JPH0550733B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a processing method for silver halide color photographic materials, and particularly to a processing method that suppresses the occurrence of color clouding that occurs during the development process. <Prior Art> Generally, after exposure, color photographic materials undergo processing steps including color development, bleaching, fixing or bleach-fixing and washing with water to produce photographic images. 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. In a subsequent desilvering step, this metallic silver is oxidized by a bleaching agent and dissolved by a fixing agent to form a soluble silver complex. In recent years, the processing of color photographic materials has become increasingly 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. However, 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 the use of a normal development accelerator has the disadvantage that fog tends to form during development or 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. There is a US patent for this kind of black and white developing agent.
N-methyl-p-aminophenol described in No. 2417514, 3-pyrazolidones described in British Patent No. 811185, N,N,N',N'- described in JP-A-50-15554
Examples include tetramethyl-p-phenylenediamine, and among these, 3-pyrazolidones are particularly preferably used as development accelerators for paraphenylenediamine color developers. Known examples of containing 3-pyrazolidones in the emulsion layer and/or non-emulsion layer of silver halide photographic light-sensitive materials include the example of use as a stabilizer described in Japanese Patent Publication No. 44-23383, and the example described in Japanese Patent Publication No. 57-49895. An example of adding a phenidone derivative to a layer containing 50% larger average silver halide grain size than other layers, and a 53rd Japanese Patent Publication (Kokai) using phenidone derivatives to prevent a decrease in color density over time of a magenta 2-equivalent coupler. −52422, JP-A-Sho
No. 56-85748, No. 56-85749, etc., and in addition to being a development accelerator, it is used for a wide variety of purposes, including preventing decomposition of magenta couplers over time and preventing fogging in emulsions. However, although black and white developing agents such as 3-pyrazolidones can provide sufficiently satisfactory performance in terms of development promotion effect and stability, for example, when 3-pyrazolidones are added to a color developer, color turbidity occurs. This also causes problems such as deterioration of the stability of the color developer. 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,
No. 64339 discloses the use of phenidone derivatives substituted at the 4-position in color photographic materials.
However, according to the results of our studies, although some effect was observed in softening development, it was insufficient in terms of preventing color clouding. In particular, heavy metal ions such as Cu ²⁺ and Fe ³⁺ ions may be mixed in in large quantities due to the structure, type, conveyance method, material, and quality of the water used in the automatic processor (hereinafter referred to as automatic processor). When an aged treatment solution is used, no effect on color turbidity is observed.
In addition, 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 various studies, we found that when color photographic materials containing phenidone derivatives are treated with a stop bath and/or a water washing bath after color development processing, color turbidity is considerably reduced; As mentioned above, in recent processing processes, the number of processing baths has been reduced in order to speed up and simplify the process, and it has been found that color turbidity tends to occur under conditions where a bleach solution or bleach-fix solution is applied after color development processing. . Therefore, the color clouding that occurs when processing a sensitive material containing a phenidone derivative for the purpose of speeding up the processing, especially when the processing conditions or processing liquid composition changes, cannot be solved using conventional techniques. It is considered to be unavoidable for the photosensitive material, but 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. <Object 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 turbidity 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 material containing at least one compound represented by the following general formula [], an organic phosphonic acid, the following general formula [], [XI], [XII] or A color developer containing at least one kind selected from an organic carboxylic acid represented by [ ] and a polyhydroxy compound represented by the following general formula [ The object of the present invention has been achieved by the above-mentioned structure. General formula [] In the formula, R ₁ represents a hydrogen atom or an acetyl group,
R represents an aryl group; R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom, an alkyl group, or an aryl group; R ₂ , R ₃ , R ₄ and R ₅ may be the same or different; It's okay. General formula [] R ₂₂ -COOM ₁ In the formula, R ₂₂ represents an aliphatic group, and M ₁ represents a hydrogen atom or a cation such as sodium, potassium, or lithium. General formula [XI] M ₁ OCO− (A ₁ ) _n −M− (A ₂ ) _o −COOM ₁ General formula [XII] In the formula, A ₁ to _{A 6} each represent a hydrocarbon group,
M is a hydrocarbon group, or a hydrocarbon group containing a thioether group or an ether group, or (B ₁ and B ₂ represent a hydrocarbon group, and A ₇ represents a hydrocarbon group.) m and n are each integers of 0 to 2, and M ₁ has the same meaning as in the general formula []. ] General formula [] In the formula, _R23 and _R24 are a hydrogen atom, a phosphoric acid group, a carboxylic acid group, _{-CH2COOH , -CH2PO3H2 ,} respectively.
or a salt thereof, X is a hydroxyl group or a salt thereof, W, Z and Y are each a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group which may have a substituent, a cyano group, a carboxylic acid group, a phosphoric acid group , an alkoxy group, a sulfonic acid group, or a salt thereof. Also, m is 0 or 1, n is an integer from 1 to 4, l
represents 1 or 2, p represents an integer of 0 to 3, and q represents an integer of 0 to 2. Note that R ₂₃ and R ₂₄ do not contain a hydrogen atom at the same time, but one of them contains a carboxylic acid group. General formula [] In the formula, T represents an atomic group necessary to complete the aromatic ring structure of benzene or naphthalene. The present invention will be explained in detail below. In the compound represented by the general formula [],
The acetyl group represented by R ₁ may be substituted with, for example, an alkyl group (methyl group, ethyl group, etc.). Note that R ₁ is preferably a hydrogen atom. Examples of the aryl group represented by R in the general formula [ ] include phenyl group, naphthyl group, tolyl group,
These groups include, for example, halogen atoms (chlorine atoms, bromine atoms, etc.), alkyl groups (methyl group, ethyl group, propyl group, etc.), and alkoxy groups (methoxy group, ethoxy group, etc.). , a sulfonyl group, an amide group (methylamide group, ethylamide group, etc.). A particularly preferred aryl group is a phenyl group. The alkyl group represented by R ₂ , R ₃ , R ₄ and R ₅ in the general formula [] is a linear or branched alkyl group having 1 carbon number.
~10 alkyl groups (eg, methyl, ethyl, butyl, etc.) are preferred, and these alkyl groups may be substituted with hydroxyl, amino, acyloxy, etc. groups. Further, as the aryl group, phenyl group, naphthyl group, etc. can be used, but phenyl group is particularly preferable, and these groups include halogen atoms (chlorine atom, bromine atom, etc.), alkyl groups (methyl group, ethyl (propyl group, propyl group), alkoxy group (hydroxyl group, methoxy group, ethoxy group, etc.). Next, the general formula used in the present invention []
Specific examples of compounds represented by are shown below. -1 -2 -3 -4 I-5 -6 -7 -8 -9 −10 −11 −12 −13 −14 −15 −16 −17 −18 −19 −20 −21 −22 −23 −24 −25 −26 −27 −28 −29 −30 −31 −32 −33 −34 −35 −36 −37 −38 −39 −40 −41 −42 −43 −44 −45 −46 −47 −48 −49 The amount of the compound represented by the general formula [] added to a silver halide color photographic light-sensitive material varies widely depending on the halogen composition, grain size, silver amount, etc. of the silver halide emulsion. Approximately 0.001 per mole of silver halide in photographic light-sensitive materials
-1 mol, preferably 0.002-0.2 mol. When there are ^two or more photosensitive silver halide emulsion layers, the amount is generally 2 x 10 ^-5 to 2 x 10 ^-3 mol, preferably 5 x 10 ^-5 to ^{10 -3} mol per m 2 . General formula []
The compound represented by the above can be incorporated into any layer constituting a silver halide color photographic material (hereinafter referred to as color light-sensitive material), such as each photosensitive emulsion layer, subbing layer, intermediate layer, protective layer, etc., and the present invention is applicable. However, it is preferable to add a compound having relatively weak diffusivity to the photosensitive emulsion layer. In order to incorporate the compound represented by the general formula [] of the present invention into a desired constituent layer of a color photosensitive material, for example, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, dimethyl It may be added by dissolving it in a suitable solvent such as formamide, dioxane, ethyl acetate, or dibutyl phthalate, dioctyl phthalate, dimethyl phthalate, tri-o-cresyl phosphate, trioctyl phosphate. It may be added by emulsifying and dispersing into a hydrophilic colloid solution using a high boiling point organic solvent such as This can also be added to the coating solution. In the case of a photosensitive emulsion layer, the compound represented by the general formula [ If the 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 Any time after the preparation and optical sensitization is acceptable. 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, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide,
Any silver halide such as silver iodobromide, silver chlorobromoiodide or a mixture thereof may be used, but silver chlorobromide is preferred since it has been found that good results have been obtained in the practice of the present invention. Obtainable. These silver halide emulsions are sensitized by noble metal salts such as ruthenium, rhodium, palladium, iridium, platinum, and gold, sulfur sensitization by sulfur compounds, selenium sensitization by selenium compounds, stannous salts, polyamine salts, etc. Various chemical sensitizations such as reduction sensitization can be performed. These emulsions can be chemically sensitized using cyanine dyes, merocyanine dyes, etc. In addition, stabilizers such as triazole compounds, azaindene compounds, benzthiazolium compounds, zinc compounds, and various other known stabilizers can be applied to these emulsions. photographic additives can be added. Any dye image-forming coupler can be used in the color light-sensitive material of the present invention. Among these, yellow dye image-forming couplers include benzoylacetanilide type, pivaloylacetanilide type, or 2-equivalent type yellow in which the carbon atom at the coupling position is substituted with a substituent that can be separated during the coupling reaction (a so-called split-off group). Dye image forming couplers can be used. Those used as magenta dye image-forming couplers include 5-pyrazolones, pyrazolotriazoles, pyrazolinobenzimidazoles,
It is a two-equivalent type magenta dye image-forming coupler having an indazolone type or split-off group. Examples of cyan dye image-forming couplers include phenolic, naphthol, pyrazoloquinazolone, or two-equivalent type cyan dye image-forming couplers having a split-off group.Cyan dye image-forming couplers particularly preferably used in the present invention include: Examples include cyan dye image-forming couplers represented by the following general formulas [] and [].
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 [] General formula [] In the above formula, Q is _-COR7 ,

[Formula] − SO ₂ R ₇ ,

【formula】

【formula】

[Formula] -CONHCOR ₇ or -CONHSO ₂ R ₇ (R ₇ is an alkyl group, an alkenyl group,
It is a cycloalkyl group, an aryl group, or a heterocycle, and R ₈ is a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocycle, and R ₇ and R ₈ are bonded to each other and 5 to 6 (which may form a membered ring), and R ₆ represents a balance group, preferably a group represented by the following general formula [']. General formula [′] Here, R' represents a straight-chain or branched alkyl group, preferably an alkyl group having 1 to 10 carbon atoms, a represents an integer of 0 to 3, and J represents a straight-chain or branched alkylene group, an arylene group. represents. 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 [] or [] used in the present invention will be listed, but the compounds are not limited thereto. F-1 F-2 F-3 F-4 F-5 F-6 F-7 F-8 F-9 F-10 F-11 As the binder forming the constituent layers of the color photosensitive material of the present invention, gelatin is preferred, but in addition to gelatin, derivative gelatin such as phthalated gelatin, phenylcarbamoylated gelatin, albumin, agar, gum arabic, alginic acid, casein, etc. , partially hydrolyzed cellulose derivatives, partially hydrolyzed polyvinyl acetate, polyacrylamide, polyvinylprolidone, and copolymers of these vinyl compounds can also be used in part. Also, for the hardening film of a binder mainly composed of gelatin, known hardening agents used for hardening gelatin films of ordinary color light-sensitive materials can be used.For example, epoxy hardening agents, ethylene imino Organic hardeners such as hardeners, activated vinyl hardeners, methanesulfonic acid hardeners, N-methylol hardeners, carbodiimide hardeners, and halogen-substituted-S-triazine hardeners. Alternatively, inorganic hardeners such as aluminum salts, chromium salts, and zirconium salts can be used. Examples of the support used in the color light-sensitive material of the present invention include transparent supports such as nitrocellulose film, acetylcellulose film, polyvinyl acetal film, polycarbonate film, polystyrene film, and polyethylene terephthalate film, and those containing carbon dioxide. Synthetic reflective supports filled with white pigments such as titanium, papers, and polymer-coated papers such as polyethylene, polypropylene, etc. are used. Next, the organic phosphonic acid used in the present invention, the general formula [], [XI], [XII] or [
] The organic carboxylic acid represented by the formula [] and the polyhydroxy compound represented by the following general formula [] are preferably used as chelating agents. Each of the above compounds will be explained in detail below. Compounds preferably used as organic phosphonic acids have the general formulas [] to [] and [], and particularly preferably used as organic sulfonic acids and organic carboxylic acids have the general formulas [], [], [XI],
[XII] and []. General formula [] In the formula, R ₉ and R ₁₀ are each a hydroxyl group, -COOM ₁
group, -PO ₃ M ₁ group, and R ₁₁ 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.), R ₁₂ is a hydrogen atom, a halogen atom, or a group listed for R ₉ above, and R ₁₃ and R ₁₄ are an aryl group or R ₁₁ The group mentioned, R ₁₅ , is
R represents the group listed in ₁₂ . M ₁ 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, R ₁₁ and R ₁₂ may be the same or different. General formula [] In the above formula, R ₁₁ ′ has the same meaning as R ₁₁ , and R ₉ , R ₁₁ to R ₁₅
and M ₁ and α have the same meanings as those in the general formula []. General formula [] In the above formula, β is an integer from 1 to 2, and L is when β=1.

[Formula] Group (However, R ₁₃ to R ₁₅ and α have the same meanings as those in the above general formula []), β=
In the case of 2, the alkylene group preferably has 1 to 4 carbon atoms.
The alkylene group M ₁ has the same meaning as in the general formula [ ]. General formula [] In the above formula, R ₁₆ is a hydrogen atom, a saturated or unsaturated aliphatic group which may have a substituent having 1 to 3 carbon atoms (for example, methyl, ethyl, propyl, vinyl,

(alkyl, carboxymethyl, hydroxymethyl, hydroxyethyl, etc.) or aryl group having [Formula] as a substituent, R ₁₇ and R ₁₈ are each a hydrogen atom, a saturated or unsaturated aliphatic group which may have a substituent (preferably an alkyl group having 1 to 10 carbon atoms), an aralkyl group, or a group that forms a ring together with a nitrogen atom. Groups formed include a piperazino group, a pyridyl group, a pyrrolyl group, a pyrazolyl group, a morpholino group, and a piperidino group. , pyrrolidinyl group, etc. Here, R ₁₇ and R ₁₈ are not both hydrogen atoms. M ₁ has the same meaning as the general formula []. General formula [] In the above formula, R ₁₂ , M ₁ and α have the same meaning as the general formula [].
R ₁₉ , R ₂₀ and R ₂₁ are each R ₁₁ of the general formula []
is synonymous with General formula [] In the above formula, R ₁₁ , R ₁₁ ′, and M ₁ have the same meanings as those in the general formula []. Further, γ represents an integer from 2 to 16. General formula [] R ₂₂ -COOM ₁ In the formula, R ₂₂ represents an aliphatic group, preferably an alkyl group (preferably having 1 to 12 carbon atoms), an alkenyl group (preferably having 1 to 6 carbon atoms), or 1 or 2
Represents an alkyl group (preferably having 1 to 12 carbon atoms) or an alkenyl group (preferably having 1 to 6 carbon atoms) having the above hydrogen group and/or carboxyl group,
M ₁ represents a hydrogen atom or a cation such as sodium, potassium, or lithium. General formula [XI] M ₁ OCO− (A ₁ ) _n −M− (A ₂ ) _o −COOM ₁ General formula [XII] In the formula, A ₁ to _{A 6} each represent a hydrocarbon group,
Preferably represents an alkylene group, and M is a hydrocarbon group, preferably an alkylene group, or a hydrocarbon group containing a thioether group or an ether group, or (B ₁ and B ₂ represent a hydrocarbon group, preferably an alkylene group, and A ₇ represents a hydrocarbon group, preferably an alkyl group). m and n are each integers of 0 to 2, and M ₁ has the same meaning as in the general formula []. General formula [] In the formula, _R23 and _R24 are a hydrogen atom, a phosphoric acid group, a carboxylic acid group, _{-CH2COOH , -CH2PO3H2 ,} respectively.
or a salt thereof, X is a hydroxyl group or a salt thereof, W, Z and Y are each a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group which may have a substituent, a cyano group, a carboxylic acid group, a phosphoric acid group , represents an alkoxy group, a sulfonic acid group, or a salt thereof. Also, m is 0 or 1, n is an integer from 1 to 4, l
represents 1 or 2, p represents an integer of 0 to 3, and q represents an integer of 0 to 2. Note that R ₂₃ and R ₂₄ do not have a hydrogen atom at the same time, and either one contains a carboxylic acid group and/or a phosphoric acid group. The carboxylic acid in the general formula [] was defined as the general formula []. Although specific compounds are illustrated below, the compounds of the present invention are not limited to these. Specific compounds of general formulas [] to [] are as follows.

[Table] ｜
_CH2 COOH

_CH3

｜
H ₂ O ₃ P−C−PO ₃ H ₂

A−9 ｜
_CH3 -C-COOH

｜
_CH2 COOH

_CH3

｜
H ₂ O ₃ P−C−PO ₃ H ₂

｜
A−10 CH ₃ −C−COOH

｜
CH－COOH

｜
_CH3

[Table] ｜
A-19 CH ₂

｜
_{K2O3P -} CH <sub>- PO3K2

H2O3P -</sub> CH _{- PO3H2}

｜
A-20 CH-PO ₃ H ₂

｜
CH ₂ PO ₃ H <sub>2

CH2 - PO3H2</sub>

｜
A−21 H ₂ O ₃ P−C−PO ₃ H ₂

｜
CH ₂ PO ₃ H ₂

【table】 /
N

A−29 ＼
｜ C ₄ H <sub>9


H2O3P -</sub> CH _{- PO3H2}

C ₈ H ₁₇

/
N

A−30 ＼
｜ C ₈ H <sub>17


H2O3P -</sub> CH <sub>- PO3H2

CH3</sub>

/
N

A−31 ＼
｜H


_{H2O3P -} CH _{- PO3H2}

C ₄ H ₉

/
N

A−32 ＼
｜H


_{H2O3P -} CH _{- PO3H2}

C ₆ H ₁₃

/
N

A−33 ＼
｜H


_{H2O3P -} CH _{- PO3H2}

【table】 /
N

\
｜ CH ₂ COOH


H ₂ O ₃ P−C−PO ₃ H ₂


A−40 |

_CH2


｜ CH ₂ COOH

/
N

\
_CH2 COOH

[Table] ｜
A−49 H ₂ N−C−CH ₂ PO ₃ H ₂

｜
PO ₃ H <sub>2

CH3</sub>

｜
A−50 HOOC−C−PO ₃ H ₂

｜
_CH2 COOH

C ₂ H ₅

｜
A−51 HOOC−C−PO ₃ H ₂

｜
_CH2 COOH

[Table] ｜
A−58 CH−COOH

｜
CH－COOH

｜
_CH3

HOOC−CH−PO ₃ H ₂

｜
_CH3 -C-COOH

A−59 ｜
CH－COOH

｜
_CH3

HOOC−CH−PO ₃ H ₂

｜
A−60 CH ₂

｜
HOOC−CH−PO ₃ H ₂

[Table] ｜
CH－COOH

｜
A−68 CH ₂

｜
HOOC−C−PO ₃ H ₂

｜
_CH2 COOH

_CH2 -COOH

｜
CH－COOH

A−69 ｜
HOOC−C−PO ₃ H ₂

｜
_CH2 COOH

HOOC−C−PO ₃ H ₂

A−70 ‖
CH－COOH

[Table] ｜
OH

【table】

[Table] ｜
_CH2 COOH

Specific compounds of general formulas [] to [XII] are as follows. B-1 Sodium citrate B-2 Oxalic acid B-3 Acetate B-4 Sodium propionate B-5 Potassium tartrate B-6 Sodium nitrilotriacetate B-7 Iminodiacetic acid B-8 Sodium hydroxyiminodiacetate B-9 Methylimino diacetate Potassium acetate B-10 Sodium ethyliminodiacetate B-11 Ethyliminodipropionic acid B-12 Propyliminodiacetic acid B-13 Ammonium ethylenediaminetetraacetate B-14 Sodium diethylenetriaminepentaacetate B-15 Propylenediaminetetraacetic acid B-16 Cyclohexanetetraacetic acid B-17 Glycol ether diamine tetraacetic acid B-18 1,3-diamino-2-propanol tetraacetic acid Specific compounds of the general formula [ ] are as follows. C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-11 C-12 C-13 C-14 The aromatic polyhydroxy compound used in the present invention can form a complex with the ferric ions in an alkaline solution in which the molar ratio of ferric ions to the compound is 1 to 3. Generally, the aromatic polyhydroxy compound comprises at least two ortho-1 positions relative to each other.
It is a compound that has hydroxyl groups on the aromatic ring. Preferably, these polyhydroxy compounds have at least two hydroxy groups located in the ortho-1 position relative to each other on the aromatic carbocycle and do not possess exocyclic unsaturation. Among the wide range of aromatic polyhydroxy compounds useful in the present invention are, for example, benzene and naphthalene compounds, i.e., the general formula []
Includes compounds that can be represented by. General formula [] In the above formula, T represents an atomic group necessary to complete the aromatic ring structure of benzene or naphthalene. The aromatic ring structure may be substituted by groups or atoms such as sulfo groups, carboxy groups or halogen atoms in addition to hydroxy substituents. Common examples of aromatic polyhydroxy compounds useful in the present invention include compounds such as those described below. D-1 Pyrocatechol D-2 4,5-dihydroxy-m-benzenedisulfonic acid D-3 4,5-dihydroxy-m-benzenedisulfonic acid disodium salt D-4 Tetrapromopyrocatechol D-5 Pyrogallol D- 6 Gallic 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-11 1,2-dihydroxybenzene-3,5
-Sodium disulfonate Compounds of general formulas [] to [] are German patented
No. 2252684, U.S. Patent No. 3400148 and Journal of Organic Chemistry Volume 38, 1867-
It is synthesized by a general synthesis method such as that described on page 1869 (1973). The general formula [] is also used in U.S. Patent No. 3,632,637, Journal of the American Chemical Society, Vol. 89 (1967), page 837, and JP-A-58
It is synthesized by a general synthesis method such as that described in No.-195845. The compounds of general formulas [] to [XII] and general formula [] can be easily synthesized by well-known synthesis methods. Organic phosphonic acids, organic carboxylic acids, and polyhydroxy compounds used as chelating agents in the present invention (hereinafter referred to as chelating agents of the present invention).
The amount added to the color developing solution varies depending on the effect and the molecular weight of the chelating agent, but generally speaking, the amount added to the color developing solution 1
Can be used in the range of 0.001 to 20g per serving, preferably
Range of 0.005-15g, more preferably 0.01-10g
Good results can be obtained by adding Furthermore, in carrying out the present invention, it is sufficient to contain at least one type of the above-mentioned chelating agent of the present invention, and it is also possible to use a combination of two or more types of chelating agents of the present invention if desired. 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 content of hydroxylamine or its salts per color developer is
Good results can be obtained up to 0.2 g, preferably up to 0.1 g. The hydroxylamine according to the present invention refers to an amine in which a nitrogen atom is directly bonded to a hydroxyl group, such as an amine containing an N-OH hydroxylamine group, and is usually used in the form of a water-soluble acid salt.
Examples of such salts are sulfates, oxalates,
These include chloride, phosphate, carbonate, and acetate.
Furthermore, hydroxylamine can be in 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 [ ]. General formula [] However, in the formula, M ₂ is a hydrogen atom or a carbon number of 1 to 3
represents an alkyl group. There are also water-soluble acid salts thereof. Additives used in the color developer of the present invention include preservatives such as sulfites, sodium hydroxide,
Accelerators consisting of alkalis such as sodium carbonate and potassium carbonate, inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole and methylbenzthiazole, and surface supernatants consisting of trace amounts of iodides and mercapto compounds. Examples include development inhibitors. Aromatic primary compound used in the color developer of the present invention
Class amine color developing agents include those known and widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. In the present invention, p-phenylenediamine represented by the following general formula [] is particularly preferably used. General formula [] In the formula, R ₂₅ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may have a substituent, and R ₂₆ and R ₂₇ represent a hydrogen atom or an alkyl group which may have a substituent, represents an aryl group or an aralkyl group, and at least one of R ₂₆ and R ₂₇ is a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an amino acid group,
It is an alkyl group having a water-soluble substituent such as a sulfonamide group or (-(-CH ₂ ) _a --O) _b --R ₂₈ . Note that R ₂₈ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a and b represent integers of 1 to 5. ) Next, typical examples of the compound represented by the general formula [] will be listed, but the invention is not limited thereto. E-1 E-2 E-3 E-4 E-5 E-6 E-7 E-8 E-9 E-10 E-11 E-12 E-13 E-14 E-15 E-16 These p-phenylenediamine derivatives represented by the general formula [ ] can be used as salts of organic acids and inorganic acids, such as hydrochloride, sulfate, phosphate, p-toluenesulfonate, sulfite, and Acid salts, benzenedisulfonic acid salts, etc. can be used. Among the compounds represented by the general formula [], R ₂₆ and/or R ₂₇ are (-(-CH ₂ ) _a --O) _b --R ₂₈
(a,
b and R ₂₈ have the same meanings as above), the objects and effects of the present invention are particularly well achieved. In addition, these compounds are generally used at a concentration of about 0.1 g to about 30 g per color developer,
More preferably, about 1 g per color developer 1
Use at a concentration of ~15g. 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, potassium carbonate, etc. It can also optionally contain alkaline agents, alkali metal sulfites, alkali metal bisulfites, 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. Bleaching agents used in the bleaching or bleach-fixing solution that follows the color developing solution include:
A variety of materials can be used, but 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 aminopolycarboxylic acid 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. Ethylenediaminetetraacetic acid Ethylenediamine-N-(β-oxyethyl) -N,N',N'-triacetic acid Propylenediaminetetraacetic acid Nitrilotriacetic acid Cyclohexanediaminetetraacetic acid Iminodiacetic acid Dihydroxyethylglycine Ethyl etherdiaminetetraacetic acid Glycol etherdiaminetetraacetic acid Ethylenediaminetetraacetic acid Propionic acid Phenylenediaminetetraacetic acid Ethylenediaminetetraacetic acid disodium salt Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt Ethylenediaminetetraacetic acid tetrasodium salt Diethylenetriaminepentaacetic acid pentasodium salt Ethylenediamine-N-(β-oxyethyl) -N, N', N '-Triacetic acid sodium salt Propylene diamine tetraacetic acid sodium salt The bleach-fix solution contains a metal complex salt of an organic acid (e.g. iron complex salt) as a bleaching agent, as well as thiosulfate, thiocyanate, thioureas, etc. A solution having a composition containing a silver halide fixing agent of 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. In addition to potassium bromide, the halogen compounds include hydrochloric acid, hydrobromic acid,
Lithium bromide, sodium bromide, ammonium bromide, potassium iodide, ammonium iodide, and the like can also be used. The silver halide fixing agent to be included in the bleach-fixing solution is a compound that reacts with silver halide to form a water-soluble complex salt, such as those used in normal fixing processing.
For example, potassium thiosulfate, sodium thiosulfate,
Thiosulfates such as ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, or thioureas, thioether-rich bromides,
Iodide is a typical example. In addition, the bleaching solution or bleach-fixing solution contains boric acid, borax,
PH buffers consisting of various salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc.
Alternatively, two or more kinds can be contained in combination. Furthermore, various antifoaming agents or surfactants can also be contained. In addition, the preservation properties of hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, or a type of stabilizer such as nitroalcohol nitrate, methanol, dimethyl-formamide, dimethyl An organic solvent such as sulfoxide can be appropriately contained. These color development and processing with a processing solution having bleaching ability must be carried out continuously, and the processing solution having bleaching ability specifically refers to a bleaching solution and a bleach-fixing solution. Further, prior to color development, black and white development, fixing treatment, etc. can also be performed. The color developing solution, bleaching solution and bleach-fixing solution having bleaching ability of the present invention can be used for color papers, color negative films, color positive films, color reversal films for slides, color reversal films for movies, TVs, etc.
It can be applied to silver halide color photographic materials such as color reversal film and color reversal paper. (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 material was prepared by sequentially coating the following layers on polyethylene resin coated paper. The amount added is expressed per 100 cm ² unless otherwise specified. (Layer-1) A layer containing 15 mg of gelatin. (Layer-2) 20 mg gelatin, 4.5 mg blue-sensitive silver chlorobromide emulsion, and 9 mg 2-(1-benzyl-2,4-dioxyimidazolidin-3-yl)-2-pivalyl-2'-Chloro-5'-[4-
(2,4-di-tertiary amylphenoxy)
butanamide]acetanilide, 0.5 mg 5,
A layer containing 3.5 mg di-n-butyl phthalate high boiling solvent in which 5-dimethyl-1,3-cyclohexanedione and 0.15 mg 2,5-di-tertiary octylhydroquinone were dissolved. (Layer-3) 10 mg gelatin, 0.45 mg 2,5-
A layer containing tertiary octylhydroquinone. (Layer-4) 15 mg of gelatin, 4.5 mg of green-sensitive silver chlorobromide emulsion, and 5.5 mg of 3-[2-chloro-
5-(1-octadecylsuccinimido)anilino]-1-(2,4,6-trichlorophenyl)-pyrazolone and 0.10 mg of 2,5-di-
Dissolved tertiary octyl hydroquinone
Layer containing 2.0 mg of tricresyl phosphate high boiling solvent. (Layer-5) 15 mg gelatin, 0.8 mg 2,5-
tertiary octylhydroquinone and 5
A layer containing 4 mg of dioctyl phthalate in which mg of ultraviolet absorber UV-1 is dissolved. (Layer-6) 15 mg of gelatin, 3.5 mg of red-sensitive silver chlorobromide emulsion, 3.8 mg of 2-[2-(2,4-di-
a layer containing 2.0 mg of dioctyl phthalate in which tertiary amylphenoxy)butyramide]-4,6-dichloro-5-methylphenol and 0.15 mg of 2,5-di-tertiary octylhydroquinone were dissolved. (Layer-7) 10 mg gelatin and 0.3 mg 2,
2.0 in which 5-tertiary octylhydroquinone and 2 mg of the following ultraviolet absorber UV-1 were dissolved.
layer containing mg of dioctyl phthalate. (UV-1) In addition, 2,4-dichloro-6-hydroxy-S-triazine sodium was used as a hardening agent in layers 1, 3,
0.16mg per 1g of gelatin in 5, 7- each
A photosensitive material was prepared by adding the material so as to give the following properties, and it was stored at 40°C and a relative humidity of 80% for 48 hours to harden the material and prepare a sample (A). In addition, the following samples (B) to (D) were also prepared at the same time as sample (A). Sample (B) Sample where Exemplified Compound-4 was added to Layer-1 (C) Sample where Exemplified Compound-15 was added to Layer-1 (D) Sample where Exemplified Compound-48 was added to Layer-1 Obtained After exposing the sample through an optical wedge,
The treatment was performed according to the following treatment steps. Standard processing process Standard processing temperature Processing time Color development 38℃ 2 minutes
Bleach fixing 38℃ 1 minute
Washing with water 30-35℃ 3 minutes
Drying: 75-80°C for about 2 minutes The composition of the treatment solution is as follows. [Color developer] Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 1.2g Sodium chloride 0.2g Potassium carbonate 30.0g 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl) Aniline sulfate 5.5g Fluorescent brightener (4,4-diaminostilbendisulfonic acid derivative 1.0g Potassium hydroxide 2.0g Add water to make 1. [Bleach-fix solution] Ethylenediaminetetraacetic acid () sodium trihydrate 70g Ethylenediaminetetraacetic acid 15g Ammonium sulfite (40% solution) 20ml Ammonium thiosulfate (70% solution) 140ml Silver powder 3.0g Color developer 400ml Adjust the pH to 7.5 with aqueous ammonia, and add water to bring the total volume to 1. Standards The color developing solution was divided into portions, and 0.1 g of a chelating agent and 2.0 g of hydroxylamine sulfate were added per color developing solution as shown in Table (1), and the pH was adjusted to 10.20.
After that, some of the color developing solution was stored in a refrigerator, and the other part was stored at 40℃ for two weeks, and then adjusted to pH 10.2 again and processed using a piece processing machine (hereinafter referred to as hand) according to the processing steps. The color turbidity and maximum density were measured. However, the degree of color turbidity is different from yellow image to blue image.
Let the reflection density obtained with green monochromatic light be DB, DG,
Obtained as DG/DB. Furthermore, for the highest density, the blue reflection density was determined. In addition, DG/DB= of sample (A) subjected to standard processing using Sakura Color Paper Processing CPK-18.
0.12, and the highest concentration was 2.60.

【table】

[Table] Use of aluminum The samples were prepared and evaluated by hand processing in the same manner as in Example (1). The results are shown in Table-(2).

[Table] As is clear from Table-(2), as the PH increases, a marked increase in color turbidity is seen in the treatments other than those of the present invention, especially at PH10.50, whereas the treatments of the present invention ) As is clear from the above, the processing other than the present invention cannot satisfy both the color cloudiness and the developability of the blue-sensitive layer on the same day and after two weeks of storage, whereas the process of the present invention can solve the above color cloudiness and developability. This fully satisfies both of the following. That is, when a light-sensitive material other than the one according to the present invention is used, there is almost no color turbidity on the same day or after two weeks of storage, but the developability is considerably poor. Furthermore, although the developability of the blue-sensitive layer was good when the sample was processed with hydroxylamine sulfate using the photosensitive material of the present invention, color turbidity was observed, and in particular, color turbidity significantly increased after two weeks of storage. ing. 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 In the standard color developer used in Example 1, 2.0 g of hydroxylamine sulfate per color developer,
When using 0.1g of sodium 1,2-dihydroxybenzene-3,5-disulfonate, as shown in Table (2), there was no tendency to change the pH, and even at high pH, there was almost no increase in color turbidity, and there was no difference between the standard treatment and the standard treatment. Almost the same. Regarding the developability, although the developability of Process Nos. 9 to 11 using sample (A) outside the present invention improved as the pH increased, it was considerably inferior to the sample according to the present invention. Therefore, it can be seen that only when sample (B) and the processing method of the present invention were used, there was less color clouding and good developability even when the pH increased. Example 3 Evaluation was carried out in the same manner as in Example 1, except that Cu ions were added to the color developing solution as shown in Table (3) and Sample B used in Example 2 was changed to Sample D.

[Table] As is clear from Table (3), with regard to Cu ions, when the amount of Cu ions mixed in is relatively small, the color turbidity increases by about 3 ppm. There is a noticeable increase in color turbidity. On the other hand, the treatment of the present invention had almost the same level of color turbidity as the comparison due to the incorporation of Cu ions, and the results were almost the same as the standard treatment. Furthermore, the developability was also evaluated, and 1 ppm of Cu ions was almost the same as no additive. 3ppm
Although a slight increase in developability was observed, the same tendency as in Examples 1 and 2 was observed. Example 4 Cu ions in the standard color developing solution were adjusted to 3 ppm,
Hydroxylamine sulfate 2.0g chelating agent listed
After adding as in (4) and measuring the highest reflective blue density,
Color turbidity was evaluated in the same manner as in Example 1, except that the storage period (40° C.) was changed to 7 days.

【table】

【table】 ‖ ‖
‖
OO
O
As is clear from Table (4), when the samples according to the present invention are subjected to color development treatment in the presence of a chelating agent and hydroxylamine sulfate, color turbidity increases regardless of the type of chelating agent. There is. Furthermore, when processing with a color developing solution containing a chelating agent other than the present invention and in which hydroxylamine is not present, it was hardly possible to prevent color turbidity. Although only the treatment method had slightly more color turbidity than the standard treatment, it showed the same degree of color turbidity as Comparison Nos. 33 to 38, and good results were obtained.

Claims (1)

[Scope of Claims] 1. After imagewise exposure of a silver halide color photographic light-sensitive material containing at least one compound represented by the following general formula [], organic phosphonic acid, the following general formula [], [XI], A color developing solution containing at least one selected from an organic carboxylic acid represented by [XII] or [] and a polyhydroxy compound represented by the following general formula [], and substantially free of hydroxylamine or a salt thereof. 1. A method for processing a silver halide color photographic light-sensitive material, which comprises processing with a processing solution having bleaching ability. General formula [] [In the formula, R ₁ represents a hydrogen atom or an acetyl group,
R represents an aryl group, R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom, an alkyl group or an aryl group, and R ₂ , R ₃ , R ₄ and R ₅ may be the same or different; Also good. ] General formula [ ] R ₂₂ −COOM ₁ [In the formula, R ₂₂ represents an aliphatic group, and M ₁ represents a hydrogen atom or a cation such as sodium, potassium, or lithium. ] General formula [XI] M ₁ OCO− (A ₁ ) _n −M− (A ₂ ) _o −COOM ₁ General formula [XII] [In the formula, A ₁ to _{A 6} each represent a hydrocarbon group,
M is a hydrocarbon group, or a hydrocarbon group containing a thioether group or an ether group, or (B ₁ and B ₂ represent a hydrocarbon group, and A ₇ represents a hydrocarbon group.) m and n are each integers of 0 to 2, and M ₁ has the same meaning as in the general formula []. ] General formula [ ] [In the formula, R ₂₃ and R ₂₄ are each a hydrogen atom, a phosphoric acid group, a carboxylic acid group, -CH ₂ COOH, -CH ₂ PO ₃ H ₂
or a salt thereof, X is a hydroxyl group or a salt thereof, W, Z and Y are each a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group which may have a substituent, a cyano group, a carboxylic acid group, a phosphoric acid group , an alkoxy group, a sulfonic acid group, or a salt thereof. Also, m is 0 or 1, n is an integer from 1 to 4, l
represents 1 or 2, p represents an integer of 0 to 3, and q represents an integer of 0 to 2. Note that R ₂₃ and R ₂₄ do not contain a hydrogen atom at the same time, but one of them contains a carboxylic acid group. ] General formula [] [In the formula, T represents an atomic group necessary to complete the aromatic ring structure of benzene or naphthalene. ]