JP2003215766A - Color developing liquid, concentrated composition and treatment method for silver halide color photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color developing liquid, a concentrated composition and a treatment method for a photosensitive material by which precipitation of crystals or contamination by tar is not caused in a treatment tank or racks even when a fast treatment or a treatment with a small replenishing amount is carried out, and to provide a concentrated composition which does not cause low temperature precipitation even when the color developing agent is dissolved in a high concentration. <P>SOLUTION: The color developer liquid for a silver halide color photographic sensitive material contains at least one kind selected from the compounds expressed by general formula 1: X-R-SO<SB>3</SB>M. In the formula, X represents hydroxyl group, halogen group, an alkoxy group which may be substituted, sulfo group or sulfonate group, sulfuric acid ester or sulfate, or sulfonyl halide, R represents a 1-5C straight or branched alkylene group, and M represents Li, Na, K or NH<SB>4</SB>. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color developing solution for silver halide color photographic light-sensitive materials (hereinafter also referred to as light-sensitive materials or light-sensitive materials), a concentrated composition, and a processing method. Specifically, even if rapid processing or low replenishment is performed, there is no precipitation even if a color developing solution for a light-sensitive material capable of suppressing crystal precipitation and tar contamination in a processing tank or rack and a color developing agent at a high concentration are dissolved. The present invention relates to a concentrated composition for a photosensitive material and a processing method.

[0002]

Generally, in order to form a color photographic image by processing a light-sensitive material, the light-sensitive material is exposed imagewise and developed with a color developer containing a paraphenylenediamine type color developing agent. At this time, the silver halide is reduced to silver and at the same time, the developing agent is oxidized, and the resulting oxide is combined with the coupler in the light-sensitive material to form an image-like dye corresponding to the developed silver. It

In a color developing solution, a development-inhibiting substance eluted from the light-sensitive material is accumulated by developing the light-sensitive material, while the color-developing agent is consumed and the concentration of the component is lowered. Therefore, in a development processing method in which a large amount of a light-sensitive material is continuously processed by an automatic developing machine or the like, in order to avoid a change in development finish characteristics due to a change in component concentration, it is necessary to keep the components of the color developing solution within a certain concentration range. Means are needed.

[0004] As such means, usually, the deficient component is supplemented,
A method of replenishing a replenisher for diluting unnecessary increasing components is adopted.

As described above, the color developing solution contains a color developing agent and reacts with the coupler in the light-sensitive material to form a dye. However, the color developing agent is easily oxidized by oxygen in the air. Usually, an antioxidant called a preservative is added to the color developing solution. Hydroxylamine salts have long been known as preservatives for color developing solutions. JP-A-1-298351 describes mono- or di-substituted hydroxylamine derivatives, and some of these compounds have already been put into practical use.

In recent years, there has been an increasing demand for shortening the processing time and reducing the replenishment amount for the purpose of environmental protection. To achieve these, it is necessary to add a color developing agent in a high concentration or raise the processing temperature. It is needed. However,
If the color developing agent is dissolved in a high concentration or the processing temperature is set to a high value, precipitation of crystals or tar-like deposits may occur at the processing liquid interface on the wall of the processing tank or the processing liquid interface on the rack that serves as a passage for the photosensitive material. However, the problem occurs that the photosensitive material is contaminated or damaged.

On the other hand, in order to supplement the components consumed by the processing of the light-sensitive material, as described above, the replenisher is supplemented to the processing tank according to the processing area of the light-sensitive material. The replenisher is usually commercialized as a concentrated composition from the viewpoint of physical distribution, and is generally referred to as a kit or a concentrate kit, which is prepared by the user by adding a predetermined amount of water before use. In particular, the color developing solution concentrate kit (concentrated composition) has been supplied in a plurality of parts in which the easily reacting components are separated so that the reaction between the components can be suppressed and the components can be stored for a long period of time. The color developing agent is usually dissolved in a low pH part from the viewpoint of storage stability. However, attempts have been made to reduce the number of parts in order to prevent user mispreparation and to reduce dissolution work, and a single-part color developing solution concentrate kit has also been released.

In the case of a single part concentrate kit, the color developing agent will also be dissolved in the high pH solution. In particular, in order to achieve low replenishment, both the pH of the replenisher and the concentration of the color developing agent need to be set higher, and the kit must inevitably have a higher pH and higher concentration. However, in the high-pH concentrate solution kit in which the color developing agent is dissolved in a high concentration, crystals tend to precipitate during low temperature storage, so that the concentration rate cannot be increased and the kit capacity becomes large.

[0009]

SUMMARY OF THE INVENTION The first object of the present invention is to:
To provide a color developing solution and a concentrated composition for a light-sensitive material and a processing method in which crystal precipitation and tar contamination do not occur in a processing tank or a rack even if rapid processing and low replenishment are performed. It is an object of the present invention to provide a concentrated liquid kit (concentrated composition) that does not cause low-temperature precipitation even when a color developing agent is dissolved.

[0010]

The object of the present invention is achieved by the following constitution. 1. A color developing solution for a silver halide color photographic light-sensitive material, which contains at least one selected from compounds represented by the following general formula 1.

General Formula 1 X—R—SO ₃ M In the formula, X is a hydroxyl group, a halogen group, an optionally substituted alkoxy group, a sulfo group or a sulfonate,
It represents a sulfuric acid ester, a sulfuric acid ester salt, or a sulfonyl halide. R represents a linear or branched alkylene group having 1 to 5 carbon atoms, and M represents Li, Na, K or NH ₄ .

2. 2. The color developing solution for a silver halide color photographic light-sensitive material as described in 1 above, which contains at least one selected from compounds represented by the following general formula 2.

[0013]

[Chemical 2]

In the formula, A represents a hydrogen atom or an optionally substituted alkyl group, B represents an optionally substituted alkylene group, and Y represents a carboxyl group, a sulfo group, a phosphono group, a hydroxyl group or an alkoxy group. Represents a group, an amino group, an ammonio group, a sulfamoyl group or an alkylsulfonyl group. These may be in salt form.

3. 2 × the compound represented by the general formula 1
The color developer for silver halide color photographic light-sensitive materials as described in 1 or 2 above, which contains 10 ⁻⁵ mol / L or more and 2 × 10 ⁻² mol / L or less.

4. 4. A color developing solution for silver halide color photographic light-sensitive materials as described in any one of 1 to 3 above, which contains at least one selected from compounds represented by the following general formula 3.

General formula 3 HO- (W-O) n-H In the formula, W is -CH_TwoCH_Two-, -CH_TwoCH_TwoCH
_Two-, -CH_TwoCH (CH _Three)-, Where n is 1 to 30
Represents the integer.

5. The compound represented by the above general formula 3 is 10
5. The color developing solution for a silver halide color photographic light-sensitive material as described in 4 above, which contains g / L or more and 100 g / L or less.

6. A color-developing concentrated composition for silver halide color photographic light-sensitive materials, comprising at least one selected from the compounds represented by the general formula 1.

7. 7. The color-developing concentrated composition for silver halide color photographic light-sensitive material as described in 6 above, which contains at least one selected from the compounds represented by the general formula 2.

8. Containing at least one selected from the compounds represented by the general formula 1 and at least one compound represented by the general formula 2, and containing a para-phenylenediamine color developing agent in the same part. A characteristic color development concentrate composition for a silver halide color photographic light-sensitive material.

9. 1 × the compound represented by the general formula 1
10. The color developing concentrated composition for silver halide color photographic light-sensitive materials as described in any of 6 to 8 above, which contains 10 ⁻⁴ mol / L or more and 1 × 10 ⁻¹ mol / L or less.

10. 10. The color-developing concentrated composition for silver halide color photographic light-sensitive materials as described in any one of 6 to 9 above, which contains at least one compound represented by the general formula 3.

11. The compound represented by the general formula 3 is 5
11. The color-developing concentrated composition for silver halide color photographic light-sensitive materials as described in 10 above, which contains 0 g / L or more and 700 g / L or less.

12. PH of the above concentrated composition is 11 or more 1
4. The color developing concentrated composition for silver halide color photographic light-sensitive materials as described in any one of 6 to 11 above, which is 4 or less.

13. A processing method for developing a silver halide color photographic light-sensitive material using the color developer according to any one of 1 to 5 above, wherein the replenishing amount of the color developer is 20 ml or more and 100 ml or less per 1 m ^{2 of the} light-sensitive material. And a method for processing a silver halide color photographic light-sensitive material.

Hereinafter, in the present specification, "color developing solution"
May be used as containing a color developing solution as a processing solution, a color developing replenishing solution and a color developing concentrated composition as a concentrate.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below.
Examples of the compound represented by the general formula 1 are listed, but the present invention is not limited thereto.

[Exemplified Compounds] 1-1 HO-CH ₂ CH ₂ -SO ₃ H 1-2 HO-CH ₂ CH ₂ -SO ₃ Na 1-3 HO-CH ₂ CH ₂ -SO ₃ K 1-4 HO _{-CH (CH 3) CH 2 -SO} 3 Na 1-5 HO-CH 2 CH (CH 3) -SO 3 Na 1-6 HO-CH 2 CH 2 CH 2 -SO 3 Na 1-7 HO-CH 2 _{CH (C 2 H 5) -SO} 3 Na 1-8 HO 3 SO-CH 2 CH 2 -SO 3 H 1-9 NaO 3 SO-CH 2 CH 2 -SO 3 Na 1-10 KO 3 SO-CH 2 _{CH 2 -SO 3 K 1-11 HO 3} S-CH 2 CH 2 -SO 3 H 1-12 NaO 3 S-CH 2 CH 2 -SO 3 Na 1-13 Cl-CH 2 -SO 3 H 1-14 _{Br-CH 2 CH 2 -SO 3} Na 1-15 Br-CH (CH 3) CH 2 SO 3 Na 1-16 ClO 2 _{-CH 2 CH 2 SO 3 H 1-17} NaO 3 S-CH 2 CH 2 -O-CH 2 CH 2 S
O ₃ Na

[0030]

[Chemical 3]

The color developer of the present invention is represented by the above general formula 1.
2 x 10 compounds^-5Mol / L or more 2 × 10^-2
It is preferable that the content is not more than mol / L. In addition, according to the present invention
The color-development concentrate contains the compound represented by the general formula 1
× 10 ^-4Mol / L or more 1 × 10^-1Contains less than mol / L
Preferably.

Next, examples of the compound represented by the general formula 2 will be shown, but the present invention is not limited thereto.

[0033]

[Chemical 4]

[0034]

[Chemical 5]

[0035]

[Chemical 6]

[0036]

[Chemical 7]

The color developer of the present invention is represented by the above general formula 2.
1 x 10 compounds^-3Mol / L or more 1 × 10^-1
Contains less than mol / L, especially 5 × 10^-3Mol / L or more
5 x 10^-2It is preferable that the content is not more than mol / L. Well
Further, the color developing concentrate of the present invention is represented by the above general formula 2.
1 x 10 compounds ^-2Includes mol / L or more and 5 mol / L or less
Having, in particular 5 × 10^-2Mol / L or more and 1 mol / L or less
It is preferable to contain.

Specific examples of the compound represented by the general formula 3 will be given below, but the present invention is not limited thereto.

Ethylene glycol diethylene glycol triethylene glycol tetraethylene glycol propylene glycol dipropylene glycol tripropylene glycol polyethylene glycol # 200 (average molecular weight 200) polyethylene glycol # 300 (average molecular weight 300) polyethylene glycol # 400 (average molecular weight 400) polyethylene glycol # 600 (average molecular weight 600) Polyethylene glycol # 1000 (average molecular weight 100
0) Polypropylene glycol (average molecular weight 400) Polypropylene glycol (average molecular weight 700)

The color developer of the present invention preferably contains the compound represented by the above general formula 3 in an amount of 10 g / L or more and 100 g / L or less. Further, the color developing concentrate of the present invention is
The compound represented by the above general formula 3 is 50 g / L or more and 700
It is preferable to contain g / L or less.

Next, the color developing agent will be described. Book
As the color developing agent used in the color developing solution of the invention,
A p-phenylenediamine compound having a water-soluble group
It is preferable from the viewpoint of obtaining the effect of the invention. Has a water-soluble group
The p-phenylenediamine compound is N, N-diethyl
P- which does not have a water-soluble group such as p-phenylenediamine
Compared to phenylenediamine compounds
It has the advantage that it does not cause skin rash. Previous
The water-soluble group is an amine of a p-phenylenediamine compound.
Having at least one on a benzene group or benzene nucleus
Specific examples of the water-soluble group include-(CH_Two) N
-CH_TwoOH,-(CH_Two) M-NHSO_Two-(C
H_Two) N-CH_Three,-(CH _Two) M-O- (CH_Two) N
-CH_Three,-(CH_TwoCH_TwoO) nCmH_Twom₁(M and
And n each represent an integer of 0 or more. ), -COOH
Group, -SO_ThreeH groups and the like are mentioned as preferable ones.

Specific examples of the color developing agent preferably used in the present invention are shown below.

[0043]

[Chemical 8]

[0044]

[Chemical 9]

[0045]

[Chemical 10]

The above color developing agent may be usually used in the form of a salt such as hydrochloride, sulfate or p-toluenesulfonate. Normal color developing solution 2 × 10 ⁻³ per liter
Although it is preferable to use it in the range of 2 × 10 ⁻¹ mol,
From the viewpoint of the effect of the present invention, 2 × per liter of color developing solution
The range of 10 ⁻² to 4 × 10 ⁻² mol is more preferable.

Next, a compound which is more remarkable in the effects of the present invention when added to the color developing solution of the present invention will be described. In the color developing solution of the present invention, it is preferable to use a triazyl stilbene-based optical brightening agent from the viewpoint of preventing tar from occurring, and the triazyl stilbene-based optical brightening agent is represented by the following general formula [A]. The compounds shown are preferably used.

[0048]

[Chemical 11]

Where X ₁₁ , X ₁₂ , Y 11 and Y ₁₂
Is a hydroxyl group, a halogen atom such as chlorine or bromine, a morpholino group, an alkoxy group (eg, methoxy, ethoxy, methoxyethoxy, etc.), an aryloxy group (eg, phenoxy, p-sulfophenoxy, etc.), an alkyl group (eg, methyl, ethyl, etc.). ), Aryl groups (eg, phenyl, methoxyphenyl, etc.), amino groups, alkylamino groups (eg, methylamino, ethylamino, propylamino, dimethylamino, cyclohexylamino, β-hydroxyethylamino, di (β-hydroxyethyl) amino) , Β-sulfoethylamino, N- (β-sulfoethyl) -N-methylamino, N- (β-hydroxyethyl) -N-methylamino, etc.), an arylamino group (eg, anilino, o-, m-, p-). Sulfoanilino, o-, m
-, P-chloroanilino, o-, m-, p-toluidino, o-, m-, p-carboxyanilino, o-, m
-, P-hydroxyanilino, sulfonaphthylamino,
o-, m-, p-aminoanilino, o-, m-, p-anidino, etc.). M represents a hydrogen atom, sodium, potassium, ammonium or lithium.

The following compounds can be specifically mentioned, but the compounds are not limited to these.

[0051]

[Chemical 12]

[0052]

[Chemical 13]

The above-mentioned triazyl stilbene whitening agent is
For example, it can be synthesized by the usual method described on page 8 of "Fluorescent brightening agent" (published in August, 1976) edited by Chemical Industry Association. The triazyl stilbene-based whitening agent according to the present invention may be either cis or trans type, but trans type is particularly preferable in the present invention.

These triazyl stilbene whitening agents are
The color developing solution of the present invention is preferably used in an amount of 0.2 to 20 g, particularly preferably 0.4 to 10 g, per liter.
Is the range.

By containing a chelating agent in the color developing solution of the present invention, deterioration of the color developing solution mainly due to contamination of heavy metal ions is prevented, and preservability is improved. In particular, the chelating agents of [E] to [H] in the following general formulas [B] to [H] are preferably used in the sense that precipitation formation with Ca or Mg in the color developing solution is difficult.

[0056]

[Chemical 14]

In the formula, E is an alkylene group, a cycloalkylene group, a phenylene group, --B ₅ --O--B _5- , --B ₅ --O
-B _{5 -O-B 5} - or _{-B 5 -Z-B} 5 - represents a. Z
Is

[0058]

[Chemical 15]

Represents B₁, B_Two, B_Three, B_Four, B₅Over
And B₆Each represents an alkylene group. A ₁′, A_Two'as well as
A_Three'Is -COOM' or -PO_Three(M ')_TwoRepresents
A_Four'And A₅′ Is a hydrogen atom, hydroxyl group, —COO
M'or -PO_Three(M ')_TwoRepresents M'is a hydrogen atom or
Represents an alkali metal atom.

[0060]

[Chemical 16]

In the formula, B ₇ represents an alkyl group, an aryl group or a nitrogen-containing 6-membered ring group. M'represents a hydrogen atom or an alkali metal atom.

[0062]

[Chemical 17]

Where B₈, B₉And B₁₀Is hydrogen source
Child, hydroxyl group, -COOM ', -PO _Three(M ')_TwoOr a
Represents a rualkyl group, L₁, L_TwoAnd L_ThreeAre hydrogen atoms,
Hydroxyl group, -COOM ', -PO_Three(M ')_TwoOr -N
(J)_TwoRepresents J is a hydrogen atom, an alkyl group, -C_TwoH
_FourOH or -PO_Three(M ')_TwoRepresents M'is a hydrogen atom
Or represents an alkali metal atom, and n and m are 0 or 1 respectively.
Represents

[0064]

[Chemical 18]

Wherein R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈
Is a hydrogen atom, a halogen atom, a sulfo group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, or -O.
R ₁₉ , -COOR ₂₀ , -CON (R ₂₁ )
(R ₂₂ ) or a substituted or unsubstituted phenyl group. R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. n is 1
Represents an integer of 3. R ₁₅ may be the same or different.

[0066]

[Chemical 19]

In the formula, R ₂₃ and R ₂₄ are each a hydrogen atom,
Represents a halogen atom or a sulfo group.

[0068]

[Chemical 20]

In the formula, R ₂₉ and R ₃₀ are each a hydrogen atom,
Phosphoric acid group, a carboxylic acid _group, -CH 2 COOH, -CH ₂
PO ₃ H ₂ or a salt thereof, X ₃ represents a hydroxyl group or a salt thereof, W ₁ , Z ₁ and Y ₁ are each a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a carboxylic acid group, a phosphoric acid group, It represents a sulfo group, or a salt thereof, an alkoxy group, or an alkyl group. Further, m ₃ is 0 or 1, and n ₃ is 1 to 4
, ₁ is 1 or 2, p ₂ is an integer of 0 to 3, and q ₁ is an integer of 0 to 2.

Some specific examples of the chelating agent represented by the general formula [B], [C] or [D] are shown below. The chelating agent used in the present invention is not limited to the following specific examples.

[0071]

[Chemical 21]

[0072]

[Chemical formula 22]

[0073]

[Chemical formula 23]

[0074]

[Chemical formula 24]

The chelating agents represented by the above general formulas [B] to [D] are used per 1 liter of the color developing solution of the present invention.
It is preferably used in an amount of 0.01 to 100 g, more preferably 0.05 to 50 g, and particularly preferably 0.1.
~ 20g.

Specific examples of the chelating agent represented by the above general formulas [E] to [H] include the following.

[0077]

[Chemical 25]

[0078]

[Chemical formula 26]

[0079]

[Chemical 27]

Among the chelating agents represented by the general formulas [E] to [H], it is more effective to use the chelating agents represented by the general formulas [E] and [H], more preferably the general formulas That is, the chelating agent represented by [H] is used.
These chelating agents can be used in combination of two or more kinds.

The above-mentioned general formula [E] used in the present invention:
The chelating agent represented by any one of [H] is the color developer 1
It is preferable to add it in the range of 1 × 10 ⁻⁴ mol to 1 mol per liter, and more preferably 2 × 10 ⁻⁴ to 1 ×.
It can be added in the range of 10 ⁻¹ mol, and more preferably in the range of 5 × 10 ^{−4 to} 5 × 10 ⁻² mol.

In the present invention, by using the compounds represented by the general formulas [B] to [H] in combination, the effect of the object of the present invention is improved. For example, the number of days of precipitation of the crystal in Example 1 is improved by about 20%.

The color developer of the present invention may contain the following developer components in addition to the above components.

As the alkaline agent, for example, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, silicate, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, boric acid, etc. may be used alone. Alternatively, they can be used in combination. Further, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, borate are used for the necessity of preparation or for the purpose of increasing ionic strength. be able to. Inorganic and organic antifoggants can be added as required.

Furthermore, if necessary, a development accelerator can be used. As the development accelerator, various pyridinium compounds represented by US Pat. Nos. 2,648,604, 3,671,247 and JP-B-44-9503, other cationic compounds, and phenosafuran are used. Such as cationic dyes, neutral salts such as thallium nitrate, US Pat. Nos. 2,533,990 and 2,53
1,832, 2,950,970, 2,57
7, 127 and Japanese Patent Publication No. 44-9504, polyethylene glycol and its derivatives, nonionic compounds such as polythioethers, and organic solvents described in Japanese Patent Publication No. 44-9509. US Pat. No. 2,30
Examples thereof include benzyl alcohol, phenethyl alcohol and acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine and amines described in No. 4,925.

However, since the color developing solution of the present invention can impart good developing performance without benzyl alcohol harmful to humans, it is preferable not to contain benzyl alcohol.

Further, an auxiliary developing agent may be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminophenolhexalphate (methol), phenidone, N, N'-diethyl-p-.
Aminophenol hydrochloride, N, N, N ', N'-tetramethyl-p-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually preferably 0.01 g to 10 g / l. In addition to these, competing couplers, fogging agents, colored couplers, development inhibitor-releasing couplers (so-called DIR couplers), development inhibitor-releasing compounds and the like can be added, if necessary. Furthermore, various additives such as other stain preventing agents, sludge preventing agents, and multi-layer effect accelerators can be used.

The color developer of the present invention has the following general formula [S
I] or [SII] compound (surfactant)
It is preferable to contain at least one of the above. General formula [SI]

[0089]

[Chemical 28]

[In the formula, A represents a monovalent organic group. B and C are

[0091]

[Chemical 29]

And may be the same or different (provided that each of a, b and c is 0, 1, 2 or 3, d is 0 or 1 and Y is a hydrogen atom or a hydroxyl group). Note that a, b, and c cannot be 0 at the same time.) m and n represent the integer of 1-100. X represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. ] General formula [SII]

[0093]

[Chemical 30]

[In the formula, M represents an alkali metal, a hydrogen atom, an ammonium salt or an alkanolamine salt, n is an integer of 1 to 100, and A represents a monovalent organic group. ]

General formulas [SI] and [SII] will be described in detail. In the general formula [SI], A is a monovalent organic group, for example, an alkyl group having 6 to 50 carbon atoms, preferably 6 to 35 carbon atoms (for example, each group such as hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl). Or an aryl group substituted with an alkyl group having 3 to 35 carbon atoms or an alkenyl group having 2 to 35 carbon atoms.

Preferable groups to be substituted on the aryl group are alkyl groups having 1 to 18 carbon atoms (eg, unsubstituted alkyl such as methyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl). Group), a substituted alkyl group such as benzyl and phenethyl or an alkenyl group having 2 to 20 carbon atoms (for example, an unsubstituted alkenyl group such as oleyl, cetyl and allyl groups)
Is mentioned.

Examples of the aryl group include groups such as phenyl, biphenyl and naphthyl, with a phenyl group being preferred. The aryl group may be substituted at any of the ortho, meta and para positions, and a plurality of groups can be substituted. B and C are respectively

[0098]

[Chemical 31]

And may be the same or different (provided that a, b and c are each 0, 1, 2 or 3, d is 0 or 1 and Y is a hydrogen atom or a hydroxyl group). Note that a, b, and c cannot be 0 at the same time.) m and n represent the integer of 1-100. X is a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and examples thereof include the groups described in A.

In the general formula [SII], M represents an alkali metal (eg, Na, K, Li, etc.), a hydrogen atom, an ammonium salt or an alkanolamine salt, and n is 1 to 1
Is an integer of 00, A is a monovalent organic group, for example, an alkyl group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms (for example, each group such as hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl). , Or 3 to 2 carbon atoms
It is an aryl group substituted with an alkyl group of 0, and the substituent preferably has 3 to 12 carbon atoms (eg, propyl, butyl, pentyl, hexyl, heptyl,
Octyl, nonyl, decyl, undecyl, dodecyl, etc.), and the aryl group is phenyl,
Examples thereof include groups such as tolyl, xynyl, biphenyl and naphthyl, with a phenyl group and a tolyl group being preferred.

The position at which the alkyl group is bonded to the aryl group may be any of the ortho, meta and para positions.

Examples of the compounds represented by the general formulas [SI] and [SII] are shown below, but the invention is not limited thereto.

(Compound represented by the general formula [SI]) SI
-1-SI-22 Japanese Patent Laid-Open No. 4-67038 No. 5
Page to page 6 Same as I-1 to I-22.

[0104]

[Chemical 32]

SI-24 to SI-27 JP-A-4-67
The same as No. 038, page 6, I-24 to I-27.

[0106]

[Chemical 33]

SI-29 to SI-30 JP-A-4-67
No. 038, page 6, same as I-29 to I-30.

[0108]

[Chemical 34]

SI-35 Same as I-35 on page 6 of JP-A-4-67038.

[0110]

[Chemical 35]

SI-38 to SI-46 JP-A-4-67
No. 038, pages 6 to 7, same as I-38 to I-46.

[0112]

[Chemical 36]

SI-48 to SI-78 JP-A-4-67
No. 038, pages 7-8, same as I-48-I-78.

(Compound represented by the general formula [SII]) S
II-1 to SII-7 JP-A-4-67038, page 9, same as V-1 to V-7.

[0115]

[Chemical 37]

Among the above exemplified compounds, SI is preferable.
-23, SI-28, SI-31, SI-32, SI-
33, SI-34, SI-36, SI-37, SI-4
7, SII-8 and SII-9.

The addition amount of the compounds represented by the general formulas [SI] and [SII] is 0.01 g / l to the color developing solution.
The range of 2.0 g / l is preferable in terms of preventing the main agent from precipitating and preventing stain.

The compounds (surfactants) represented by the above general formulas [SI] and [SII] are preferably contained in a concentration range of 1/5 to 10 times the critical micelle concentration in the color developer. .

The critical micelle concentration of the surfactant here is a very narrow concentration range in which the decrease in the surface tension of the solution sharply decreases with an increase in the concentration of the surfactant, and the hydrophobic micelle in a color developing solution. In the presence of a substance, the surface tension may have a minimum value in this concentration range, and in that case, the concentration of the minimum value is defined as the critical micelle concentration.

Since the color developing agent is generally inferior in water solubility and unstablely dispersed in the color developing solution, it tends to be oriented at the hydrophobic interface and is significantly precipitated at the liquid interface and the container wall interface. It is considered that the surfactant orients itself to the hydrophobic interface and prevents the interfacial deposition of the color developing agent. Therefore, when the surfactant is less than ⅕ times the critical micelle concentration in the color developing solution, the effect of preventing interfacial precipitation of the color developing agent is thin,
On the other hand, when the concentration exceeds the critical micelle concentration by 10 times, a large amount of the surfactant exists in the solution in a micelle state, which rather lowers the solubility of the color developing agent.

In the present invention, the above general formula [SI],
By using the compound represented by [SII] in combination,
The effect of the object of the present invention is improved. For example, the number of days of precipitation of the crystal in Example 1 is improved by about 20%.

The color developer of the present invention preferably contains an aromatic sulfonic acid or a salt thereof. The aromatic sulfonic acid or salt thereof in the present invention refers to a compound in which a sulfonate is directly bonded to an unsaturated conjugated ring showing aromaticity. There may be one or more sulfonic acid groups or sulfonates. The ring exhibiting aromaticity may contain a hetero atom and may have an arbitrary substituent. 1
One compound may have a plurality of rings exhibiting aromaticity and may be a polymer. Examples of the sulfonate include alkali metal salts such as lithium, sodium and potassium, and ammonium salts.

The aromatic sulfonic acid or salt thereof preferably used in the present invention includes compounds represented by the following general formula [I] or [J].

[0124]

[Chemical 38]

[In the formula, at least one of A to F represents a sulfonic acid group or a sulfonate, and the rest represent a hydrogen atom, a halogen atom, or a saturated or unsaturated alkyl group. ]

[0126]

[Chemical Formula 39]

[In the formula, at least one of G to N is a sulfonic acid group or a sulfonate, and the rest are any of a hydrogen atom, a halogen atom, and a saturated or unsaturated alkyl group. ] In formula [I] or [J], A to F or G to
The saturated or unsaturated alkyl group representing N preferably has 1 to 10 carbon atoms. The carbon chain may be linear or may have a side chain.

Specific examples of the compounds represented by formula [I] or [J] are shown below, but the invention is not limited thereto. All the exemplified compounds are shown as sodium salts,
Some or all of them may be sulfonic acid or other salt.

[0129]

[Chemical 40]

[0130]

[Chemical 41]

The addition amount of the aromatic sulfonic acid or its salt used in the color developing solution of the present invention is
It is in the range of 10 to 200 g / l, preferably 20 to 1
It is in the range of 00 g / l.

In the present invention, the above-mentioned general formula [I],
By using the compound represented by [J] in combination, the effect of the object of the present invention is improved. For example, the number of days of precipitation of the crystal in Example 1 is improved by about 20%.

The concentrated color developing composition or color developing solution of the present invention comprises an imagewise image comprising a support and one or more silver halide emulsion layers containing imagewise distributed developable silver halide emulsion grains. It has the utility of providing color development to exposed silver halide photographic elements. A wide variety of photographic elements containing different types of emulsions (both color negative and color reversal films and papers, and color motion picture films and prints) can be processed using the present invention. These emulsion types are well known in the art (see Research Disclosure).

The present invention is particularly useful for processing high chloride (greater than 70 mole percent chloride, and preferably greater than 90 mole percent chloride, based on silver content) emulsions of color photographic paper. Such color photographic papers can contain any useful amount of silver coated in one or more emulsion layers, and in some embodiments have a low silver amount (ie, 0.8 g silver / g).
elements (less than m ² ) are processed using the present invention.

Color development of the imagewise exposed silver halide photographic element is carried out under suitable time and temperature conditions and in suitable processing equipment to produce the desired developed image, a color developer prepared in accordance with the present invention. Contact with. Then one or more, in a particular desired order as known in the art,
Using conventional operations including, but not limited to, a development stop step, a bleach step, a fixing, a bleach / fix step, a washing (or rinsing) step, a stabilizing step and a drying step.
Additional processing can be done. Useful processing steps of various processing protocols, including conventional Process C-41 processing for color negative films, Process RA-4 for processing color papers, and Process E-6 for processing color reversal films, and their useful conditions. And materials are well known.

The processing time and temperature for each processing step of the present invention are generally those used in the art. For example, color development generally involves 20-6.
It is carried out at a temperature of 0 ° C. Maximum overall color development time is 4
It can be 0 minutes, the preferred time is 75-450
Seconds. For color photographic paper processing, it is desirable that the overall color development time is shorter (for example, 45 seconds or less). At least 4 parts of the color developing concentrate composition of the present invention are used.
It is possible to prepare a working concentration solution or a replenisher by appropriately diluting the solution up to 12 times. Dilution ratio is 4 times to 1
It is preferably 0 times, and water is usually used as the diluent. It can be diluted during or before treatment.

The addition amount of each compound used in the present invention is described as a concentration as a color developing solution unless otherwise specified, and in a concentrated composition, it is determined in consideration of its dilution ratio. Just go.

[0138]

[Example] Example 1 The following processing solutions for color paper were prepared.

[0139] Color developer   Diethylenetriamine pentaacetic acid 5 sodium 3.0 g / l   Triazinyl stilbene optical brightener 1.0g / l   sodium p-toluenesulfonate 5.0 g / l   Sodium sulfite 0.4g / l   Compound represented by general formula 1 (described in Table 1) (addition amount described in Table 1)   Diethylhydroxylamine or   Compound represented by general formula 2 (described in Table 1) 0.015 mol / l   Color developing agent (1) 0.02 mol / l   Potassium carbonate 35.0g / l   KCl 3.5g / l   Adjust to pH 10.3 with sulfuric acid or KOH

Add 200 ml of the above color developing tank solution to a beaker.
The bottom 2/3 of the rectangular plate made of vinyl chloride was immersed in a liquid and stored at 40 ° C. for 3 days and 7 days, and the stains deposited on the liquid interface of the plate were visually evaluated. The evaporated water was replenished every day. The results are shown in Table 1.

[0141]

[Table 1]

The evaluations in the table are as follows. ◎ = No deposit ○ = Slightly visible dirt △ = Clearly there is a deposit, × = Crystalline is precipitated. DEHA = diethylhydroxylamine

From Table 1, it can be seen that the interfacial precipitation property is improved by adding the compound represented by the general formula 1 of the present invention. The addition amount is preferably 2 × 10 ⁻⁵ mol / L or more and 2 × 10 ⁻² mol / L or less. Further, it is understood that the effect of the present invention becomes more remarkable by using the compound represented by the general formula 2.

Example 2 Experiment No. 1 of Example 1 In 1-7, as a compound represented by the general formula 3, diethylene glycol (DEG) and polyethylene glycol average molecular weight 600 (PEG # 600) were added as shown in Table 2, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

[0145]

[Table 2]

From Table 2, the effect of the present invention is remarkable when the compound represented by the general formula 3 is added, and particularly 10 to 1
It is preferable to add in the range of 00 g / l.

Example 3 The following processing solutions for color paper were prepared.

[0148] Color development replenisher   Diethylenetriamine pentaacetic acid 5 sodium 3.0 g / l   Triazinyl stilbene optical brightener 2.0g / l   Sodium p-toluenesulfonate 10.0 g / l   Diethylene glycol 20.0 g / l   Sodium sulfite 1.0g / l   Compound represented by general formula 1 (addition amount is shown in Table 3)   Exemplified compound 2-18 0.025 mol / l   Color developing agent (1) 0.030 mol / l   Potassium carbonate 35.0g / l   Adjust to pH 11.2 with sulfuric acid or KOH

[0149] Color development tank liquid   Diethylenetriamine pentaacetic acid 5 sodium 3.0 g / l   Triazinyl stilbene optical brightener 1.0g / l   Sodium p-toluenesulfonate 10.0 g / l   Diethylene glycol 20.0 g / l   Sodium sulfite 0.4g / l   Compound represented by general formula 1 (addition amount is shown in Table 3)   Exemplified compound 2-18 0.015 mol / l   Color developing agent (1) 0.016 mol / l   Potassium carbonate 35.0g / l   KCl 3.5g / l   Adjust to pH 10.3 with sulfuric acid or KOH

[0150] Bleach-fix replenisher and tank solution   Ammonium sulfite (40% aqueous solution) 100.0 g / l   Ammonium thiosulfate 120.0 g / l   Ethylenediaminetetraammonium iron acetate 75.0 g / l   Acetic acid 10.0 g / l   Adjust the pH of the replenisher to 5.0 and the tank to 6.0 with sulfuric acid or ammonia water.

[0151] Stabilizing replenisher and tank fluid   Hydroxyethylidene-1,1-diphosphonic acid disodium salt                                                           4.0 g / l   Diethylenetriamine pentaacetic acid 5 sodium 2.0 g / l   Sodium sulfite 1.0g / l   Optical brightener Chinopearl SFP (Ciba Specialties)                                                           1.0 g / l   Adjust to pH 7.0 with sulfuric acid or ammonia water

A color paper (QA-A7 paper made by Konica) exposed by a conventional method was run under the following processing conditions.

Process Tank capacity Processing temperature Processing time Replenishment amount Color development 12.5L 40.2 ± 0.3 ° C. 22 seconds 80 ml / m ² Bleach-fixing 12.3 L 37 ± 2 ° C. 22 seconds 80 ml / m ² Stabilization 1 11 .8L 35 ± 3 ° C. 22 seconds Cascade flow stabilization 2 12.0L 35 ± 3 ° C. 22 seconds Cascade flow stabilization 3 12.5L 35 ± 3 ° C. 22 seconds 200 ml / m ² dry 70-85 ° C. 30 seconds

The running experiment was carried out by processing 10 m ² of color paper per day until the total replenishment amount of the color developing replenisher became equal to the tank volume (1 round). The evaluation was conducted by visually observing the precipitation of crystals on the liquid interface of the color developing tank and the portion in contact with the rack at the end of running, and the adhesion of stains to the color paper. The results are shown in Table 3.

[0155]

[Table 3]

Evaluation of tank / rack deposition was as follows. ⊚ = No deposit, ◯ = Slightly visible stain, Δ = Clearly deposit, × = Crystallized substance is deposited.

Evaluation of paper stains was as follows. ◎ = No stain, ○ = About 1 in 100 sheets shows a slight stain, △ = About 1 in 10 shows a slight stain, X = Stain is visible on almost all prints.

From Table 3, even in actual running in an automatic processor, by adding the compound represented by the general formula 1,
It can be seen that the interfacial depositability is improved and the stain on the print is small.

Example 4 Experiment No. 3 of Example 3 was used. In 3-1 and 3-5, the replenishment amount of the color developing agent was changed as shown in Table 4, and the same evaluation was performed. The amount of the color developing agent added to the color developing replenisher was adjusted so that the concentration of the color developing agent in the tank solution was 0.016 mol / l.

[0160]

[Table 4]

From Table 4, the replenishment amount of the color developing agent is the photosensitive material 1
It can be seen that the effect of the present invention is more remarkable in the case of 20 to 100 ml per m ² .

Example 5 The following processing agents for color paper were prepared.

[0163] Color developer concentrate   Triethanolamine 100g / l   Compound represented by General Formula 1 (described in Table 5) (addition amount described in Table 5)   Exemplified compound 2-18 0.15 mol / l   Color developing agent (17) 0.10 mol / l   Triazinyl stilbene optical brightener 7g / l   1-Hydroxyethylidene-1,1-diphosphonic acid tetrasodium 7 g / l   Lithium chloride 10g / l   200 g / l potassium carbonate   KCl 3.5g / l   Adjust to pH 12.5 with KOH

200 ml of the above color developer concentrate was placed in a polyethylene bottle, sealed, and stored in a low temperature room at 5 ° C. After 1 day and 3 days, the presence or absence of a precipitate was confirmed. The results are shown in Table 5.

[0165]

[Table 5]

The evaluations in the table are as follows. ○ = no precipitate, △ = Slight precipitation is observed, × = Crystalline precipitates.

From Table 5, it can be seen that the addition of the compound represented by the general formula 1 of the present invention improves the low temperature precipitation property of the concentration kit. The addition amount is 1 × 10 ⁻⁴ mol / L or more 1 × 10
^-1 mol / L or less is preferable.

Example 6 The following processing agents for color paper were prepared.

[0169] Color developer concentrate   Triethanolamine 30g / l   Compound represented by General Formula 3 (described in Table 6) (addition amount described in Table 6)   Exemplified compound 1-2 0.01 mol / l   Exemplified compound 2-18 0.25 mol / l   Color developing agent (17) 0.16 mol / l   Triazinyl stilbene optical brightener 10g / l   1-Hydroxyethylidene-1,1-diphosphonic acid tetrasodium                                                             10 g / l   Lithium chloride 15g / l   Potassium carbonate 300g / l   KCl 5g / l   Adjust to pH 12.5 with KOH

Example 5 was carried out on the above color developer concentrate.
The same evaluation as was done.

[0171]

[Table 6]

From Table 6, it can be seen that the low temperature precipitation property is improved by adding the compound represented by the general formula 3 even if the concentration rate of the kit is increased. The addition amount of the compound represented by the general formula 3 is preferably 50 g to 700 g per 1 L of the concentrated liquid.

Example 7 Experiment No. 6 of the sixth example. With the same composition as 6-6, the pH of the concentrated solution was changed with sulfuric acid or KOH as shown in Table 7,
The same evaluation as in Example 5 was performed.

[0174]

[Table 7]

From Table 7, it is understood that the effect of the present invention is more remarkable when the pH of the concentrated solution is 11-14.

Example 8 The following processing solutions for color paper were prepared.

[0177] Color developer concentrate (Part A)   Triethanolamine 30g / l   Diethylene glycol 200g / l   Exemplified compound 1-2 0.01 mol / l   Diethylhydroxylamine or     Exemplified compound 2-18 0.25 mol / l   Triazinyl stilbene optical brightener 10g / l

[0178] (Part B)   Color developing agent (1) 0.16 mol / l   Potassium sulfite 5g / l

[0179] (Part C)   1-Hydroxyethylidene-1,1-diphosphonic acid tetrasodium 10 g / l   Lithium chloride 15g / l   Potassium carbonate 300g / l   KCl 5g / l

Color developing solution replenisher solution 700 ml of water was added to the above color developing agent concentrate parts A, B and C.
Was added to each to prepare a replenisher.

[0181] Color development tank liquid   Triethanolamine 3g / l   Diethylene glycol 20g / l   Exemplified compound 1-2 0.001 mol / l   Diethylhydroxylamine or     Exemplified compound 2-18 0.015 mol / l   Color developing agent (1) 0.010 mol / l   Triazinyl stilbene type optical brightener 1g / l   1-Hydroxyethylidene-1,1-diphosphonic acid tetrasodium 1 g / l   Lithium chloride 1.5g / l   Potassium carbonate 30g / l   KCl 3.5g / l   Adjust to pH 10.3 with sulfuric acid or KOH

Bleach-fixing replenisher and tank solution The same treatment liquid as in Example 4 was used.

Stabilizing Replenisher and Tank Liquid The same treatment liquid as in Example 4 was used.

A color paper (QA-A7 paper manufactured by Konica) exposed by a conventional method was run under the following processing conditions.

Process Tank capacity Treatment temperature Treatment time Replenishment amount Color development 12.5L 40.2 ± 0.3 ° C. 45 seconds 100 ml / m ² Bleach-fixing 12.3 L 37 ± 2 ° C. 45 seconds 80 ml / m ² Stabilization 1 11 .8L 35 ± 3 ° C. 45 seconds Cascade flow stabilization 2 12.0L 35 ± 3 ° C. 45 seconds Cascade flow stabilization 3 12.5L 35 ± 3 ° C. 45 seconds 200 ml / m ² dry 70-85 ° C. 45 seconds

The running experiment was carried out by processing 10 m ² of color paper per day until the total replenishing amount of the color developing replenisher became the same as the tank capacity (1 round). Similarly to Example 3, when visually observing the precipitation of crystals at the liquid interface of the color developing tank and the portion in contact with the rack at the end of running, and the adhesion of stains to the color paper, the same good result was obtained. In particular, the effect was remarkable when the exemplified compound 2-18 was used instead of diethylhydroxylamine as a preservative.

Example 9 The following processing agents for color negative films were prepared.

[0188] Color developer concentrate   Diethylene glycol 300g / l   Exemplified compound 1-2 0.01 mol / l   Exemplified compound 2-18 0.20 mol / l   Color developing agent (18) 0.15 mol / l   Sodium sulfite 60g / l   Diethylenetriamine pentaacetic acid 70g / l   Potassium bromide 10g / l   Potassium carbonate 350g / l   Adjust to pH 12.5 with KOH

When the low temperature storability of the above color developer concentrate was evaluated in the same manner as in Example 5, no precipitate was formed even after 3 days and good results were obtained.

Claims (13)

[Claims] 1. A color developer for a silver halide color photographic light-sensitive material, which contains at least one compound selected from the compounds represented by the following general formula 1. Formula 1 X—R—SO ₃ M In the formula, X is a hydroxyl group, a halogen group, an optionally substituted alkoxy group, a sulfo group or a sulfonate,
It represents a sulfuric acid ester, a sulfuric acid ester salt, or a sulfonyl halide. R represents a linear or branched alkylene group having 1 to 5 carbon atoms, and M represents Li, Na, K or NH ₄ . 2. At least one selected from the compounds represented by the following general formula 2 is contained:
A color developing solution for silver halide color photographic light-sensitive materials as described in 1. [Chemical 1] In the formula, A represents a hydrogen atom or an optionally substituted alkyl group, B represents an optionally substituted alkylene group, and Y represents a carboxyl group, a sulfo group, a phosphono group, a hydroxyl group, an alkoxy group or amino. Group, ammonio group,
It represents a sulfamoyl group or an alkylsulfonyl group.
These may be in salt form. 3. The compound represented by the general formula 1 is added to 2 × 10 5.
^The color developer for silver halide color photographic light-sensitive materials according to claim 1 or 2, which contains ^-5 mol / L or more and 2 x 10 ^-2 mol / L or less. 4. A compound represented by the following general formula 3
At least one of the above is included.
To 3) a silver halide color photographic light-sensitive material
Color developer. General formula 3 HO- (W-O) n-H In the formula, W is -CH_TwoCH_Two-, -CH_TwoCH_TwoCH
_Two-, -CH_TwoCH (CH _Three)-, Where n is 1 to 30
Represents the integer. 5. A compound represented by the above general formula 3 in an amount of 10 g /
The color developer for silver halide color photographic light-sensitive materials according to claim 4, which contains L or more and 100 g / L or less. 6. A color-developing concentrated composition for a silver halide color photographic light-sensitive material, which contains at least one compound selected from the compounds represented by the general formula 1. 7. The method according to claim 6, further comprising at least one selected from the compounds represented by the general formula 2.
A silver halide color photographic light-sensitive material as described in 1. 8. A para-phenylenediamine color developing agent is contained in the same part, which contains at least one compound selected from the compounds represented by the general formula 1 and at least one compound represented by the general formula 2. A silver halide color photographic light-sensitive material color development concentrate composition. 9. The compound represented by the general formula 1 is added to 1 × 10.
^-4 mol / L or more and 1 * 10 < ^-1 > mol / L or less is contained, The color development concentrated composition for silver halide color photographic light-sensitive materials in any one of Claims 6-8. 10. A color-developing concentrated composition for a silver halide color photographic light-sensitive material according to claim 6, which contains at least one compound represented by the general formula 3. . 11. 50 g of the compound represented by the above general formula 3
/ L or more and 700 g / L or less are contained, The color development concentrated composition for silver halide color photographic light-sensitive materials of Claim 10 characterized by the above-mentioned. 12. The color-developing concentrated composition for silver halide color photographic light-sensitive materials according to claim 6, wherein the concentrated composition has a pH of 11 or more and 14 or less. 13. A processing method for developing a silver halide color photographic light-sensitive material using the color developer according to claim 1, wherein the replenishing amount of the color developer is 1 m of the light-sensitive material. 20 ml or more and 100 ml or less per ² pieces. A method for processing a silver halide color photographic light-sensitive material.