point alcohols, ketones, lower esters,
Compounds such as ethers, dimethylformamide, pyridine and dimethylsulfoxide can be used depending on the properties of the slip agent. Further, if necessary, high boiling point organic solvents such as those described in RD 17643, RD 18716, and JP-A-62-215272 can also be used. Furthermore, during dispersion, any known anionic, cationic, amphoteric, or nonionic surfactant may be used depending on the properties of the slip agent. Examples of these are the aforementioned RD17643,
It includes compounds described in JP-A No. 18716 and JP-A-62-215272.

In the color photosensitive material of the present invention, the thickness of the top layer containing a slipping agent, such as the protective layer of the photosensitive layer or the back layer, is preferably 0.000. 1 to 10μ, more preferably 0.2
~3μ. In addition, when the top layer containing a slip agent is a protective layer, the number of the protective layer may be one layer, but two protective layers are provided, and the top layer containing the slip agent is covered with the other layer. Preferably, the layer structure does not contain a slip agent.

Various hydrophilic colloids are used as the binder for the slip agent-containing layer of the present invention and/or for other photographic layers, such as gelatin, colloidal albumin, casein, carboxymethyl cellulose,
Cellulose derivatives such as hydroxyethyl cellulose, agar, sodium alginate, sugar derivatives such as starch derivatives, synthetic or hydrophilic colloids such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide, or derivative moieties thereof Examples include hydrolyzates. Compatible mixtures of two or more of these colloids are used if necessary.

Among these, gelatin is the most commonly used.

The photographic emulsion layer and other layers used in the present invention contain synthetic polymer compounds, such as latex-like water-dispersed vinyl compound polymers, in particular compounds that increase the dimensional stability of photographic materials, either singly or in combination. (of different types of polymers) or in combination with hydrophilic water-permeable colloids.

There are many types of polymers, such as U.S. Pat.
No. 376,005, No. 2,739,137, No. 2,8
No. 53,457, No. 3, 062, 674, No. 3,
No. 411,911, No. 3,488.708, No. 3,5
No. 25,620, No. 3,635,715, No. 3,60
No. 7,290, No. 3,645,740, British Patent No. 1
, 186. No. 699, No. 1,307,373, etc. Among these descriptions are alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, sulfoalkyl acrylate,
Sulfoalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, alkoxyalkyl acrylate, alkoxy methacrylate, styrene, butadiene, vinyl chloride, vinylidene chloride, maleic anhydride, and itacone anhydride. Cobolymers and homobolymers selected from acids are commonly used.

By curing the binder with various crosslinking agents,
It is common practice to ensure that they remain. Various crosslinking agents can be used, but curing agents generally known in the art (Research Disclosure Magazine 17
6, page 26 (I978)) can be used. Gelatin is desirable as a binder, and as a hardening agent, 2,4-dichloro-6-hydroxy-1.
3. 5-triazine or a compound having an active vinyl group, halo-substituted formamidinium salts, or carbamoylammonium salts can be preferably used.

Examples of compounds having an active vinyl group include JP-A-53-41221, JP-A-53-5-7257,
JP 51-126124, JP 49-13563
No., JP-A-51-44164, JP-A-52-2105
No. 9, U.S. Patent No. 3,490,911, U.S. Pat. No. 3,539,644, U.S. Pat.
No. 7, JP-A No. 54-30022, JP-A No. 5-3-.
6 6 9 6 0, Japanese Patent Publication No. 52-46495, Japanese Patent Publication No. 4 7-8 7 3 6, U.S. Patent No. 36357
No. 18, No. 3040720, West German Patent No. 872153
Examples include the compounds described in No.

Examples of compounds having a halo-substituted formamidinium group include JP-A No. 60-225148 and JP-A No. 61-Sho.
Mention may be made of the compounds described in No. 240236.

As a compound having a carbamoylammonium group,
For example, Special Publication No. 56-12853, Special Publication No. 58-3
2 6 9 9 can be mentioned.

The color sensitive material of the present invention contains brighteners such as stilbene, triazine, oxazole, and coumarin compounds in the non-light-sensitive photographic constituent layer; and ultraviolet absorbers such as penzotriazole, thiazolidine, and cinnamic acid ester compounds. various photographic filter dyes known as light absorbers; optionally as anti-adhesion agents, e.g. British Patent No. 1,320,564;
No. 5, U.S. Pat. No. 3,121.060 and U.S. Pat. No. 3,617,2.
Surfactants such as those described in No. 86 may be included. Further, as a matting agent, inorganic compounds such as silver halide, silica, and barium strontium sulfate, and polymer latexes such as polymethyl methacrylate having appropriate particle sizes can be included. These matting agents may be contained in the outermost layer according to the present invention, or in any layer below it.

The photographic light-sensitive material of the present invention can be used as an antistatic agent in the photographic constituent layers including the photographic emulsion layer, particularly in the outermost layer related to the present invention, for example, as disclosed in Japanese Patent Application No. 60-24-9021, No. 6
Fluorine-containing surfactants or polymers described in JP-A No. 1-32462, JP-A-60-7 6742, JP-A No. 6-0-8
0 8 4 6, 60-80848, 6 0
-8 0 8 3 9, 60-76741, 5
No. 8-208743, Japanese Patent Application No. 6l-113398, No. 6
1-16056, 6l-32426, etc., or JP-A-57-20-4540, Japanese Patent Application No. 61-32462.
Conductive polymers or latexes (nonionic, anionic, cationic, or amphoteric) described in this issue can be preferably used. Also, as inorganic antistatic agents, ammonium,
Halogen salts, nitrates, etc. of alkali metals and alkaline earth metals, conductive tin oxides, zinc oxides, or composite oxides in which antimony, etc. are doped with these metal oxides as described in JP-A-57-118242, etc. can be preferably used.

In addition, use the necessary amounts of known antifoggants, antistain agents, thickeners, pH regulators, graininess improvers, color mixing inhibitors, antioxidants, development speed regulators, etc., depending on the purpose. I can do it.

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 light to be exposed, namely yellow for blue, magenta for green, and cyan for red. By including so-called color force blur, subtractive color reproduction can be performed. However, the coloring hues of the photosensitive layer and the coupler may not correspond as described above.

Silver halide emulsions used in the present invention include silver iodobromide,
Silver bromide, silver chlorobromide or silver chloride can be preferably used. The halogen composition of the emulsion may be different or the same among the grains, but if an emulsion having an equal 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 the silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in any part of the silver halide grains, and grains with a core inside the silver halide grains and surrounding cores. Particles with a so-called laminated structure in which the shell (one layer or multiple layers) has different halogen groups, or structures with different halogen groups in a non-layered manner inside or on the surface of the particle (if it is on the surface of the particle, Particles having a structure in which portions of different compositions are joined on the edges, corners, or surfaces of the substrate can be appropriately selected and used. 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 halogen composition are clear boundaries, mixed crystals are formed due to compositional differences, resulting in unclear boundaries. Alternatively, the structure may be actively made to have continuous structural changes.

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 monodispersed 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), irregular crystal shapes such as spherical or plate-like, or a combination of these shapes 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/
Emulsions in which the projected area of tabular grains having a thickness of 5 or more, preferably 8 or more, exceeds 50% of the total grains can also be preferably used.

The silver halide emulsion used in the present invention is P. Glafki
Chfmie et Physique Ph
otographique (Paul Montel
Publishing, 1967), G. F. Written by Duffin Ph.
otographic emulsion shell
istry (Focal Press, 1966), V. L. Written by Zelikman eL al
King and CoatingPhotograph
hic Emulsion (published by Focal Press, 1964) and the like. 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 form of the simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is formed can be kept constant, that is, a so-called controlled 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 emulsion grain formation or physical ripening process.

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 10-1 to 10-ffi moles 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 spectral sensitizing dye that absorbs light in a wavelength range corresponding to the desired spectral sensitivity. Spectral sensitizing dyes used at this time include, for example, F. M. Heter by Harmer
ocyclic compounds-Cyanine
dies and related compounds
ds (John Wiley & Sons (New
York, London, 1964). Examples of specific compounds and spectral sensitization methods are described in the above-mentioned Japanese Patent Application Laid-open No. 62-21.
Those described in the upper right column of page 22 to page 38 of the specification of Japanese Patent No. 5272 are 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.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Additive species RD 17643 RD 187
16l Chemical sensitizer Page 23 Page 648 Right column 2
Sensitivity enhancer Same as above 3 Spectral sensitizers, pages 23-24 Page 648 right column - Super sensitizers
Page 649 Right column 4 Brightener Page 24 5 Antifoggant Pages 24-25 and stabilizer 6 Light absorber, filter dye, UV absorber 7 Stain inhibitor 8 Dye image stabilizer 9 Hardener 10 Binder 1 Plasticizer , lubricant l2 Coating aid, surfactant Page 650 Left to right column Page 651 Left column Same as above Page 650 Right column Same as above Page 649 Right column - Page 650 Left column Page 649 Right column - Page 25 Right column Page 25 Page 26 Page 26 Page 27 Page 26-27 Page 25-26 l3 Static inhibitor Page 27 Same as above The emulsion used in the present invention is a so-called surface latent image type emulsion in which the latent image is mainly formed on the grain surface, or a latent image is mainly formed on the grain surface. It may be any type of so-called surface latent image type emulsion formed inside.

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.

As the magenta coupler of the present invention, various magenta couplers can be used, but in particular, the following general formula (M
It is preferable to use at least one magenta coupler selected from the group of compounds represented by -1) or (M-11).

General formula (M-1) General formula (M-II) In general formula (M-1), R+67 and R +os
represents an aryl group, and R1. , represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and Y3 represents a leaving group.

R 1 o 7 and R1. . The permissible substituents on the aryl group (preferably phenyl group) are the substituents R,.

are the same as the substituents allowed for, and when there are two or more substituents, they may be the same or different. R+
a I is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, particularly preferably a hydrogen atom. Preferably, Y is of the type that leaves off with either a sulfur, oxygen or nitrogen atom, for example as described in U.S. Pat.
, 351,897 and WO 088/04795 are particularly preferred.

n represents 0 or l.

In general formula (M-I1), RIIO represents a hydrogen atom or a substituent. Y4 represents a hydrogen atom or a leaving group,
Particularly preferred are halogen atoms and arylthio groups. Za,
Zb and Zc represent methine, substituted methine, =N-, or one NH-, and one of the Za-Zb bond and Zb-Zc bond is a double bond, and the other is a single bond. Zb-Z
The case where the c bond is a carbon-carbon double bond includes the case where it is part of an aromatic ring. Rl1. or Y, when forming a dimer or more multimer, and also when Za, Zb or Z
When c is a substituted methine, it includes the case where the substituted methine forms a dimer or more multimer.

Among the birazoloazole couplers represented by the general formula (M-II), the imidazo (I,2 -b) pyrazoles are preferred;
Pyrazolo (I) described in U.S. Pat. No. 4,540,654
．． 5-b) (I, 2. 4) }Riazoles are 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 birazolotriazole ring to create a birazolotriazole coupler, which is described in JP-A-61-65246. birazoloazole couplers containing a sulfonamide group in the molecule, birazoroazole couplers having an alkoxyphenyl sulfonamide ballast group as described in JP-A-61-147254, and European Patent Publication No. 226. It is preferable to use birazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position, such as those described in , No. 849 and No. 294,785.

Specific examples of couplers represented by general formulas (M-, I) and (M-I1) are listed below.

N-4) αto7) (M-5) ωto8) CiF CH. CH. N-9) (M-10) CM-11) C1 CM-13) (Il Yellow couplers include, for example, U.S. Pat. No. 3.93
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401,752, Special Publication No. 5
No. 8-10739, British Patent No. 1,425,020,
No. 1,476,760, etc. are preferred.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052,212.
No. 4,146,396, No. 4,228,23
No. 3, No. 4, 296, 200, No. 2,36
No. 9.929, No. 2,801,171, No. 2.77
No. 2,162, No. 2,895,826, No. 3, 7
No. 72,002, No. 3,758,308, No. 4,
No. 334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 1
No. 21,365A, U.S. Patent No. 3,446,622;
Same No. 4,333,999, Same No. 4,451,
No. 559, No. 4,427,767, European Patent No. 16
1. , No. 626A and the like are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are disclosed in Research Disclosure Na17643, ■-G section, U.S. Patent No. 4,163,670, and Japanese Patent Publication No. 5.
No. 7-39413, U.S. Patent No. 4,004,929,
No. 4,138,258, British Patent No. 1,146,3
The one described in No. 68 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366,237 and British Patent No. 2.125.
, 570, European Patent No. 96,570, and German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820; U.S. Pat. No. 4,080,211; U.S. Pat.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
No. 57-154234, No. 60-184248, and U.S. Pat. No. 4,248.962 are preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140;
No. 2,131,188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, etc., and U.S. Pat. No. 4,283,47.
No. 2, No. 4,338,393, No. 4,310,6
Multi-equivalent coupler described in No. 18 etc., JP-A-60-185
Examples include a DIR redox compound-releasing puller described in European Patent No. 173,302A, which releases a dye that recovers its color after separation, and the like.

The above-mentioned coupler is contained in the silver halide emulsion layer constituting the photosensitive layer, usually in an amount of 0.1 to 1.0% per mole of silver halide.
0 mol, 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
) 2-20, refractive index (25°C) 1.5-1. It is preferable to use a high-boiling organic solvent and/or a water-insoluble polymeric compound of No. 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) W, -COO-W. (In the formula, W, W, and W are each substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group,
Represents an aryl group or a heterocyclic group, W, is W,,OW
+ or S-W. , n is an integer from 1 to 5, and when n is 2 or more, W, may be the same or different from each other. In general formula (E), W, and W form a fused ring. may be formed).

The high boiling point organic solvent used in the present invention has a melting point of 100°C or less and a boiling point of 140°C, even if it is not represented by general formulas (A) to (E).
Any of the above water-immiscible compounds can be used as long as they are good solvents for couplers. The melting point of the high boiling point organic solvent is preferably 8
The temperature is below 0°C. 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 into loadable latex polymers (
For example, it can be emulsified and dispersed in an aqueous hydrophilic colloid solution by impregnating it with a water-insoluble polymer (eg, US Pat. No. 4,203,716) or by dissolving it in a water-insoluble but organic solvent-soluble polymer.

Homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO 88/00723 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,
Subirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and silylation and alkylation of the phenolic hydroxyl groups of these compounds. Typical examples include ether or ester derivatives. Also, (bissalicylaldoximato)nickel complex and (bis-N,N-dialkyldithiorubamate)
Metal complexes such as nickel complexes can also be used.

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

Hydroquinones are covered by U.S. Patent No. 2,360,2
No. 90, No. 2,418.613, No. 2,700.
No. 453, No. 2.701,197, No. 2,728
, No. 2,732,300, No. 2,735,765, No. 3,982,944, No. 4,430,425, British Patent No. 1,363,92
1, U.S. Patent No. 2,710,801, U.S. Patent No. 2,81
6,028 etc., 6-hydroxychromans, 5-
Hydroxycoumarans and spirochromans are disclosed in U.S. Patent Nos. 3,432,300, 3,573,050, 3,574,627, and 3,698,9.
No. 09, No. 3.764.337, JP-A-52-15
No. 2225, etc., spiroindanes are disclosed in U.S. Patent No. 4,
No. 360.589, p-alkoxyphenols are disclosed in U.S. Pat. No. 2,735,765 and British Patent No. 2,066.
, No. 975, JP-A-59-10539, JP-A-57-
No. 19765, etc., and hindered phenols are disclosed in U.S. Patent No. 3,700.455, JP-A-52-72224, U.S. Pat.
No. 3, etc., gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Patent Nos. 3 and 4, respectively.
No. 57,079, No. 4,332,886, Special Publication No. 5
Hindered amines are disclosed in U.S. Pat. No. 3,336,135, U.S. Pat. No. 4,268, etc.
593, British Patent No. 1,326,889, British Patent No. 1.
No. 354,313, No. 1,410,846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. 58-114036, No. 59-53846, Japanese Patent Publication No. 59-783
4, etc., metal complexes are described in U.S. Patent No. 4,050,
No. 938, No. 4,241,155, British Patent No. 2,
027, 73 1 (A), etc., respectively. 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, penzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533,7
94), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3,314.794, U.S. Pat. No. 3,352,
681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, those described in U.S. Pat. No. 3,705,805 and 3,707,395). (as described in U.S. Pat. No. 4,045,229), butadiene compounds (as described in U.S. Pat. No. 4,045,229), or benzoxide compounds (such as those described in U.S. Pat. 271,307) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler), an ultraviolet absorbing polymer, or the like may be used. These ultraviolet absorbers may be mordanted in specific layers.

Among these, penzotriazole compounds substituted with the aforementioned aryl group are preferred.

In addition to the above-mentioned couplers, it is particularly preferable to use the following compounds. Particularly preferred is the combination with a virazoloazole 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 the generation of stains and other side effects due to the formation of coloring pigments 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 k! with p-aningine. (in trioctyl phosphate at 80°C) is 1. Oi/mol・sec-fX10
-'J! It is a compound that reacts within the range of /mol Sec.
It can be measured by the method described in No. 45.

When k2 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if kt is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, it may not be possible to prevent the side effects of the remaining aromatic amine developing agent, which is the objective of the present invention.

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

General formula (Fl) R. - (A). -X General formula (F n) Rs C=Y I B In the formula, R1 and Rt each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents l 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 U). Represents a promoting group. Here R1, X, Y
and R 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 (Fl) and (F II), see JP-A-63-158545,
2-2 8 3 3 3 8, European Patent Publication 2983
Those described in specifications such as No. 21 and No. 277589 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 (Gl) R-Z In the formula, R 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 (Gl), 2 is determined by Rearson's nucleophilicity "CH,I value (R.G. Rearson, etal..J.
Am. Chem. Soc. , 9 0, 3 1
A group in which 9 (I 9 68)) is 5 or more, or a group derived therefrom is preferred.

For specific examples of compounds represented by the general formula (Gl), see European Patent Publication No. 255722, Japanese Patent Application Laid-Open No. 1430-1980
No. 48, No. 62-229145, patent application No. 63-138
No. 724, No. 62-214681, European Patent Publication 29
Those described in No. 8321, No. 277589, etc. are preferred.

Further, details of the combination of 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 water-soluble dyes or dyes that become water-soluble through photographic processing as filter dyes in the hydrophilic colloid layer or for various purposes such as preventing irradiation and halation. You can. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, Tokukai Sho 4
The oxonol dyes, hemioxonol dyes and merocyanine dyes described in US Pat. No. 8-85130 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. Includes 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-based paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate, or cellulose nitrate. , polyamide film, 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 metal plate, metal foil, or metal thin 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. 63-2 4 2 4 7, No. 63-2
It is described in No. 4251 and No. 63-24255.

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

As a light-reflecting substance, 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 a 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 (%) is R. It can be determined by the ratio S/1 of the standard deviation S of R1 to the average value α). The number (n) of target unit areas is preferably 6 or more. Therefore, the coefficient of variation s
/R can be found.

In the present invention, the coefficient of variation of the occupied area ratio (%) of pigment fine particles is 0. It is preferably 15 or less, particularly 0.12 or less. O. If it is less than Oa, the dispersibility of the particles can be said to be "uniform".

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-2 2-amino-5-diethyl-minotoluene D-3 2-amino-5-(N-ethyl-N-laurylamino)toluene D-4 4-(N-ethyl-N-laurylamino)toluene D-4 N-(β-hydroxyethyl)amino]aniline D-5 2-Methyl-4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline D-6 4-amino-3-methyl-N-ethyl N-C
β-(methanesulfonamido)ethyl]-aniline D-7 N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8 N,N-dimethyl-p-phenylenediamine D-9 4-amino-3- Methyl-N-ethyl-N-methoxyethylaniline D-10 4-amino-3-methyl-N-ethyl-N
-β-1ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N
-β-Butoxyethylaniline Among the above p-phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl-N-[β-(
methanesulfonamido)ethyl]-aniline (exemplified compound D-6) and 2-methyl-4-[N-ethyl-N-
(β-hydroxyethyl]amine]aniline (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 primary amine developing agent used is preferably about 0.1 g to about 20 g per developer solution 11.
More preferred is a concentration of about 0.5 g to about 15 g.

In the color developer according to the present invention, a compound represented by the following general formula [E] is more preferably used in order to improve the effects of the present invention.

General formula [E] (E-9) 1-diethylamino-2-bropano (
In the formula, Rll is a hydroxyalkyl group having 2 to 6 carbon atoms, and Rl! and R. are each a hydrogen atom, carbon number l~6
an alkyl group, a hydroxyl group having 2 to 6 carbon atoms, a benzyl group or a C. H! ．． -N<X', n is an integer of 1 to 6, and X1 and X' are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or
6 shows the hydroxyalkyl group. ) Said general formula (E)
Preferred specific examples of the compound represented by are as follows.

(E-1) Ethanolamine, (E-2) Diethanolamine, (E-3)
}liethanolamine, (E-4) diisoprobanolamine, (E-5) 2-methylaminoethanol, (E-6) 2-dimethylaminoethanol, (E-7) 2-dimethylaminoethanol, ( E-8) 2-diethylaminoethanol, (E-10) 3-diethylamino-l-propanol, (E-11) 3-dimethylamino-l-probanol, isopropylaminoethanol, 3-amino-l -probanol, 2-amino-2-methyl-1,3-propanediol, ethylenediaminetetraisopanol, benzyldiethanolamine, 2-amino-2-(hydroxymethyl)-1,3-propanediol, 1.3-diaminobutanol, 1,3-bis(2-hydroxyethylmethylamino)monoprobanol These compounds represented by the general formula [E] have the desired effect of the present invention per color developer 11 (E-12) (E-13) (E-14) (E-15) (E-16) (E-17) (E-18) (E-19) It is preferably used in the range of 3 g to 100 g, more preferably 6 g to It is used in a range of 50g.

The color developer according to the present invention has the following general formula [F1■] and CF
A compound represented by -ID is more preferably used.

General formula CF-1) General formula CF-n) In the formula, Rl4, R. , R. and R+7 are each a hydrogen atom, a halogen atom, a sulfonic acid group, or a carbon atom number of 1 to 7
an alkyl group, -OR. ．． , represents. Also, R. , R.
,R,. and R! + represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, respectively. However, RIG is
When representing H or a hydrogen atom, R. is a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -OR,
．． , represents.

Said R. , R. , R. The alkyl group represented by R1 includes those having substituents, such as methyl group, ethyl group,
iso-probyl group, n-probyl group, t-butyl group,
Examples include n-butyl group, hydroxymethyl group, hydroxyethyl group, methylcarboxylic acid group, benzyl group, and R. , R. , Lo and R. The alkyl group represented by is as defined above, and further includes an octyl group and the like.

Also R. , R I 5% The phenyl group represented by R 1g and R, 7 includes a phenyl group, a 2-hydroxyphenyl group, a 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.

(F-I-1) 4-isobrobyl-1,2-dihydroxybenzene (F-1-2) 1. 2-dihydroxybenzene-3,5-disulfonic acid (F-1-3) 1,2,3-trihydroxybenzene-5-carboxylic acid (F-1'-4) 1,2,3-trihydroxybenzene- 5-t-butyl-1,2.3-trihydroxybenzene-5-carpoxy n-butyl ester (F-1-6) Hydroxybenzene (F-1-7) 1.2-dihydroxybenzene-3.4.6-trisulfonic acid (F-n-1) 2.3-dihydroxynaphthalene-6-sulfonic acid (F-II-2) 2,3.8-trihydroxynaphthalene-6-monosulfonic acid (F-If-3) 2,3-dihydroxynaphthalene-6-carboxylic acid (F-I1-4) 2,3-dihydroxy-8-isoprobylnaphthalene (F-n-5) 2.3-dihydroxy-8-chloronaphthalene-6-
Among the above-mentioned sulfonic acid compounds, 1,2-dihydroxybenzene-3.
Examples include 5-disulfonic acid, and it can also be used as alkali metal salts such as sodium salts and potassium salts. (F-I-2 of specific exemplary compounds)).

In the present invention, the general formulas CF-11 and CF-
The compound represented by II1 is 5ff per liter of color developer.
It can be used in the range of 1 g to 5 g, preferably 15 to 10 g, more preferably 25 to 7 g.

In addition to the compound of the general formula (I) of the present invention, the color developer of the present invention may contain preservatives such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, etc. A sulfite or a sulfite adduct of the carbonyl compound of the present invention can be added as necessary.

The preferred amount added is 0.001g per 11 color developer.
~10g, more preferably 0.01g~5g.

In addition, hydroxamic acids described in Japanese Patent Application No. 61-186559, hydrazines described in Japanese Patent Application No. 61-170756,
Hydrazines, No. 61-188742 and No. 61-2
Phenols described in No. 03253, No. 61-18874
It is preferable to add α-hydroxyketones and α-aminoketones described in No. 1 and/or various saccharides described in No. 61-180616. In addition, when used in combination with the above compounds, Japanese Patent Application No. 61-147823 and No. 61-166674
No. 61-165621, No. 61-164515, No. 61-170789, and No. 61-168159
Monoamines described in No. 61-173595, etc.
Diamines described in No. 61-164515, No. 61-186560, etc., No. 61-185621, and No. 6
Polyamines described in No. 1-169789, No. 61-18
Polyamines described in No. 8619, No. 61-197760
Nitroxy radicals described in No. 61-186561
and the alcohols described in No. 61-197419, the oxidims described in No. 61-198987, and the alcohols described in No. 61-198987, and
Preferably, the tertiary amines described in No. 265149 are used.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-56-94
Polyethyleneimines described in No. 349 may be contained as necessary.

The amount of these preservatives added is preferably 0.5 to 50 g, more preferably 1.0 to 30 g per 11 color developer.
g1 Particularly preferably 1. It is 5-20g.

The color developer used in the present invention preferably has a pH of 9
~l2, more preferably 9 to 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 salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) etc. can be mentioned.

The amount of the buffer added to the color developer is 0. 1 mole/
It is preferably 0.1 or more, particularly 0.1 or more. 1 mol/1~
Particularly preferred is 0.4 mol/It.

In addition, various caloric acid agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or for improving 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,
Nitrilo-N,N,N-tris (methylenephosphonic acid)
, ethylenediamine-N. N, N', N'-tetrakis (methylenephosphonic acid), 1,3-diamino-
2-propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotriprobionic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediamineorthohydroxyphenylacetic acid, 2-phosphonobutane-1, 2. 4
-tricarboxylic acid,! -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, preferably ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1. 3-diaminopropanoltetraacetic acid, ethylenediamine-N, N, N',
N'-tetrakis (methylenephosphonic acid) and 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
The amount is about 0.1g/10g.

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
7-5 9 8 7, 3 8-7 8 2 6, 44-12380, 45-9019, and U.S. Patent No. 3,813,247, etc.; 2-49829 and 50-15554, JP-A No. 50-137726, JP-A No. 44-30074, JP-A No. 56-156826 and 5 2-4 3 4 2 4 expressed in No. 9 etc.
ammonium salts, p-aminophenols described in U.S. Pat. No. 2,610,122 and U.S. Pat. No. 4,119,462, U.S. Pat.
128, 182, 4,230,796, 3
, 253,919, Japanese Patent Publication No. 41-11431, U.S. Pat. No. 16088, No. 42-25201, U.S. Patent No. 3,128,183, Japanese Patent Publication No. 41-11
431, 42-23 883, and U.S. Patent No. 3,532,501, other 1-phenyl-3-virazolidones, hydrazines, meso-ionic compounds, ionic compounds, imidazole etc. can be added as necessary.

The color developer may contain benzyl alcohol or may be substantially free of benzyl alcohol. "Substantially not containing" means containing 2.0 ml or less per 11 color developing solutions, more preferably not containing at all. Substantially not containing it causes less variation in photographic properties, especially an increase in stain, during continuous processing, and more favorable results can be obtained.

It is preferable to use halogen ions (chloride ions and/or bromide ions) in the color developer for the purpose of preventing fogging and the like. In particular, chloride ions contained in the color paper developer are preferably 1. OX10-”~1,
More preferably 4XlO-''~I
Contains XIO-'mol/i. Chloride ion concentration is 1.
More than 5.times.10-' mol/l has the disadvantage of slowing development and does not achieve the object of the present invention of rapid development and high maximum density. In addition, if the amount is less than 3,5X10-2 mol/1, it is not possible to prevent staining, and furthermore, the fluctuation in photographic properties (especially the minimum density) due to continuous processing is large and the amount of residual silver is large. It does not achieve the purpose of

Furthermore, in the present invention, preferably 3.0 x 10-5 mol/bromine ion is added to the color developer for color paper.
i ~1. Contains oXIo-' mol/l. More preferably 5. O X 1 0-' ~5 X 1 0-
"mol/l, more preferably 1.OX10-'
~3X10-'mol/i. Bromine ion concentration is IX
If it is more than 3.OXlO-' mol/l, the development will be delayed and the maximum density and sensitivity will be reduced; if it is less than 3.OXlO-' mol/l, it will not be possible to prevent staining and furthermore, it will be difficult to prevent staining due to continuous processing. However, the object of the present invention cannot be achieved because of large fluctuations in photographic properties.Especially when the chloride ion concentration is 4X1
The effect of the present invention is most remarkable in the case of a color developer having a bromide ion concentration of 0-" to IXIO"" mol/l and a bromide ion concentration of 5.OXlO-' to sxio-' mol/l.

Here, chloride ions and bromide 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, of which chloride ion is preferred. Sodium and potassium chloride.

It may also be supplied in the form of a countersalt of the fluorescent brightener added to the developer. As a supply material for bromide ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium 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 chloride ions and bromide 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 chloride 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 penzotriazole,
6-nitropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitropenzotriazole, 5-chloropenzotriazole,
Representative examples include nitrogen-containing heterocyclic compounds such as 2-thiazolylpenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer applied to the present invention preferably contains a fluorescent brightener. As a fluorescent whitening agent, 4.4'-
Diamino-2,2'-disulfostilbene compounds are preferred. Addition amount is 0-10g/1, preferably 0.1g
~6g/1.

Furthermore, various surfactants such as alkylsulfonic acids, arylsulfonic 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 300 seconds,
Preferably, the effect of the present invention is significant in 20 seconds to 200 seconds. Further, the effects of the present invention are particularly remarkable at a treatment temperature of 33 to 45°C, preferably 36 to 40°C.

The amount of replenishment of color developer during continuous processing varies depending on the photosensitive material, but in the case of color print materials such as color paper, it is 20 to 220 ml per 1, preferably 25 to 1
60 ml, particularly preferably 30-110 mj7, is preferable in that the effects of the present invention can be effectively exhibited.

Furthermore, the color developer of the present invention has relatively better performance than combinations other than those of the present invention under any condition of its liquid aperture ratio (air contact area (crl)/liquid volume (cd)). From the viewpoint of liquid stability, the liquid opening ratio should be 0 to 0.
0. 1an-' is preferred. In continuous processing,
Practically speaking, the range is 0.001cm-' to 0.05. The range is preferably from cm to 1, more preferably 0.0 0 2 CI
l1-'~0. 0 3 as-'.

It is generally known that when hydroxylamine is used as a preservative, decomposition occurs due to heat or trace metals even if the aperture ratio of the color developer is reduced. 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 for a long time or used as a replenisher for a long time. Therefore, in this case, it is preferable that the liquid aperture ratio is small, from 0 to 0.002.
cm-' is most preferred.

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 even in such a processing method, if the structure of the present invention is followed, excellent performance can be achieved. I can do it.

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., potassium 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; water-soluble such as thioether compounds and thioureas such as ethylene bisthioglycolic acid and 3,6-dithia-1,8-octanediol 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, preference is given to using thiosulfates, especially ammonium thiosulfates. The amount of fixing agent per 11 is preferably in the range of 0.3 to 2 moles, more preferably in the range of 0.5 to 1.0 moles.

The pH range of the bleach-fix solution or fixer solution in the present invention is as follows:
3 to 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 stains are 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-fixing solution of the present invention has a processing time of IO seconds to 120 seconds, preferably 20 seconds to 60 seconds, particularly for color paper. Also, the replenishment amount is 30ml to 250ml per photosensitive material d.
1 preferably 401 ml to 150 mj7. Generally, as the amount of replenishment decreases, an increase in staining and poor desilvering tend to occur, but according to the present invention, the amount of replenishment of bleach-fix solution can be reduced without causing such problems. I can do it.

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 system is described in the Journal of the Society of Motion.
Picture and Television Engineers (
Journal of the Society of
Motion Picture and Television
sion Engfneers) Volume 64, p. 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 greatly reduced, but the increased residence time of water in the tank causes bacteria to propagate and the generated suspended matter to adhere to the photosensitive material. Problems such as this arise. 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 inthiazolone compounds, thiabendazoles, and chlorinated sodium isocyanurate described in JP-A No. 57-8542, and other chlorine-based disinfectants such as penzotriazole, "Chemistry of Antibacterial and Antifungal Agents" by Hiroshi Horiguchi, ,
It is also possible to use the disinfectants described in "Sterilization, sterilization, and anti-mold technology of microorganisms" edited by the Sanitation Technology Society, and "Encyclopedia of anti-bacterial and anti-mold agents" edited by the Japanese Society of Anti-bacterial and Anti-fungal 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 is selected at 0'C.

Even in such short-time water washing, according to the present invention, there is no increase in stain and good photographic properties 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. 5-7-8 543 and 58
-14834, 59-184343, 60-2
No. 20345, No. 60-238832, No. 60-23
No. 9784, No. 60-239749, No. 61-405
The known method described in No. 4, No. 61118749, 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 treatment, a further stabilization treatment may be carried out, and an example of this is used as a final bath for color photosensitive materials for photographing. Stabilizing baths containing formalin and surfactants may be mentioned.

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 processing step of 0 minutes or less, preferably 7 minutes or less.

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating liquid was prepared as follows.

First layer coating solution preparation Yellow coupler (ExY) 19, Ig, color image stabilizer (Cpd-1) 3.3 g and color image stabilizer (Cpd-7)
) to 0.7 g of ethyl acetate 27.2 eC and solvent (So
lv-1) 9.6g was added and dissolved, and this solution was added to 10% solution containing 8cc of sodium dodecylbenzenesulfonate.
% gelatin aqueous solution (185 cc). On the other hand, silver chlorobromide emulsion (cubic, average grain size 0, 3=7 mixture of 88 μm and 0.70 μm (silver molar ratio)
.

The coefficient of variation of the grain size distribution is 0.08 and 0.10, and each emulsion contains 0.2 mol% of silver bromide locally on the grain surface), and the blue-sensitive sensitizing dye shown below is added to the large size per mol of silver. For the emulsions, 2.0 x 10-4 moles were added, and for small size emulsions, 2.5 x 10-' moles were added, followed by sulfur sensitization. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below.

Coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. As the gelatin hardening agent for each layer, l-oxy-3,5-dichloros-}ryazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

For blue-sensitive emulsion layer green-sensitive emulsion layer and layer,! -(5-methylureidophenyl)-5-
8.5X10-' mol, 7.7XIO-' mol, respectively, of mercaptotetrazole per mol of silver halide;
2.5 x 10-' moles were added.

Further, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1.3.3a,7-tetrazaindene was added per mole of silver halide, respectively, to IXIO-'
The following dyes were added to the emulsion layer for irradiation prevention:

and red-sensitive emulsion layer To the red-sensitive emulsion layer, the following compound was added in 2.6 x 10-'' mol per mol of silver halide.

Furthermore, the composition of each layer is shown below: blue-sensitive emulsion layer, green-sensitive emulsion layer, red-sensitive emulsion (layer structure S.). The number is the coating amount (g/rrr)
represents. The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (Ti○,) and a blue dye (ulmarine blue)] First layer (blue-sensitive layer) Said silver chlorobromide emulsion 0.30 gelatin l. 86 yellow coupler (ExY) 0.82 color image stabilizer (Cpd-
1) 0.14 solvent (Solv-1)
0.41 color image stabilizer (Cpd-7)
0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Sol
v-1) 0.16 solvent (Solv-
4) 0.08 third layer (green-sensitive layer) Silver chlorobromide emulsion (cubic, 1:3 mixture (Ag molar ratio) of one with an average grain size of 0.55 μm and one with an average grain size of 0.39 μm. Grain size The coefficient of variation of the distribution is 0.IO and 0.0
8. Each emulsion has A g B r 0. (8 mol% was locally contained on the particle surface)
0.12 Gelatin 1.
24 magenta coupler (ExM) 0.20
Color image stabilizer (Cpd-2) 0.03 color image stabilizer (Cpd-3) 0.15 color image stabilizer (Cpd-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 mixing prevention agent (
Cpd-5) 0.05 Solvent (Solv-
5) 0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (cubic, 1=4 mixture (Ag molar ratio) of one with an average grain size of 0.58 μm and one with an average grain size of 0.45 μm. Grain size The coefficient of variation of the distribution is 0.09 and 0.1
l, each emulsion has A g B r 0. (6 mol% was locally contained on a part of the surface of the acupuncture needle)
0.23 gelatin 1.34
Cyan coupler (ExC) 0.32 color image stabilizer (Cpd-6) 0.17 color image stabilizer (Cpd-7) 0.40 color image stabilizer (Cp
d-8) 0.04 solvent (Solv-6)
0. 1 5 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0. 1.6 Color mixing inhibitor (Cpd-5) O. 02 Solvent (Solv
-5) o. OA 7th layer (protective layer) Gelatin l,33 Polyvinyl alcohol acrylic 0.17 Modified copolymer (degree of modification 17%) Slip agent (compound names are listed in Table I) (ExY) Yellow coupler 0.17 0 .03 (Solv-5) Solvent COOCs H+t (CH!) I COOC. H. , (Solv-6) Solvent The sample prepared as above was designated as 101.

CH. Samples 102 to 106 were then prepared by changing the slip agent in the seventh layer as described in Table 1. Here, the method for preparing the coating liquid for the seventh layer will be explained. In each of these methods, the following dispersion liquid is prepared, and this dispersion liquid is added to the coating liquid for the seventh layer, so that the coating amount of the slip agent is adjusted to It was set to 0.03g/rrr.

゛の゛ Legal slip agent (listed in Table 1) 2.0g ethyl acetate 5.0mi' triisoprobylnaphthalene 2.0g sodium sulfonate gelatin (I0wtX) 50mjl
'Give the supernatant liquid a vigorous mechanical agitation to reduce the average particle size of the dispersion to 0. It was set to 5μ. The average particle diameter was measured using an automatic particle size distribution analyzer (Mastersizer (manufactured by Malvan))
It was determined by measuring.

The yellow, magenta, and cyan densities of samples 101 to 106 prepared as described above were 1. Exposure was applied so that the amount of light became 0, and continuous processing was performed according to the following processing method.

The processing amount is based on the cumulative replenishment amount of the color development stage being 3 of the tank capacity.
The amount was increased until it doubled.

Processing process Hosei Color Development 35℃ 45 seconds bleach fix 30~36°0 45 seconds rinse ■ 30~37℃ 20 seconds rinse ■ 30~37℃ 20 seconds rinse ■ 30~37℃ 20 seconds drying 70~ 80℃ 60 seconds per photosensitive material (3 tank countercurrent method for rinsing ■→■)
800 i 800 m/ethylene diamine-N, N, N', N'-tetrakis (methylenephosphonic acid) 3. 5g additive (see Table 3) 0.04mol sodium chloride
5.0g Potassium carbonate 25g 25g8.
0g 0.09mol Goshiki 1 Tomoe Medicine Tank capacity 40yd 61 161d 81 4l 4l 4l 20〇1N-ethyl-N-(β methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0g 11.0g ethanolamine 0.06mol 0.
09mol fluorescent whitening agent (WHITEX-4 manufactured by Sumi) 2.0 4.
0 Add water 1000 d 1000
JpH (25℃') 10.25
10.90 warm water and water for both mother liquid and replenisher liquid
400ml
Ammonium thiosulfate (70%) 100mI! Sodium sulfite 17g Iron (III) ammonium ethylenediaminetetraacetate 55g Add disodium ethylenediaminetetraacetate water to 1000mlp
H (25℃) 6.0g Yuegoma
Both the mother liquor and the replenisher are ion-exchanged water (calcium and magnesium are less than 3 ppm each). At the beginning and end of continuous processing, pass through an optical wedge at 32°C.
Process the sample exposed to 00°K, 200CMS,
The increase in minimum density of yellow images with continuous processing was investigated.

Next, the presence or absence of floating substances in the color developer was examined.

Finally, in order to test the image preservation of the processed sample, after the continuous processing was completed, the sample was exposed to light through the optical wedge described above and then stored for one week at 60°C/70% RH. Then, we investigated the increase in the minimum density of magenta images over time. The results obtained are shown in Table 1.

In ammonium table 1, the treated sample is 60℃/70%R
After aging for two weeks under H conditions, the minimum magenta density was examined and the image storage properties were compared. The following compounds were used as comparative compounds for color developer additives (preservatives).

Comparative Compound 1: Hydroxylamine sulfate 2: Diethylhydroxylamine In Table 1, the treatment method of the invention gave favorable results with no increase in minimum concentration and no suspended matter. In addition, when using an organosiloxane compound as a slip agent, (N(L3-9, 15, 17, l
9), more favorable results were obtained with excellent image storage stability.

Example 2 On a subbed cellulose triacetate film support,
Sample 801, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Assemblage of photosensitive layer) Is the coating amount g/r+ of silver for silver halide and colloidal silver? Amounts are expressed in units, and for the coupler additive and gelatin in g/rrr, and for sensitizing dyes in moles per mole of silver halide in the same layer. Note that the symbols indicating additives have the meanings shown below. However, if a substance has multiple effects, one of them is listed as a representative.

Uv: ultraviolet absorber, Solv: high boiling point organic solvent, Ex
F: dye, ExS: sensitizing dye, ExC: cyan coupler, ExM: magenta coupler ExY: yellow coupler, Cpd. Additive 1st layer (antihalation layer) Black colloidal silver 0.15 Gelatin 2.9UV-1
0. 03UV-2
0. 06UV-3
0. 07Solv-2
0. 08ExF-10.01 ExF-20.01 2nd layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform-Agl type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 37%, plate-like particles, diameter/thickness ratio 3.0) Coated silver amount 0.4 Gelatin 0. 8ExS
-1 2.3xlO-'ExS-2
1.4X10-'ExS-5
2.3xlO-'ExS-7
8. OXIO-'ExC-10.17 ExC-20.03 ExC-30.13 Third layer (mid-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core shell ratio 2:
1 internal high Agl type, equivalent sphere diameter 0.65 μm, coefficient of variation of 1 sphere equivalent diameter 25%, plate-shaped particles, diameter/thickness ratio 2.0)
Coated silver amount 0.65 silver iodobromide emulsion (Ag1 4
Mol%, uniform AgI type, equivalent sphere diameter 0.4 μm, coefficient of variation of one sphere equivalent diameter 37%, plate-shaped particles, diameter/thickness ratio 3.0) Coated silver amount 0. 1 gelatin l. OExS-1
2X10”ExS-2
1.2810-'ExS-5
2XtO"ExS-7
7X10"ExC-10.31 ExC-20.01 ExC-30.06 4th layer (high sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 6 mol%, core shell ratio 2:
1 internal height AgI type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 2.5)
Coated silver amount 0.9 gelatin
0.8Ext-11.6X10-"ExS-2 1.6X10"'Ex
S-5 1.6X10-'ExS-
7 6X10-'ExC-10
, 07 ExC-4 ゛0.05
Solv-1 0.07S
olv-2 0.20Cp
d-7 4. sxto-'5th
Layer (middle layer) Gelatin 0. 6UV-
4 0. 03UV-5
0. 04cpd-i
o. 1 Polyethyl acrylate latex 0.08Solv-1
0.05 6th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform-Agl type, equivalent sphere diameter 0.4 μm, coefficient of variation of 1 sphere equivalent diameter 37%, plate-like grains, diameter /thickness ratio 2.0) Coated silver amount 0, 18 Gelatin 0. 4ExS
-3 2XlO-'ExS-4
7X10-'ExS-5
1 X 1 0-'ExM-13
0.12ExM-70.0
3 ExY-80.01 Solv-1 0.09So
lv-4 0.01 7th layer (
Medium-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag! 4 mol%, core-shell ratio 1:
1 surface height Agl type, equivalent sphere diameter 0. 5 μm, coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter/thickness ratio 4.0) Gelatin ExS-3 ExS-4 ExS-5 ExM-5 ExM-13 ExM-7 ExY-8 Solv-1 Coated silver Amount 0. 0, 2×1 7XI IXI O. 0. 0. 0. 0. 27 6 0″4 0-4 0-4 07 1l 04 02 l4 Solv-4 0.02
8th layer (high sensitivity green emulsion layer) Silver iodobromide emulsion (Ag 18.7 mol%, silver ratio 3:4:2
Multi-layer structured particles, Agl content from inside to 24 mol, 0 mol, 3 mol%, equivalent sphere diameter 0.7 μm, coefficient of variation of 1 sphere equivalent diameter 25%, plate-shaped particles, diameter/thickness ratio 1.6) Amount of coated silver 0.7 Gelatin 0.8ExS-4
5.2X10-'ExS-5
1XIO″4Ex'S -'8
0. 3X10'ExM-50
．． 08 ExM-13 0.03ExM
-6 0.03ExY-80
．． 02 ExC-10.02 ExC-40.01 Solv-1 0. 25S
olv-2 0. 06Sol
v-4 0.01Cpd
-7 1XIO” 9th layer (middle layer) Gelatin 0.6CM-i
o, 04 polyethyl acrylate latex 0. l2Solv-1
0.02 10th layer (donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (Ag1 6 mol%, internal high Agl type with core-shell ratio 2:1, equivalent sphere diameter 0.7 μm)
m, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 2.0) Coated silver amount 0.68 Silver iodobromide emulsion (Agl 4 mol%, uniform AgI type, equivalent sphere diameter 0.4 μm) , coefficient of variation of equivalent sphere diameter 37%, plate-like particles, diameter/thickness ratio 3.0) Coated silver amount 0.19 Gelatin l. OExS-3
6 X 1 0-'ExM-
10 0.19Solv-1
0. 20th 11th
Layer (yellow filter layer) Yellow colloidal silver 0.06 Gelatin 0. 8Cpd-2
0.13Solv-1
0. 13Cpd-10.07 Cpd-6 0. OQ2H-
1 0.13 12th layer (
Low-speed blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag 14.5 mol%, uniform Agl type, equivalent sphere diameter 0.7 μm, coefficient of variation of 1 sphere equivalent diameter 15%, plate-like grains, diameter/thickness ratio 7.0) Coated silver amount 0.3 Silver iodobromide emulsion (Ag1 3 mol%, uniform Agl type, equivalent sphere diameter 0.3 μm, coefficient of variation of one sphere equivalent diameter 30%, plate-like grains, diameter/thickness ratio 7.0) Coated silver Amount 0.15 Gelatin 1.8ExS-
6 9X10-'ExC-10
．． 06 ExC-40.03 ExY-90.14 ExY-11 0.
89Solv-1
0. 42 13th layer (middle layer) Gelatin 0.7ExY-1
2 0. 20Solv-1
0. 34 14th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 10 mol%, internal high Agr type, equivalent sphere diameter 1.0 μm, coefficient of variation of one sphere equivalent diameter 25%)
, multiple twinned plate-like particles, diameter/thickness ratio 2.0) Coated silver amount 0.5 Gelatin 0.5ExS-6
1 X l O-'ExY-
90.01 ExY-11 0. 20E
xC-10.02 Solv-1 0.
10th layer I5 (first protective layer) Fine grain silver iodobromide emulsion (Ag1 2 mol%, uniform Ag summer type, equivalent sphere diameter 0.07 μm) Coated silver amount 0.12 Gelatin 0.9 UV-4
0. 11UV-5
0. 16Solv-5
0. 02H-1
0.13Cpd-5
0.10 Polyethyl acrylate latex 0.09 16th layer (second protective layer) Fine grain silver iodobromide emulsion (AgI 2 mol%, uniform AgI
Mold, equivalent sphere diameter 0.07 μm) Coated silver amount 0.36 Gelatin 0.55 Slip agent (
Compound name (listed in Table 2) 0.28-1
0.17 In addition to the above ingredients, each layer contains
Emulsion stabilizer Cpd-3 (0.07g/r+?)
, surfactant CPCI-4 (0.03g/tr
? ) was added as a coating aid.

17th Layer (Back Layer) A back layer having the following composition was coated on the layer opposite to the layer coated with the cellulose triacetate emulsion layer (1st layer to 16th layer).

Cellulose diacetate 0. 5 methylene dichloride L. O (d) Acetone
65 Cd>methanol
34 (In!) Methyl methacrylate/dodecyl 0.2 methacrylate = 2 0/8 0 copolymer (molecular weight 100,000) Slip agent (compound names are listed in Table 2) 0.07 Solv-
L Solv-2 Tricresyl phosphate dibutyl phthalate UV-4 Solv-5 Trihexyl phosphate ExF-1 N (Six Ha)t x:y=70:30 (wt ExF-2 ExS-1 ExS-2 ExS-6 ExS-7 ExS-8 ExS-3 ExS-4 ExS-5 ExC-1 ExC-2 CH. ExC-3 ExM-5 ExM-10 ExY-9 CH. ExM-6 ExM-7 ExY-11 ExM -13 CHs cpct-s Cpd-3 1I H Cpd-4 O Cpd-6 CH,=CH-So.-CH2-CONH-CH.CH
t=CH-SO2-C}l! -CONH-CH.
The sample prepared as described above is designated as 201, and then
Sample 202 was prepared in the same manner as 201 except that the slip agents in the 6th layer and the 17th layer were changed.

Each sample was exposed to light so that the yellow, magenta, and cyan densities were each 0.8, and continuous processing was performed according to the following processing method. The amount of processing was continued until the cumulative amount of replenishment of the color developer reached three times the tank capacity.

Processing method step Processing time Processing temperature Replenishment amount゜Color development 3
Minutes 15 seconds 38°C 16+nl bleach
40 seconds 38℃ 5 constant Arrival (I)
40 seconds 38℃ fixation (2) 40 seconds
38°C 3〇Wash <1) 30 seconds
38°C water washing (21 30 seconds 38°C
301 Stable 30 seconds 38°C
201 Drying 1 minute at 55°C All of the overflow liquid was introduced into the bleach-fixer (2).

In the above process, the amount of bleach-fix solution carried into the washing process was 2 ml per 1 m length of the photosensitive material having a width of 35 m/m.

The crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the treatment liquid is shown below.

(Color developer) Mother solution (g) Replenisher (g)
) Diethylenetriamine 1.0 1.1 Pentaacetic acid l-hydroxyethyl 3.0 3.2 Den-1. 1-diphosphonate Sodium sulfite 4.0 4.9 Potassium carbonate 30.0 30.0 Potassium bromide 1.4 Potassium iodide 1.5■ Additives 3. OX10
-'mol 4.5X 10-''mol 4-(N-ethyl-N-β-hydroxyethylamino)-2= pH by adding methylaniline sulfate solution (bleach solution) 4.5 l.01 10.05 Mother liquor ( g) 1,3-diaminopropanetetraacetic acid ferric ammonium hydrate (I. 3-DPTA ・Fe(III)) 1,3-diaminopropanetetraacetic acid ammonium bromide ammonium nitrate acetic acid (9゛8%) Water In addition, pH (adjusted with aqueous ammonia (27%)) 144.0 2.8 84.0 90.0 60. 1.0l 4.0 8.0 1.01 10.20 Replenisher (g) 206.0 4.0 120.0 125.0 88. 1.0l 3.2 (Fixer) Mother liquor (g) Replenisher (g) 1.3-Diaminobroban 4.5 22.5
Ammonium sulfite tetraacetate 12.0 20.0 Ammonium thiosulfate 290. mj 320. d
Aqueous solution (700g/f) Aqueous ammonia (27%) 6. d 15
．． d Add water L. 11.1pH
6.8 8.0 (rinsing water)
Common tap water for mother liquor and replenisher was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strongly basic anion exchange resin (Amberlite IRA-4 manufactured by Rohm and Haas).
Water was passed through a mixed bed column packed with 00) to reduce the concentration of calcium and magnesium ions to 3/l or less, and then 20/l of sodium isocyanurate dichloride and 150/l of sodium sulfate were added. did.

The pH of this solution was in the range of 6.5-7.5.

(Stabilizing solution) Common formalin for mother solution and replenisher solution (37%) Polyoxyethylene-p-monononyl phenyl ether (unit: g) 2. 0ml 0. 3 Ter (average degree of polymerization 10) Ethylenediaminetetraacetic acid di 0. Add 05 sodium salt water to 1.01 pH
s. o-s. 4800°K through an optical wedge at the beginning and end of continuous processing.
Samples exposed to IOCMS were processed to determine the increase in minimum density of the yellow image with successive processing. The presence or absence of floating substances in the color developing solution was also examined.

Finally, in order to examine the image storage stability of the processed sample, we processed the sample that had been subjected to the above exposure after continuous processing, and stored the obtained sample at 60°C/70% RH for 3 days, and the magenta image The increase in the minimum concentration of was investigated. The obtained results are shown in the second
Shown in the table.

As is clear from Table 2, in the treatment method of the present invention, no suspended matter is found in the treatment solution after continuous treatment, and
Favorable results with excellent processing stability and image storage stability were obtained.

In particular, when the slip agent represented by the general formula n-1 or II-2 was used, more favorable results were obtained, particularly excellent processing stability and image storage stability.

Example 3 Paper support laminated on both sides with polyethylene (thickness 10
A color photographic material was prepared in which the following first to fourteenth layers were coated on the front side of the film (0 micron), and the fifteenth to sixteenth layers were coated on the back side. The polyethylene on the first layer coating side contains titanium oxide as a white pigment and a trace amount of ultramarine as a bluish dye (the chromaticity of the surface of the support is Lll, am
, 88.0, -0.20, and -0.75 for the bs system. ).

(Photosensitive layer composition) The fraction and coating amount (unit: Cg/d) are shown below. Regarding silver halide, the coating amount is shown in terms of silver.

The emulsion used in each layer was prepared according to the manufacturing method of emulsion EMI. However, as the emulsion for the 14th layer, a Lipman emulsion without surface chemical sensitization was used.

1st layer (antihalation layer) Black colloidal silver ... 0.10 Gelatin ... 0.70 2nd layer (
Intermediate layer) Gelatin... 0.70 Third layer (low sensitivity red sensitive layer) Silver bromide spectrally sensitized with red sensitizing dye (ExS-1.2.3) (average grain size 0.25μ, Size distribution [coefficient of variation 18%, octahedral)... 0.04 Silver chlorobromide spectrally sensitized with red sensitizing dye (ExS-1. 2. 3) (silver chloride 5 mol%, average particle size 0
．． 40μ, size distribution lO%, octahedron)
... 0.08 gelatin
... 1. OO cyan coupler (ExC-1, 2
, l:1)... 0.30 Antifading agent (Cpd-1, 2, 3, 4 equivalents) 0. l8 Stain inhibitor (Cpd-5)...0. 0
0 3 coupler dispersion medium (Cpd-6)...- 0.
03 coupler solvent (Sotv-1, 2, 3 equivalents)...
0.12 4th layer (high sensitivity red sensitive layer) Silver bromide spectrally sensitized with red sensitizing dye (ExS-1.2.3) (average grain size 0.60μ, size distribution 15%, octahedral ) ... 0.14 gelatin
... 1.00 cyan coupler (Ex
C-[2, 1:l)...0.30 Antifading agent (Cpd-1, 2, 3, 4 equivalents)...O
．． ta Coupler dispersion medium (Cpd-6)... 0.03 Coupler solvent (Solv-1, 2, 3 equivalents)... 0.
12 5th layer (intermediate layer) Gelatin... 1.00 Color mixing prevention agent (Cpd-7)... 0.08 Color mixing prevention agent solvent (Solv-4, 5 equivalent)... 0.16 Polymer latex (Cpd-8) ... 0.10 6th layer (low sensitivity green sensitive layer) Silver bromide (
Average particle size 0.25μ, size distribution 8%, octahedral)
... 0.04 green sensitizing dye (ExS-4
) spectrally sensitized silver chlorobromide (silver chloride 5 mol%, average grain size 0.40 μ, size distribution 10%, octahedral)...
・0.06 Gelatin...0.80 Magenta coupler (listed in Table 3)...0. IO Antifading agent (Cpd-9, 26, etc. 11)...0.
15 Stain inhibitor (Cpd-10, l1, l2, 13 in 1
0:7:7:1 ratio)...0. 0 2 5 coupler dispersion medium (Cpd-6) ... 0.05 coupler solvent (Solv-4, 6 equivalent) ... 0.15 7th layer (high sensitivity green sensitive layer) Green sensitizing dye (ExS -4) spectrally sensitized with silver bromide (
Average particle size 0.65 μ, size distribution 16%, octahedral) ... 0.10 gelatin
... 0.80 Magenta coupler (listed in Table 3) ... 0.10 Anti-fade agent (Cpd-9, 26 equivalents) ... 0.15 Anti-stain agent (Cpd-10, 1112, 13 to 10
:7:7:1 ratio)...0. 0 2 5 coupler dispersion medium (Cpd-6) ... 0.05 coupler solvent (Solv-4, 6 equivalent) 0.15 8th layer (intermediate layer) 9th layer (yellow filter layer) same as 5th layer ) Yellow colloidal silver 0. l2 Gelatin... 0.07 Color mixing prevention agent (Cpd-7)... 0.03 Color mixing prevention agent solvent (Solv-4, 5 equivalents)... 0.10 Bolimar latex (Cpd-8) ・... 0.07 10th layer (intermediate layer) 11th layer (low-sensitivity blue-sensitive layer) same as the 5th layer Silver bromide (average grain Size 0.40 μ, size distribution 8%, octahedral) ... 0.07 blue sensitizing dye (E x S
- Silver chlorobromide (silver chloride 8 mol%, average grain size 0.60μ, size distribution 11%,
Octahedron)... 0. l4 Gelatin...0.80 Yellow coupler (ExY-12 equivalent)...0.35 Antifading agent (Cpd-14)...0. 10 stain inhibitor (Cpd-5, 15 in a 1:5 ratio)
... 0. 0 0 7 Coupler dispersion medium (Cpd-6) ... 0.05 Coupler solvent (So!v-2) = - 0.10 12th layer (
Highly sensitive blue sensitive layer) Brominated gelatin spectrally sensitized with blue sensitizing dyes (ExS-5, 6) [(average particle size 0.85 μ, size distribution 18%, octahedral) ... 0.15 gelatin
... 0.60 Yellow Cabler (ExY-1
, 2 equivalents)... 0.30 Anti-fading agent (Cpd-14)... 0.10 Anti-staining agent (Cpd-5, 15 in a 1:5 ratio)
... 0. 0 0 7 Coupler dispersion medium (Cpd-6) ... 0.05 Coupler solvent (Solv-2) - 0.10 13th layer (ultraviolet absorption layer) Gelatin ... 1.00 Ultraviolet absorber (CM-2 , 4, 16 equivalents)... 0.5
0 Color mixing inhibitor (Cpd-7, 17 equivalents)... 0.03 Dispersion medium (Cpd-6)... 0.02 Ultraviolet absorber solvent (Solv-2, 7 equivalents)... 0.
08 Anti-irradiation dye (Cpd-13, 19, 20
, 21127 in a 10:10:13:15:20 ratio)
... 0.05 14th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0.1
μ) ... 0.03 Slip agent (listed in Table 3) ... 0.05 Gelatin
... 1.80 gelatin hardening agent (H-1, H
-2 equivalents)...0. l8 15th layer (back layer) Gelatin... 2,50 Ultraviolet absorber (Cpd-2, 4, 16 equivalent)... 0.50 Dye (Cpd-18, l9, 20, 21, 27, etc.) amount)
...0.06 16th layer (back protective layer) Polymethyl methacrylate particles (average particle size 2.06)
4μ) and silicon oxide (average particle size 5μ) equivalent amount
... 0.05 gelatin
... 2. OO gelatin hardener (H-1, H-
2 equivalents)... 0.14 How to make emulsion EM-1 An aqueous solution of potassium bromide and silver nitrate was simultaneously added to an aqueous gelatin solution with vigorous stirring at 75°C over 15 minutes.
Octahedral silver bromide grains with an average grain size of 0.40 μm were obtained. This emulsion contains 0.3 g of 3,4-dimethyl-1 per mole of silver.
．． 3-Thiazoline-2-thione, 6 ■ sodium thiosulfate and 7 ■ chloroauric acid (tetrahydrate) were added in sequence at 75°C.
Chemical sensitization treatment was performed by heating for 0 minutes. The particles obtained in this way are used as cores and further elongated in the same precipitation environment as the first time, until the average particle size is 0. A 7μ octahedral monodisperse core/shell silver bromide emulsion was obtained. The coefficient of variation in particle size was approximately 10%.

This emulsion contains 1.0 molar silver per mole of silver. 5 ■ sodium thiosulfate and l. A chemical sensitization treatment was carried out by adding 5 quartz of chloroauric acid (tetrahydrate) and heating at 60° C. for 60 minutes to obtain an internal latent image type silver halide emulsion.

Each photosensitive layer contains ExZK-1 and ExZK- as nucleating agents.
Cpd-22 was used in an amount of 10-'10-'' wt.
C (Dupon) and sodium alkylbenzenesulfonate, and succinic acid ester and Magefac F-120 (manufactured by Dainippon Ink) were used as coating aids. (Cpd-23, 24, 25) was used as a stabilizer in the silver halide and colloidal silver containing layers. This sample was designated as sample number 601. The compounds used in the examples are shown below.

ExS-1 ExS-3 Cpd 4 (Jl-i S On H-N (C! Hs)s Cpd-1 Cpd-2 n=100 ~ 1000 Cpd-12 Cpd-13 Cpd-15 cpd-18 Cpd-22 Cpd -23 Cpd-25 Cpd-26 Cpd-17 Cpd-24 Cpd-19 Cpd-20 Cpd-21 ExC-1 Solv-I Solv-2 Solv-3 Solv-4 Solv-5 Solv-6 (2-ethylhexyl) Seba Catrinonyl phosphate (3-methylhexyl) phthalate Tricresyl phosphate Butyl phthalate Trioctyl phosphate Solv-7 H-1 H-2 ExZK-1 ExZK-2 Di(2-ethylhexyl) phthalate 1.2-bis (vinylsulfonylacetamido)ethane 4.6-dichloro-2-hydroxy-1. 3.
5-}Ryazine Na salt 7-(3-ethoxythiocarbonylaminobenzamide)-9-methyl-■ Rope mouth hagil-1. 2,
3. 4-tetrahydride acridinium triple olomethane sulfonate 2- (4- {3- [3-(3- (5- (3-
(2-chloro-5-(I-dodecyloxylponylethoxylponyl)phenylcarbamoyl]-4-hydroxy-1-naphthylthio}tetrazol-1-yl]phenyl)ureido]benzenesulfonamide 1 phenyl] 1 l -Formylhydrazine Sample 301 was prepared as described above, and then sample 302 was prepared by changing the magenta couplers in the sixth and seventh layers as shown in Table 3.

After cutting and processing the silver halide color photographic light-sensitive material prepared as described above and imagewise exposure, the cumulative replenishment amount of the color developing solution is determined by the method described below using an automatic developing machine. Continuous treatment was carried out until the amount increased to three times the amount. On the other hand, a sample that had been subjected to wet exposure with a three-color separation filter was processed before and after the start of continuous processing.

Processing time Temperature Mother tank capacity Full color development 135 seconds 38°C 151300
m//r/bleach fixing 40/33〃3〃30ro〃
Washing (I) 40"33'7 3
/Washing (2) 40l/33〃3ll320〃Drying 30l'80'' The method of replenishing the washing water is to replenish it to the washing bath (2), and then add it to the washing bath (2).
A so-called countercurrent replenishment system was used in which the overflow liquid of 2) was introduced into the washing bath (I). At this time, the amount of bleach-fix solution brought into the washing bath (I) from the bleach-fix bath for photosensitive materials is 3
5mJ/rrr, and the ratio of the amount of washing water replenishment to the amount of bleach-fix solution brought in is 9. It was 1x.

The composition of each treatment solution was as follows.

Ethylenediaminetetrakismethylenephosphonic acid 12. Od O. 70g 0. 003g 2.4g 2.5g 3. OxlO-” Moldiethylene glycol Benzyl alcohol Potassium bromide Penzotriazole Sodium sulfite Glucose preservative (Exemplary compound (7)) Triethanolamine N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-1 .5g 6.0g 6.0g 1.5g ?〇14.4d ■g 0.004g 2.9g 3.0g 3.6 XIO-2 mole 7.2g 7.2g Aminoaniline sulfate Potassium carbonate Fluorescent whitening pH (25℃) 30.0g 25.Og 1.0g 1.2g 1000J IOOOJ 10.25 10.80 Ethylenediaminetetraacetic acid 2 4.0g The same sodium Dihydrate ethylenediaminetetraacetic acid/Fe 70.0g (III
) ・Ammonium dihydrate ammonium thiosulfate
l8〇1 (700 g/l) p Sodium toluenesulfinate 20. Og thorium sodium bisulfite 20. 0g 5-merkabuto-1.3.4- 0.5g triazole ammonium nitrate 10. 0g and 1000dpH (25℃)
6. Both the soil mother liquor and the replenisher were mixed with tap water filled with an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-400 manufactured by Rohm and Haas). Water was passed through a bed column to reduce the concentration of calcium and magnesium ions to 3 .mu./l or less, and then 20 .mu./l of sodium isocyanurate dichloride and 5 g/l of sodium sulfate were added. The pH of this solution is 6.5-7
．． It was in the range of 5.

After the continuous processing, the presence or absence of contaminants adhering to the conveying roller that comes into contact with the photosensitive material at the exit of the color developing tank was examined.

In addition, in order to examine the processing stability in continuous processing, a sample exposed to 3200°K and 250 CMS through an optical wedge was processed before and after continuous processing, and an increase in the minimum density of a yellow image was investigated. Furthermore, in order to examine the image preservation properties of samples processed after continuous processing, samples exposed through the optical wedge described above were processed after continuous processing.
It was stored for one week under conditions of 0° C. and 770% RH, and an increase in the minimum density of a magenta image was examined. The results obtained are shown in Table 3.

Magenta Cobbler Test Compound l. Name of invention Test compound 2, Exemplary compounds M-16, M-24, M-30 1:1:1
(weight ratio) As is clear from Table 3, the mixture of general formula (M-I) or (M
When a sample containing a magenta coupler represented by -n) is used, and a lubricant represented by general formula n-1 or n-2 is used, both processing stability and image storage stability are extremely favorable. The results were obtained.

Silver halide color photographic materials Processing method

Claims (1)

[Scope of Claims] After exposing a silver halide color photographic light-sensitive material, aromatic first
In the method of processing with a color developing solution containing a class amine color developing agent, the color developing solution contains at least one compound represented by the following general formula (I), and the silver halide color photographic light-sensitive material A method for processing a silver halide color photographic material, wherein the outermost layer of the silver halide color photographic material contains at least one type of slip agent. 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: R represents a hydrogen atom or an optionally substituted alkyl group. )