JPS60162254A - Method for processing silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To perform quick processing with decreased color turbidity by developing and exposing a silver halide color photosensitive material contg. the compd. expressed by the specific general formula then processing the material with a color developing soln. then subjecting the material to a bleaching process. CONSTITUTION:A silver halide color photosensitive material contg. at least one kind of the compd. expressed by the formula I (R1 denotes a hydrogen atom or acetyl group, R denotes an aryl group, R2, R3, R4 and R5 denote a hydrogen atom, alkyl group or aryl group, R2, R3, R4 and R5 may be respectively the same or different) is imagewise exposed. The material is then processed with a color developing soln. contg. at least one kind selected from org. phosphonic acid, org. carboxylic acid and polyhydoxy compd and consisting substantially of hydroxyl amine or the salt thereof and thereafter the material is processed with a processing soln. having bleaching power.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for processing silver halide color photographic materials, and particularly to a processing method that suppresses the occurrence of color stains that occur during the development process.

<Prior Art> In general, color photographic materials are processed to form photographic images through processing steps including color development, bleaching, fixing or bleach-fixing, and washing with water, in which the material is processed with a developer containing an N-paraphenylenediamine color developing agent.

In the color development processing step, a color image is formed by a coupling reaction between an oxidized color developing agent and a color coupler, and at the same time, metallic silver is produced in the photographic step. This metallic silver is oxidized by bleaching agent in the subsequent desilvering process,
A soluble silver complex is formed and dissolved by the fixing agent.

In recent years, the processing of color photographic materials has become progressively faster, and methods have been used to speed up the processing, such as increasing the temperature of the color development process and reducing the number of processing baths. One method that has recently attracted particular attention is a method of using a development accelerator in the color developer when developing using a paraphenylenediamine color developer.

It is well known that when a developer accelerator is used, it tends to cause fog during development or during storage. However, among such development accelerators, black and white developing agents exhibiting superadditive properties in color development can provide a development accelerating effect with relatively low fog formation compared to other accelerators.

As such a black and white developing agent, U.S. Patent No. 2,417
N-methyl-p-terminophenol described in No. 514, 3-pyrazolidones described in British Patent No. 811,185, H, N, H' described in JP-A No. 150-15554.
, N'-tetramethyl-p-phenylenediamine, and among these, 3-pyrazolidones are particularly preferably used as development accelerators for color developers based on phenylenediamine.

A known example of containing 3-pyrazolidones in an emulsion layer and/or a non-emulsion layer of a silver halide photographic light-sensitive material is the example of use as a stabilizer described in Japanese Patent Publication No. 44-23383, No. 57-49895. In addition, there is an example in which phenidone derivatives are added to a layer that is 50% larger than the average grain size of silver halide contained in other layers, and a phenidone derivative is used to prevent a decrease in color density over time in a magenta 2-equivalent cuffler. 53-
No. 52422, JP-A-56-85748, JP-A No. 56-8
No. 5749, etc. In addition to being used as a development accelerator, it is used for a wide variety of purposes, including preventing the decomposition of magenta couplers over time and preventing fogging in emulsions.

However, in terms of development promotion effect and stability, it is rated 3-3.
Although black and white developing agents such as pyrazolidones can provide sufficiently satisfactory performance, for example, when 3-pyrazolidones are added to a color developer, there may be problems such as color staining and deterioration of the storage stability of the color developer. arise. On the other hand, when 3-pyrazolidones are added to a color photographic material, color turbidity similar to that which occurs when 3-pyrazolidones are added to a developer is observed, which poses a serious problem in terms of photographic performance.

Therefore, in order to solve the above problem, Japanese Patent Application Laid-Open No. 56-6433
No. 9 discloses the use of phenidone derivatives substituted at the 4-position in color photographic materials.

However, according to the results of our study, although some effect was observed on the softening phenomenon, it was insufficient in terms of preventing color stains. In particular, Ou", IFe'+
When a large amount of heavy metal ions such as ions are mixed in, or when an aged treatment liquid is used, no effect on color staining is observed at all. Furthermore, in recent years there has been a tendency to develop in highly active conditions such as high temperature and/or high pH in order to speed up the process, but in this case as well, the effects of the above-mentioned methods are extremely insufficient.

Furthermore, as a result of extensive studies, we found that color photographic materials containing phenidone derivatives, after color JA image processing,
When processing with a stop bath and/or a water washing bath, the color turbidity will peel off and be reduced, but as mentioned above, in recent processing steps, the number of processing baths has been reduced in order to speed up and simplify the process, and the color development processing step is continued. It has been found that color turbidity tends to occur under conditions where bleaching solution or bleach-fixing solution is used.

Therefore, the color turbidity that occurs when a sensitive material containing a 7-done derivative is processed for the purpose of speeding up the processing, particularly when the processing conditions or processing liquid composition changes, cannot be solved using conventional technology. This is considered to be irreversible for the photosensitive material, and the reality is that it has not yet been put to practical use.

Therefore, there has been a strong desire for a processing method that can be processed quickly, has very little color turbidity even with changes in processing conditions and processing solutions, and is stable.

<Objective of the Invention> The object of the present invention is to provide a method for processing silver halide color photographic light-sensitive materials quickly and with less color turbidity. It is an object of the present invention to provide a stable processing method with little color discoloration even when processing is performed under highly active conditions such as pH and high temperature.

<Structure of the Invention> The present invention provides a silver halide color photographic light-sensitive phase material containing at least one compound represented by the following general formula [I], and at least one compound selected from organic phosphonic acids, organic carboxylic acids, and polyhydroxy compounds. After treatment with a color developer containing seeds and substantially free of hydroxylamine or its salt (hereinafter referred to as the color developer solution of the present invention), subsequent treatment with a treatment solution having bleaching ability. The object of the present invention is achieved by this structure.

In the formula, R1 represents a hydrogen atom or an acetyl group, R represents an aryl group, R,, R□R4 and H each represent a hydrogen atom, an alkyl group, or an aryl group, R,
, R, , R4 and R1 may be the same or different.

The present invention will be explained in detail below.

In the compound represented by general formula [I], the acetyl group represented by R8 may be substituted with, for example, an alkyl group (methyl group, ethyl group, etc.).

Note that R is preferably a hydrogen atom.

Examples of the aryl group represented by R in the general formula [I] include phenyl, naphthyl, tolyl, xylyl, and the like, and these groups also include, for example, halogen atoms (chlorine, bromine, etc.). , an alkyl group (methyl group, ethyl group, propyl group, etc.), an alkoxy group (methoxy group, ethoxy group, etc.), a sulfonyl group, a ryomido group (methylamide group, ethylamide group, etc.). A particularly preferred aryl group is a phenyl group.

The alkyl group represented by R1+ RJ+ R4 and R in the general formula [I] has 1 to 1 carbon atoms in the straight or branch line.
0 (71 Furkyl group (for example, methyl group, ethyl group, methyl group, etc.) is preferable, and these alkyl groups may be substituted with a hydroxyl group, a ryomi group, an acyloxy group, etc. As a phenyl group, a naphthyl group, etc. can be used, but a phenyl group is particularly preferable, and these groups have a halogen atom (
chlorine atom, bromine atom, etc.), alkyl group (methyl group, ethyl group, propyl group), alkoxy group (hydroxyl group,
It may be substituted with a methoxy group, an ethoxy group, etc.

Next, specific examples of the compound represented by the general formula [I] used in the present invention will be shown.

I-a I 6 I-7■-5 00H.

■-111-12 U1i.

■-17■-18 0H.

I-251-26 ■-27■-28 I-329I 30 00,H.

Oh.

■-41I-42 0H.

I43 ■-44 ■ 45 l-46 1 ■-47I -48 ■-49 Addition of the compound represented by the general formula [I] to the silver halide color photographic light-sensitive material is carried out by adding the compound represented by the general formula [I] to the silver halide emulsion. It varies widely depending on the halogen composition, grain size, silver sensitivity, etc., but it is approximately 0.001 to 1 mol, preferably 0.0 mol per mol of silver halide of the copper halide color photographic light-sensitive material.
02 to 0.2 mol. In addition, when the number of photosensitive silver halide emulsion layers is 2 or more, generally 2 x 10 per d is used.
"-2X xo"-v The preferred compound is a silver halide color photographic light-sensitive material (hereinafter referred to as a color light-sensitive material) such as each light-sensitive emulsion layer, subbing layer, intermediate layer, and layer. Although the effects of the present invention can be obtained by adding the compound to any constituent layer, it is preferable to add the compound having relatively weak diffusivity to the photosensitive emulsion layer.

In order to incorporate the compound represented by the general formula [I] of the present invention into a desired constituent layer of the color S optical material, for example, methanol, ethanol,
Impropatol, acetone, methyl ethyl ketone, dimethylformamide, dioxane, ethyl acetate, etc. may be dissolved in a suitable solvent and added;
It may be added by emulsifying and dispersing it in a tree-philic colloid solution using a high-boiling point organic solvent such as tallate, dioctyl heptatarate, dimethyl heptatalate, trilocresyl phosphate, trioctyl phosphate, Furthermore, when it is contained in the photosensitive emulsion layer, it can be emulsified and dispersed simultaneously with the coupler and then added to the coating solution.

In addition, in the case of a photosensitive emulsion layer, the compound represented by the general formula [I] of the present invention may be added to the coating solution after the preparation of the photosensitive silver halide emulsion; If the sexual silver halide emulsion is a surface latent image type emulsion, it may be chemically ripened and optically sensitized; if the silver halide emulsion is an internal latent image type emulsion, the silver halide emulsion This can be done at any time after the emulsion has been prepared and optically sensitized. On the other hand, when added to a non-photosensitive layer, it can be added at any time before coating.

However, it is generally preferable to add it immediately before coating.

Silver halide emulsions used in the present invention include silver chloride,
Any silver halide such as silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver iodide or a mixture thereof may be used. However, silver chlorobromide is preferred to obtain good results in carrying out the present invention.

These silver halide emulsions are sensitized with noble metal salts such as ruthenium, rhodium, palladium, iridium, platinum, and gold, sulfur sensitization with sulfur compounds, selenium sensitization with selenium compounds, stannous salts, and polyamines. Various chemical sensitizations such as reduction sensitization using salts and the like can be performed. These emulsions can be optically sensitized by cyanine dyes, merocyanine dyes, etc., and are further stabilized by triphosphorozole compounds, asaindene compounds, benzthiazolium compounds, zinc compounds, etc. and various other known photographic additives may be added.

Any dye image type φ5 coupler can be used in the color light-sensitive material of the present invention. Among these, yellow dye self-image couplers include benzoyl ryoseto ryide dilide type,
Using Viva pilacetanilide type or 2-equivalent type ix o-dye image-forming couplers in which the carbon atom at the coupling position is substituted with a head substituting group (so-called split-off group) that can be separated during the coupling reaction. I can do it. The magenta dye image-forming couplers used are 5-virazo quaternary, pyrazolotrizole, pyrazolinobenzimidazole, indasilone, or two-equivalent magenta dye image-forming couplers having a split-off group.

Cyan dye image-forming couplers include phenolic thread,
A 2-equivalent type cyan color, 1g image-forming coupler having a naphthol type, pyrazoloquinazolone thread or split-off group, and particularly preferably used in the present invention, the cyan dye image-forming coupler has the following general formula [■]
, [III]. When the above-described cyan dye image-forming coupler is used in carrying out the present invention, it effectively acts against color turbidity of a cyan dye image.

General formula [■] H! General formula [1■] H or -0ONH8O,R, (R is an alkyl group, an alkenyl group, a cycloalkyl group, an aryol group or a hetero group
f14T a'), 1% is a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocycle, and R1 and R may be combined with each other to form a 5- to 6-membered ring. and R6 represents a palust group, preferably a group represented by the following general formula [1].

General formula [■1] Here, R1 represents a straight or branched alkyl group, preferably an alkyl group having 1 to 10 carbon atoms, and a is 0 to 3
represents an integer of; represents a straight chain or branched alkylene group or arylene group. P represents a hydrogen atom or a group that can be separated by coupling with an oxidized product of an aromatic primary amine color developing agent.

Next, specific exemplary compounds of the cyan coupler represented by the general formula [II] or [■] used in the present invention will be listed, but the compounds are not limited thereto.

F-1 04H0 -2 0M -3 H -4 ? -5 0, Hl '? -6 H ? -7 H O1H6 ? -8 0M −10 0H.

-11H Gelatin is preferable as the binder forming the constituent layers of the color photosensitive material of the present invention, but in addition to gelatin, 7
Derivative gelatin such as tallated seratin, phenylcarbamoylated gelatin, albumin, agar, gum arabic,
Alginic acid, casein, partially hydrolyzed cellulose derivative, partially hydrolyzed polyvinyl acetate, polyacrylamide,
Polyvinylpyrrolidone and copolymers of these vinyl compounds can also be used in part. In addition, the gelatin film of a normal color photosensitive material is used as the hardening film of the gelatin-based binder. Known hardeners used for decoding can be used, such as epoxy hardeners, ethyleneimino hardeners, activated vinyl hardeners, methanesulfonic acid hardeners, N-methylol hardeners, etc. It is possible to use organic hardeners such as IJ azine-based film hardeners, carbodiimide-based hardeners, and halogen-substituted film hardeners, or inorganic hardeners such as aluminum salts, chromium salts, and zirconium salts. can.

The support used in the color photosensitive material of the present invention includes:
For example, transparent supports such as p-7 film, acetyl cellulose film, polyvinyl acetal film, polycarbonate film, polystyrene film, and polyethylene terephthalate film, and synthetic reflective materials in which these supports are filled with white pigments such as titanium dioxide. As a support, paper and polymer ha paper such as polyethylene, polypropylene, etc. are used.

Next, the books used in the present invention will be described in detail.

Compounds preferably used as organic phosphonic acids and organic carboxylic acids have the general formulas [f%'l ~ [XIn], and more preferably used compounds have the general formulas OV] and [IX]
.

[XT], [■] and [X110.

General formula [IV] Pn, Ml R12R+4 In the formula, R0 and R3 are each a hydroxyl group, -Co(IM,
group, -PO, M, '4, and R11 represents a hydrogen atom or a saturated or unsaturated aliphatic group which may have a substituent having 1 to 3 carbon atoms (for example, methyl, ethyl, propyl, vinyl, allyl, hydroxymethyl, hydroxyethyl, carboxymethyl, carboxyethyl, phosphonomethyl, etc.), RI! is a hydrogen atom, a halogen atom 1, or the group listed above for R0, and R1 and R are an aryl group or R1
The group mentioned in 1, Flys, is the group that was removed in 1ast. M represents a hydrogen atom or a cation such as sodium, potassium, or lithium. Furthermore, α represents an integer of 0 to 3, and in the molecular structure, R11 and R1 may be the same or different.

General formula [■COPO, MIB,, R, 4 In the above formula, R1'l has the same meaning as R11, and "#+ R11 to R and 'l + α have the same meaning as those in the above general formula [Iv] .

General formula [■ P.O., M.

In the above formula, β is an integer from engineering to 2, and L is IB where β=1.
and αI4 are coaxial with those of the general formula [V], and when β=2,
Alkylene group, preferably an alkylene group having 1 to 4 carbon atoms,
Ml has the same meaning as the general formula [V] above.

General formula [■] P.O., M.

In the above formula, Rn is a hydrogen atom, a saturated or unsaturated aliphatic group optionally having a substituent having 1 to 3 carbon atoms (for example, methyl, ethyl, propyl, vinyl, 1'lll dimethyl, hydroxymethyl, and dooxyethyl). % ``lt*'' 1 m position, respectively a hydrogen atom, a saturated or unsaturated aliphatic group which may have a substituent (preferably an alkyl group having 1 to 1 o carbon atoms), an aralkyl group or nitrogen Represents a group that forms a ring together with an atom, and examples of the groups formed include a piperazine group, a pyridyl group, a pyrrolyl group, a pyrazolyl group, a morpholif group, a piperidino group, a pyrrolidinyl group, etc. Here, "l?", its
are never both hydrogen atoms.

M has the same meaning as the general formula [[V]].

General formula [Ml co 000M, R,,R,.

In the above formula, R□+ Ml and α have the same meanings as in general formula [Iv]. R
1.

R, ◎ and Tori each have the same meaning as R11 in the general formula [M].

General formula [IX] R1'1 R proverbial formula "II # RI'l #" I kl It is synonymous with the general formula [v] Nosore et al.

Further, r represents an integer from 2 to 16.

General formula [X] R,,-000M.

In the formula, R□ represents an aliphatic group, preferably an alkyl group (
preferably 1 to 12 carbon atoms), an alganyl group (preferably 1 to 6 carbon atoms), or one or more hydroxyl groups and/or
or an alkyl group (preferably having 1 to 12 carbon atoms) having a carboxyl group, or an alkenyl group (preferably having 1 to 12 carbon atoms);
6), and Ml has the same meaning as in the above general formula [IV].

General formula [XI] M, nCo -(A1)mM (At)n-000M+
General formula [X[I] In the formula, A and ~A6 each represent a hydrocarbon group, preferably an alkylene group, an MLI hydrocarbon group or a hydrocarbon group containing an alkylene group, a thioether group, or an ether group, Alternatively, h and Ay represent a hydrocarbon group, preferably an alkyl group. m and n are each 0
The integer M of ˜2 is the same as in the general formula [IV].

General formula [XIII] In the formula, R1l and ed are each a hydrogen atom, a phosphoric acid group, a carboxylic acid group, -0H,0nOH, -OH, P(l complex G:
i represents a salt thereof, or a hydroxyl group or a salt thereof, w, z
and Y are each hydrogen atom, )10gen atom, hydroxyl group,
It represents an alkyl group, a cyano group, a carboxylic acid group, a phosphoric acid group, an alkoxy group, a sulfonic acid group, or a salt thereof, which may have a substituent. Also m +'x o or 1, n
represents an integer of 1 to 4, l represents 1 or an integer of Gt 2, PG or 0 to 3, and q represents an integer of 0 to 2. Note that the current Dr R14 contains a hydrogen atom and/or a carboxylic acid group and/or a 1'' acid group on either side. (G is limited to these).

Specific compounds G of general formulas [IV] to [Hiki] are as follows.

-IA-2 OH -3A-4 ■ OH -5A-6 A-7A-f3 A-9A-10 0H,0OOH0H-000H 0H.

OH, OH.

H, O, P-0-PO, H, HO-OH-FO, H.

0H-000H 0H-0(IOH Hs A-15A-16 0H-CoOHOH, -000H H, O, P-C! -P.O., H.

0H,0OOH H, O, P-0-POsHt 0HIPO@H.

OH,0OOH A -21A -22 A -23A -24 A -25A -26 H,O,P-OH-PO,H,H,O,P-OH-Pn
,H.

A -27A -28 H, O, P-OH-PO, H, H, O, P-OH-PO
,H.

A -29A -'50 H, O, P-OH-PO, H, H, O, P-OH-PO
,H.

A -31A -32 H@O@P-OH-PO3H1HIO, P-OH-P(
+, H1H, 0, P-OH-PO, H, H, O, P-O
H-PO,H.

H snow 0@M’-0H-POsH* A-36A-37 A-38A-39 A-4Q A-41 A-42A-43 0H.

−44 H,01P-0-PO,H.

0H.

−45 -46 Po, H, OH, OOOH A-51A-52 (!Ht00(IHOH,0OOH C10,.

1 cH, Cool OH, -0-000H0H,0OOH OHs OH.

A-59A-60 0H.

(!HiOOOH OH, PO3H, HOOO-OR-Pυ$ to 1 A -
67A-68 0H, GOOHHOOO-0-PO,H.

0H,0OOH HOOO-0-PO,H.

0H,0OOH OH, OH, -000H 0H-00(IH 0H.

0H,0OOH A-75A-76 A-77A-78 0H,OH 0H,0OOH A-79A-80 0HOH H,0,P-0-FO,H.

H A-83A-84 C4’ll　0Hy(+OOH 1 N) i, OH A-89A-90 0H.

A-9L A-92 0H, OH, 0OOH -93 HOOO-OH-PO,H.

0H-000H Nawate OH, 0OOH Specific compounds of general formulas [X] to [XI[] are as follows.

B-1 Sodium citrate B-2 Oxalate B-3 Acetate B-4 Sodium propionate B-5 Potassium tartrate B-6 2) LiloEil sodium B-7 Iminodiacetate B-8 Sodium hydroxyiminodiacetate B-9 Potassium methyliminodiacetate B-10 Sodium ethyliminodiacetate B-11 Ethyliminodipropionic acid B-12 Propyliminodiacetate B-13 Ammonium ethylenediaminetetraacetate B-14
Sodium diethylenetriaminepentaacetate B-15 Propylenediaminetetraacetic acid B-16 Cyclohexanetetraacetic acid B-17 Glycol ether diamine tetraacetic acid B-181
,3-diamino-2-propatoltetraacetic acid The specific compound G of the general formula [XIII] is as follows: -1 -2 -3 0H,0OOH01(,0OOOHH,0OOH-4 -5 -6- 7 0HtO0ONa OH,OOONa 0-8 0T(,0OOHOH,0OOH -9 0H,PO,N~ OH,0OONa OH,00ONa OH,0OOHOH,0L)OH -12 00(180OOH) The aromatic polyhydroxy compound used in the present invention is: The molar ratio of ferric ion to the compound is 1 to 3
It is possible to form a complex with the ferric ion in an alkaline solution of . Generally, aromatic polyhydroxy compounds are compounds having at least two hydroxy groups on the aromatic ring that are ortho-positioned to each other. Preferably, these polyhydroxy compounds are compounds having at least two hydroxy groups located ortho-positioned to each other on the aromatic carbocycle and possessing no exocyclic unsaturation. Among the wide range of aromatic polyhydroxy compounds useful in this invention are, for example, benzene and naphthalene compounds, i.e.
Compounds that can be represented by the general formula [X[V] are included.

General Formula [XIV] In the above formula, T represents an atomic group necessary to complete the aromatic ring structure of benzene or 7-talene.

The above aromatic m structure may be substituted with a group or atom such as a sulfo group, a carboxy group, or a halogen atom in addition to the hydroxy 1 substituent. Common examples of aromatic polyhydroxy compounds useful in the present invention include:
It includes compounds such as:

D-1 Villcatechol D-24,5-dihydroxy-m-benzenedisulfonic acid D-34,5-dihydroxy-m-benzenedisulfonic acid disodium salt D-4 Tetrabromopyrocatechol D-5 Pyrogallol D-6 Gallic acid Acid D-7 Methyl gallate D-8 Propyl gallate D-9 2,3-dihydroxynaphthalene-6-sulfonic acid D-10 2,3,8-trihydroxynaphthalene-6-
Sulfonic acid D-111,2-dihydroxybenzene-3,5-sodium disulfonate Compounds of general formulas [Iv] to [IXII are German Patent No. 22
No. 52,684, US Pat. No. 3,400,148 and Journal of Organic Chemistry Vol. 38, 186.
It is synthesized using the general synthesis method described in λ et al., pages 7-1869 (1973).

Further, general formula [XIII] is described in U.S. Patent No. 3,632,637, Journal of the American Chemical Society 89 (1967) page 837, and JP-A-58-195845 J+. It can be synthesized using various general synthesis methods.

The compounds of general formulas [X] to [X[I] and general formula [XIV] can be easily synthesized by well-known synthesis methods.

Organic phosphonic acids, organic carboxylic acids, and polyhydroxy compounds (
Hereinafter, it will be referred to as the chelating agent of the present invention. ) may be added to the color developing solution depending on the effect and the molecular weight of the chelating agent, etc., but it can be used in the range of 0.001 to 20 i per 11 of the color developing solution, preferably in the range of 0.005 to 15 J7, and more preferably Good results can be obtained by adding 0.01 to log.

Further, in carrying out the present invention, it is sufficient that at least one kind of the above-mentioned chelating agent of the present invention is contained, and if desired, two
It is also possible to use a combination of more than one type of chelating agent of the present invention, and in that case, the amount of chelating agent added to the color developer is preferably within the above range.

In the present invention, it is an essential condition that the color developer does not substantially contain hydroxylamine and its salts, but being substantially free generally means that the color developer does not contain hydroxylamine or its salts in order to maintain the stability of the color developer. This refers to the amount of hydroxylamine and its salts within a range that does not affect storage stability, but specifically, the amount of hydroxylamine or its salts is up to 0.2 g per 11 color developing solution. Preferably, good results can be obtained up to 0.1 g.

The hydroxylamine according to the present invention is an amine in which the nitrogen atom is directly bonded to a hydroxyl group, such as
It means an amine containing 7 human proxylamide groups of H, and is usually used in the form of a water-soluble acid salt. Examples of such salts include sulfates, oxalates, chlorides, phosphates, carbonates, acetates, and the like. Furthermore, hydroxylamine can be in a substituted or unsubstituted form; for example, the nitrogen atom of hydroxylamine can be substituted with an alkyl group. Hydroxylamine can be represented by the general formula [XV].

General formula [XV] M, -N-OR However, in the formula, M represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In addition, its water-soluble acid salt is also present. As an additive used in the color developing solution of the present invention, #! Preservatives such as sulfates, accelerators from alkali such as sodium hydroxide, sodium carbonate, potassium carbonate, inorganic or organic such as potassium bromide, 2-methylbenzimitazole, methylbenzthiazole, etc. Examples include surface overdevelopment inhibitors comprising trace amounts of iodide and mercapto compounds.

The aromatic primary amine color developing agents used in the color developer of the present invention include known ones that are widely used in various color photographic processes. These developers include minophenol and p-phenylenediamine derivatives.

In the present invention, p-phenylenediamine represented by the following general formula [XVD] is particularly preferably used. General formula [XvI] NH.

In the formula, R1l represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may have a substituent, and Rts and R1 represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group, or an alkyl group which may have a substituent. It represents the luxir group, and at least one of the capitals is alkyl groups or ++ OHT ninth nine ] □.

Note that a represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, 7, and a and b represent an integer of 1 to 5. The following are specific examples, but are not limited to these.

-1 -2 NH7 NHL NH meeting N.H.

N) 1 layer Le - 8 N.H.

N.H.

-11 n-11 NH The p-phenylene derivatives represented by the general formula cxvr+ can be used as salts of organic acids and inorganic acids, such as hydrochloride,
Sulfate, phosphoric acid m, P-toluenesulfone am, Mf[salt, oxalate, benzenedisulfonate, etc. can be used.

Among the compounds represented by the general formula cxvn, the compound and/or Rty or one++OHt introduction"left Rxs C&,
t) and R, #[, and the same meanings as above, the desired effects of the present invention are particularly well achieved. Additionally, these compounds generally exhibit color development Il! About 0.1 for liquid 11! i to about 30 J, more preferably at a concentration of about 1 g to 1511 for color developer 1j.

In addition to the primary aromatic amine color developer, the alkaline color developer of the present invention further contains various components normally added to color developers, such as sodium hydroxide, sodium carbonate, and potassium carbonate. The composition may optionally contain alkaline agents such as alkali metal sulfites, alkali gold monobisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, and the like. The pH value of this color developer is usually 7 or more, most commonly about 10 to about 13. A variety of compounds can be used; for example, a metal complex salt of an organic acid has the effect of oxidizing the metallic silver produced by development and converting it into silver halide, and at the same time coloring the uncolored portion of the coloring agent.
Its structure is one in which metal ions such as iron, cobalt, and copper are coordinated with amide/polycarboxylic acids or organic acids such as oxalic acid and citric acid. The most preferred organic acids used to form such metal complex salts of organic acids include the following.

Ethylene diamine triacetate ethylenediamine-N-(β-oxyethyl-H,
N', N'-) dipropylene diacetate diacetate nitrilotriacetate cyclohexane diamine diacetate iminodiacetate dihyde tetraxyethylglycine ethyl ether diamine Ethylenediaminetetraacetic acid disodium salt Ethylenediaminetetraacetic acid tetra(trimethylammonium salt Ethylenediaminetetraacetic acid tetrasodium salt Diethylenetriaminepentaacetic acid pentasodium salt Ethylenediamine-N-(β-oxyethyl-N,
The bleach-fix solution contains the above-mentioned metal complex salts of organic acids (e.g., iron complex salts) as a bleaching agent, as well as thiosulfate and thiocyanic acid. A liquid having a composition containing a silver halide fixing agent such as a salt or a thiourea is applied. In addition, a bleach-fix solution consisting of a composition in which a small amount of a halogen compound such as potassium bromide is added in addition to a bleaching agent and the above-mentioned silver halide fixer, or conversely, a composition in which a large amount of a halogen compound such as potassium bromide is added. Further, a special bleach-fix solution having a composition consisting of a combination of a bleaching agent and a large amount of a halogen compound such as potassium bromide can also be used. As the halogen compound mentioned above, in addition to potassium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide, potassium iodide, ammonium iodide, etc. can also be used.

Silver halide fixing agents to be included in the bleach-fixing solution include compounds that react with halides to form water-soluble complex salts, such as potassium periosulfate, sodium thiosulfate, and ammonium thiosulfate, which are used in ordinary fixing processes. thiosulfates such as potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, or thioureas, thioether-rich bromides,
Iodide is a typical example.

The bleaching solution or bleach-fixing solution may contain various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. The pH buffering agent may be contained singly or in combination of two or more. Furthermore, various antifoaming agents or surfactants can also be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as polycarboxylic acid, or a type of stabilizer such as nitroalcohol nitrate, methanol, dimethylformide, etc. , an organic solvent such as dimethyl sulfate 7 oxide, etc. may be appropriately contained.

These color development and processing with a processing solution having bleaching ability may need to be carried out continuously, and the processing solution having bleaching ability specifically refers to a bleaching solution and a bleach-fixing solution.

Furthermore, prior to color development, black and white development, fixing treatment, etc. may be performed.

The color developing solution and the bleaching solution and bleach-fixing solution having bleaching ability of the present invention include color paper, color negative film, color positive film, color reversal film for slides, color reversal film for movies, color reversal film for TV, reversal color paper, etc. It can be applied to silver halide color photographic photosensitive materials.

(Example) Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example-(1) A silver halide color photographic light-sensitive material was prepared by sequentially coating the following layers on polyethylene resin coated paper.

The amount added is expressed per 100 d unless otherwise specified.

(Layer containing gelatin #-171519.

(@-2) 20 ■ gelatin, 4.5NT9 blue-sensitive silver chlorobromide emulsion, and 9 ■ 2-(1-benzyl-2,4-dioxyimidazolidin-3-yl)-2-bivalyl - 21-di-tertiary-amylphenoxybutane-5'-[4-(2,4-di-tertiary-amylphenoxybutanylide), 0.5% of 5,5-dimethyl-1,3-cyclohexane dione, and 2°5-di- of 0.151n9
Contains 3.5 μm of sea n-butyl phthalate high boiling point solvent in which tertiary octylhydroquinone is dissolved.

layers.

(Layer-3) 10 ~ gelatin, 0.45 Da 2,5-
A layer containing di-tert-octylhydroquinone.

(Layer-4) 15 μg of gelatin, 4.5 g of green-sensitive silver chlorobromide emulsion, and 5.5 μg of 3-[2-chloro-5-(
1-octadecylsuccinimidonoanilino] -1-(2゜4.6-)riftetralophenylnopyrazofourine and 0.1101n of 2.5-di-tertiaryoctylhydroquinone were dissolved, - Layer containing 2,0# tricresyl phosphate high boiling solvent.

(Nj-5) 15 Da Seratin, 0.8 to 2.5-
A layer containing 41v dioctyl phthalate dissolved in di-tertiary octylhydroquinone and the 5 da UV absorber UV-1.

(Layer-6) 15 ■ gelatin, 3.5 ~ red-sensitive silver chlorobromide emulsion, 3.8 ■ 2-[2-(2゜4-di-tertiary-milphenoxybutyramide]-a) , a-dichloro-5-methylphenol, and 2,01119 dioctyl 7-talate dissolved in 0.15 to 2,5-di-tert-octylhydroquinone.

(Layer - 7J 1 oz gelatin, and 0.3 oz 2.
A layer containing 5-di-tertiary octyl hydrequinone and 2.0 dioctyl 7-talate dissolved in 2Iv of the following ultraviolet absorber UV-1.

01HIl(t) 2,4-dichloro-6-hydroxy-8 as a hardening agent
-) Add sodium chloride to N11+3+'+7 in an amount of 0.16In9 per 1g of gelatin to prepare a photosensitive material, and store it at 1.40℃ and 80% relative humidity for 48 hours, A sample (A) was prepared by working the dura mater.

In addition, the following samples (B) to fD) were also created at the same time as sample (A).

Sample (B) Sample in which exemplified compound i-4 was added to layer-1 Sample (0) ■-15 Sample (D) l-48 The obtained sample was passed through an optical wedge to expose the exposed layer, and was processed according to the following processing steps. .

Standard treatment process Standard treatment temperature Treatment time The composition of the treatment liquid is as follows.

[Color developing solution] [Divide the standard color developing solution into bleaching formula solution, and as shown in Table (1), chelating agent 0.1 g and hydroxylamine sulfate 2.0 per 16 color developing solutions! ! and the pH was adjusted to 10.20.

After that, some of the color developing solution was kept refrigerated, and the other part was kept for 2 hours.
After being stored at 40° C. for a week, each sample was readjusted to pH 10 and 2, and treated with Piece Treatment 41 (hereinafter referred to as hand skin) according to the treatment steps described above, and color turbidity and maximum density were measured.

However, the degree of color turbidity is determined by the reflection density of a yellow image with blue and green monochromatic light as DE and DG, and D, G / DB.
I thought so. Furthermore, the highest density was determined by the blue reflection density.

In addition, DG/DB=Table (1
) As is clear from the above, processing other than the present invention can be done on the same day or stored 2a.
However, the present invention satisfies both the color cloudiness and the developability of the blue-sensitive layer, whereas the present invention satisfies both the color cloudiness and the developability. That is, when using a photosensitive material other than the present invention, the color becomes cloudy on the same day and after storage. The developability of TFL is quite poor.

Furthermore, although sample processing using the photosensitive material of the present invention using hydroxylamine sulfate resulted in good developability of the blue-sensitive layer,
Difficulty in color was observed, and in particular, the discoloration showed a remarkable increase after storage on two transparent surfaces.

It can be seen that only when the photosensitive material according to the present invention is combined with the processing, the color cloudiness on the same day and after storage for two weeks shows a value close to that of the standard processing, and the developability is also good.

[Example-2] Color developer 1# was added to the standard color developer used in Example (1).
Hydroxylamine aWNz, og, 1.2 per liquid 11
Using 0.1 g of sodium dihydroxybenzene-3,5-disulfonate, the pH was adjusted as shown in Table (2), and the hand skin was treated and evaluated in the same manner as in Example (1).The results are shown in Table (2). 2).

As is clear from Table (2), as the pH becomes higher in the treatments other than the present invention, there is a noticeable increase in color dullness, especially at p) 110.50, whereas in the present invention, there is no tendency as compared to that of the present invention. Even at high pH, no increase in dark-colored turbidity was observed, and the result was almost the same as the standard treatment.

Also, regarding the developability, although the development properties of processed samples 9 to 11 using sample (A) outside the present invention improve as the pH increases, they are considerably inferior to the samples according to the present invention.

Therefore, it can be seen that only when the sample (E) and the processing method of the present invention were used, there was little color staining even when the pH increased, and the developability was also good.

[Example-3] C- ions were added to the color developer solution as shown in Table (3), and the sample B used in Example (2) was changed to the sample sample.
-(3) As is clear from Table (3), when the amount of Ou'' ions mixed in is relatively small, the color turbidity increases, but i1
When the amount of contamination reaches about 5 ppm, a significant increase in color turbidity is observed. On the other hand, the treatment of the present invention had almost the same level of color turbidity as the comparison due to the contamination of 0U ox ions, and almost no results were obtained compared to the standard treatment.

In addition, the developability was also evaluated, but Ou + ion lpp
m is almost the same as no additives. Example (1), although a slight increase in developability was observed at 3 ppm.

It showed the same tendency as (2).

[Example-4] The Ou+ ions in the standard color developing solution were adjusted to 3 ppm, and 2.0 g of hydroxylamine sulfate chelating agent was added as shown in Table (4).
Evaluation table for color turbidity was prepared in the same manner as in Example (1) except that the storage period (40'G) was changed to 7 days.
(4) (Note) Comparison (■) Sodium tripolyphosphate (■)
Sodium Tetrapolyphosphate O00 As is clear from Table-(4), when the sample according to the present invention is subjected to color development treatment in the presence of a chelating agent and a sulfate of human tetraxylamine, regardless of the type of chelating agent, Color turbidity is increasing. Moreover, when processed with a color developing solution containing a chelating agent other than the present invention and without human tetraxylamine, color staining could hardly be prevented, whereas surprisingly, the present invention using the chelating agent of the present invention Only the processing method (2) showed good results, with slightly more color turbidity than the standard treatment, but the same level of color turbidity as Comparative Mums 33 to 38.

Claims (1)

[Scope of Claims] After exposing a silver halide color photographic light-sensitive material containing at least one compound represented by general formula [I] in one image, an organic phosphonic acid, an organic carboxylic acid, and a polyhydroxy compound are produced. A silver halide characterized in that it is treated with a color developing solution containing at least one selected from the following and substantially free of hydroxylamine or its salt, and then subsequently treated with a processing solution having bleaching ability. A method of processing color photographic materials. General formula [I] [In the formula, the horse represents a hydrogen atom or a cetyl group, R represents a γ-lyl group, R1+ "It R4 and R6 each represent a hydrogen atom, an alkyl group, or a lyl group,"
11 "41" 4 and R1 may be the same or different. ]