JPH1165055A - Processing liquid composition for amplified development and picture forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve graininess, by causing a composition to contain at least one kind of water-soluble surfectant. SOLUTION: A composition contains at least one kind of surfectant. By this, uniformity in diffusion of a color developing agent or of an oxidizing agent for amplified development in a photosensitive material is improved and local generation of coloring reaction is relaxed. Water-soluble surfectant are divided into ionic surfectant and non-ionic surfectant, and the ionic surfectants are further divided into anionic surfectants and cationic surfectants by ion kinds of parts exhibiting surface activity in a water solution. Any of them can be used and also a combination of two or more of them can be used. A compound expressed by an expression, and the like are among preferable surfectant. In the expression, A2 is a univalent organic radical, for example, an aryl radical substituted by an alkyl radical and the like the number of whose carbon atoms is 6 to 50, preferably 6 to 35, and further preferably, a phenyl radical. B or C denotes an ethylene oxide and the like while m and n each denote an integer 0 to 100. X1 is a hydrogen atom, an alkyl radical, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing solution composition for amplification and development having improved graininess and an image forming method.

[0002]

2. Description of the Related Art Silver halide photographic materials (hereinafter, also simply referred to as "photosensitive materials") have extremely excellent characteristics, such as high sensitivity and excellent gradation, as compared with other printing materials. It has been widely used today. The silver halide photographic light-sensitive material has the characteristics described above. Further, the amount of photosensitive silver halide in the light-sensitive material can be reduced, the time required for desilvering processing can be shortened or omitted, and halogen is a preferable means in terms of effective use of resources. A method of forming an image by subjecting a silver halide photographic light-sensitive material to amplification and development processing has been known for a long time. As an example of the amplification development processing, there is a method in which an oxidized color developing agent is generated with an oxidizing agent such as hydrogen peroxide / cobalt (III) complex using developed silver as a catalyst, and then an image dye is formed by reaction with a coupler. . Among them, a method using hydrogen peroxide as an oxidizing agent for amplification and development is preferable because it has high amplification efficiency and can greatly reduce the burden on the environment.

However, generally, when the amount of the photosensitive silver halide in the photosensitive material is reduced, the number of silver halide grains per unit area is reduced, so that there is a problem that the graininess is reduced. Reduce the amount of silver halide,
As means for preventing the number of silver halide grains from decreasing, for example, a method using so-called tabular silver halide grains having a large aspect ratio in JP-A-6-301128 or the like, or a cubic crystal in EP-A-0 718 686. A method is disclosed in which the length of one side of silver halide grains is reduced to reduce the volume per silver halide grain.

[0004] However, even if the number of silver halide grains is kept constant by these means, the graininess tends to deteriorate more easily in the amplification development processing than in the ordinary color development processing. Was rare.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a processing solution composition for amplification and development having improved graininess and an image forming method.

[0006]

The above objects of the present invention have been attained by the following constitutions.

(1) A processing solution composition for amplification and development comprising at least one water-soluble surfactant.

(2) A processing solution for amplification and development comprising at least one compound selected from the compounds represented by the following general formula (A).

[0009]

Embedded image

Wherein L represents an alkylene group which may be substituted, A represents a carboxyl group, a sulfo group, a phosphono group,
Phosphinic acid group, hydroxyl group, amino group which may be alkyl-substituted, ammonium group which may be alkyl-substituted,
R represents a carbamoyl group which may be substituted with alkyl, or a sulfamoyl group which may be substituted with alkyl; R represents a hydrogen atom or an alkyl group which may be substituted; (3) A processing solution composition for amplification development, comprising a water-soluble coupler capable of performing a coupling reaction with at least one oxidized form of a color developing agent.

(4) A processing solution composition for amplification and development comprising at least one kind of radical scavenger.

(5) The processing solution composition for amplification and development as described in (1) above, wherein the water-soluble surfactant is a nonionic or anionic surfactant.

(6) The processing solution composition for amplification and development according to any one of the above (1) to (5), comprising at least one oxidizing agent for amplification and development.

(7) The processing solution composition for amplification development as described in (2) above, which contains at least one kind of color developing agent.

(8) The processing solution composition for amplification development as described in (3) or (4) above, wherein the composition does not substantially contain a color developing agent.

(9) At least one layer of a dye-donor substance and a photosensitive silver halide having a silver chloride content of at least 80 mol% on a support is provided in an amount of 0.001 g / m ^{2 to} 0.1 in terms of silver.
After imagewise exposing a silver halide photographic light-sensitive material having a color image forming layer containing g / m ² , amplification using the processing solution composition for amplification and development according to any one of 1 to 8 above. An image forming method, comprising developing.

Hereinafter, the present invention will be described in detail. The present invention relates to a processing solution composition for amplification development (hereinafter, also simply referred to as “amplification developer”) and an image forming method using the same. Here, the processing solution composition for amplification development is a photographic processing solution composition used for performing amplification development processing on a photosensitive material.

In the present invention, the amplification development process is a process in which a latent image generated by exposure of a photosensitive material is developed with a color developing agent or a black-and-white developing agent to form developed silver, and a chemical reaction using the developed silver as a catalyst is performed. Is used to form or release an image dye.For example, an image dye is formed by a coupling reaction between a coupler and an oxidized color developing agent formed by a redox reaction of a color developing agent and an oxidizing agent using a developed silver catalyst as a catalyst. And the like.

Amplifying development requires a color developing agent and an oxidizing agent for amplification. These may be used together in the same processing solution, or may be prepared as separate processing solutions. May be done. When the color developing agent and the oxidizing agent for amplification development are each prepared as separate processing solutions, a method of simultaneously or sequentially supplying these processing solutions to the photosensitive material using a spray method or a coating method, or a method of supplying each processing solution. For example, a method in which the photosensitive material is sequentially passed through a tank filled with the above. In the present invention, when the color developing agent and the oxidizing agent for amplification development are prepared as separate processing solutions, each processing solution is referred to as a processing solution composition for amplification development.

The present invention according to claim 1 is characterized in that the amplification developer contains at least one water-soluble surfactant. The mechanism by which the effect of the present invention of improving the granularity is obtained by the amplification developer containing a water-soluble surfactant is not clear, but the presence of the surfactant causes the color developing agent or amplification in the photosensitive material. It is speculated that one of the reasons is that the uniformity of diffusion of the oxidizing agent for development is improved and the occurrence of a local coloring reaction is reduced.

The water-soluble surfactant referred to in the present invention is a so-called amphoteric substance having two groups of hydrophilic groups and hydrophobic groups in the molecule, which are incompatible with each other in solubility in a solvent. Point. Water-soluble surfactants are classified into ionic surfactants and non-ionic surfactants depending on whether they are water-soluble and ionic, and ionic surfactants are further divided into ionic species that show surface activity in aqueous solution. Are classified into an anionic surfactant, a cationic surfactant, and a nonionic surfactant. Any of these surfactants can be used to achieve the object of the present invention, and two or more surfactants can be used in combination.

The surfactants preferably used in the present invention include compounds represented by the following general formulas [I] to [X] and [XI].

[0023]

Embedded image

In the formula, A ₂ is a monovalent organic group, for example, an alkyl group having 6 to 50, 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 2 to 35 carbon atoms or an alkenyl group having 2 to 35 carbon atoms.

A preferred group to be substituted on the aryl group is an alkyl group 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 (eg, an unsubstituted alkenyl group such as oleyl, cetyl and allyl group, and a substituted alkenyl group such as styryl group). Examples of the aryl group include phenyl, biphenyl, naphthyl and the like, and a phenyl group is preferable.

The aryl group may be substituted at any of the ortho, meta and para positions, and a plurality of groups may be substituted.

B or C is ethylene oxide or propylene oxide or

[0028]

Embedded image

Represents the following. (However, n ₁ , m ₁ and l ₁ are respectively 0, 1, 2 or 3).

M and n represent an integer of 0 to 100.

X ₁ is a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and examples thereof include the groups described for A ₂ .

[0032]

Embedded image

In the formula, R ¹ represents a hydrogen atom, an aliphatic group or an acyl group, and R ² represents a hydrogen atom or an aliphatic group.

E ¹ represents ethylene oxide, E ² represents propylene oxide, E ³ represents ethylene oxide, X represents a carboxy group, —O—,

[0035]

Embedded image

Wherein R ³ is an aliphatic group, a hydrogen atom or R ³ is an aliphatic group, a hydrogen atom or

[0037]

Embedded image

And R ⁴ represents a hydrogen atom or an aliphatic group.

L ₁ , l ₂ , m ₁ , m ₂ , n ₁ , n ₂ are each 0 to
Represents an integer of 100.

[0040]

Embedded image

In the formula, R ¹ represents an aliphatic group (for example, a saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl group), and X represents

[0042]

Embedded image

Wherein R ² and R ³ represent a hydrogen atom or a group defined by R ¹ , 1 is 0 or 1, M is a hydrogen atom or an alkali metal (Na, K), an ammonium ion, Represents an organic ammonium ion. L ₀ represents an alkylene group.

[0044]

Embedded image

In the formula, R ¹ represents an aliphatic group (for example, a saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl group), and X represents

[0046]

Embedded image

Wherein R ² and R ³ represent a hydrogen atom or a group defined by R ¹ , and l and m ′ are each 0 or 1;
L ₀ represents an alkylene group, Y represents an oxygen atom, and M represents an alkali metal (Na, K, Li).

[0048]

Embedded image

In the formula, M is an alkali metal (Na, K, L
i), n is 1 to 100, and A ₂ is a monovalent organic group, for example, an alkyl group having 6 to 20, preferably 6 to 12 carbon atoms (for example, hexyl, heptyl, octyl, nonyl, decyl) , Undecyl or dodecyl) or an aryl group substituted with an alkyl group having 3 to 20 carbon atoms, and the substituent is preferably an alkyl group having 3 to 12 carbon atoms (for example, propyl, butyl, Each group such as pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl), and the aryl group includes each group such as phenyl, tolyl, xinyl, biphenyl or naphthyl, preferably a phenyl group or Is a tolyl group. The position where the alkyl group is bonded to the aryl group may be any of the ortho, meta and para positions.

[0050]

Embedded image

In the formula, R ₄ , R ₅ and R ₆ are a substituted or unsubstituted alkyl group, and R ₄ and R ₅ or R ₅ and R ₆ may each form a ring. A is

[0052]

Embedded image

(R ₇ represents a hydrogen atom or an alkyl group,
n represents an integer of 1, 2, 3).

[0054]

Embedded image

In the formula, R ₁ has the same meaning as A _{2 in} formula (I). R ₂ represents a hydrogen atom or an alkyl group (for example, a methyl group or an ethyl group), m and n are each 0, 1 or 2, and A is an alkyl group or a substituted or unsubstituted aryl group. X is -COOM or -SO ₃ M, M represents a hydrogen atom or an alkali metal.

[0056]

Embedded image

In the formula, R ₄ , R ₅ , R ₆ and R ₇ are a hydrogen atom, a substituted or unsubstituted alkyl group or a phenyl group. And X ^- represents a halide ion, hydroxide ion, sulfate ion, carbonate ion, nitrate ion, acetate ion, a anion such as p- toluenesulfonic acid ion.

[0058]

Embedded image

Wherein one of R ₆ and R ₇ is a hydrogen atom,
Alkyl group, the other (where M represents. A cation hydrogen atom or a monovalent) formula -SO ₃ M represents a group represented by.

A ₁ represents an oxygen atom or a group represented by the formula —NR ₁₀ — (R ₁₀ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). R ₈ and R ₉ each have 4 to 3 carbon atoms
Represents an alkyl group of 0. However, the alkyl group represented by R ₈ , R ₉ or R ₁₀ may be substituted by a fluorine atom.

[0061]

Embedded image

In the formula, R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ each represent a hydrogen atom alkyl group, and M is a group represented by the general formula [II
I]. n and p each represent 0 or an integer of 1 to 4, and are values satisfying 1 ≦ n + p ≦ 8.

Examples of the compounds represented by formulas [I] to [X] and [XI] are shown below, but are not limited thereto.

[0064]

Embedded image

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

[0071]

Embedded image

[0072]

Embedded image

[0073]

Embedded image

[0074]

Embedded image

[0075]

Embedded image

[0076]

Embedded image

[0077]

Embedded image

[0078]

Embedded image

[0079]

Embedded image

[0080]

Embedded image

[0081]

Embedded image

[0082]

Embedded image

[0083]

Embedded image

The amount of the water-soluble surfactant according to the present invention is not particularly limited, but is preferably 0.05 to 20 g / l, and more preferably 0.25 to 15 g / l. Is remarkable, and foaming is small, which is particularly preferable.

The water-soluble surfactant according to the present invention may contain at least one kind, but two or more kinds may be used in combination.

The amplification developer according to the present invention may contain the above-mentioned water-soluble surfactant in advance, or may contain a surfactant eluted from the photosensitive material during the amplification development processing. However, the effect of the present invention is particularly remarkable when a water-soluble surfactant is contained in the amplification developer in advance.

The water-soluble surfactant according to the present invention is preferably a nonionic or anionic surfactant. Nonionic surfactants have a high effect of the present invention, and precipitate during continuous processing. Possibility is low and preferred.

The mode in which the water-soluble surfactant according to the present invention is contained in an amplification developer containing at least one kind of oxidizing agent for amplification development described later is particularly preferable because the effect of the present invention is high.

A known antifoaming agent can be used in the amplification developer of the present invention, if necessary.

The present invention according to claim 2 is characterized in that the amplification developer contains at least one compound selected from the compounds represented by formula (A). By the amplification developer containing the compound represented by the general formula (A),
The mechanism by which the effect of the present invention of improving the graininess is obtained is not clear, but the oxidized color developing agent generated by the reaction between the color developing agent and the oxidizing agent for amplification in the photosensitive material due to the presence of the compound is locally localized. It is speculated that one of the reasons is that the phenomenon that exists in large quantities is moderated.

In the general formula (A), L is a group having 1 to 1 carbon atoms.
0 represents a linear or branched alkylene group which may be substituted, and preferably has 1 to 5 carbon atoms. Specifically, groups such as methylene, ethylene, trimethylene, and propylene are preferred examples. Examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, and an ammonium group which may be alkyl-substituted, and preferred examples thereof include a carboxyl group, a sulfo group, a phosphono group, and a hydroxyl group. A represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, an amino group which may be alkyl-substituted, an ammonium group which may be alkyl-substituted, a carbamoyl group which may be alkyl-substituted, or an alkyl-substituted group. It represents a good sulfamoyl group, and preferred examples thereof include a carboxyl group, a sulfo group, a hydroxyl group, a phosphono group, and a carbamoyl group which may be alkyl-substituted. Examples of -LA include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group,
Sulfobutyl group, phosphonomethyl group, phosphonoethyl group, hydroxyethyl group can be mentioned as preferred examples, carboxymethyl group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group,
A phosphonoethyl group is a particularly preferred example. R represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, and having 1 to 5 carbon atoms.
Is preferred. Examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, an amino group which may be substituted with alkyl, an ammonio group which may be substituted with alkyl, a carbamoyl group which may be substituted with alkyl, and alkyl substitution. Represents a sulfamoyl group which may be substituted.
There may be two or more substituents. Preferred examples of R include a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group.
Hydrogen atom, carboxymethyl group, carboxyethyl group,
Particularly preferred examples include a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group. L and R may combine to form a ring.

Next, typical examples of the compound represented by formula (A) are shown below, but the present invention is not limited to these compounds.

[0093]

Embedded image

[0094]

Embedded image

[0095]

Embedded image

[0096]

Embedded image

[0097] There is no particular limitation on the amount of the compound represented by the general formula according to the present invention (A), 1.5 × 10 ^-3 mol to
The effect of the present invention is remarkable when the amount is preferably 1.5 × 10 ⁻¹ mol / l, and more preferably 3.0 × 10 ⁻³ mol to 9.0 × 10 ⁻² mol / l, and it is particularly preferable.

The compound represented by formula (A) according to the present invention may contain at least one kind, but may use two or more kinds in combination.

The amplification developer according to the present invention may contain the compound represented by the above general formula (A) in advance, and may be eluted from the photosensitive material during the amplification development processing. However, the effect of the present invention is particularly remarkable if it is previously contained in the amplification developer, which is preferable.

The compound represented by the general formula (A) according to the present invention is particularly effective in the case where it is contained in an amplification developer containing at least one oxidizing agent for amplification development described below, in which the effect of the present invention is high. preferable.

The compound represented by the general formula (A) according to the present invention is particularly preferably contained in an amplification developer containing at least one color developing agent described below, since the effect of the present invention is high.

The compound represented by the general formula (A) can be synthesized by subjecting commercially available hydroxylamines to an alkylation reaction (nucleophilic substitution reaction, addition reaction, Mannich reaction, etc.). Patent 11596
No. 34, “Inorganica Chemica Acta” (I
norganica Chimica Acta), 9
3 (1984) 101-107 and the like.

The present invention according to claim 3 is characterized in that the amplification developer contains a water-soluble coupler capable of performing a coupling reaction with at least one oxidized form of a color developing agent.

In the present invention, the term "water-soluble coupler" refers to a solution prepared by dissolving anhydrous potassium carbonate at a concentration of 20 g / l and adding 1 mmol / l of a 25 ° C. aqueous solution adjusted to pH 10.0 with a small amount of sulfuric acid and potassium hydroxide. These are defined as couplers that dissolve.

The water-soluble coupler according to the present invention preferably has at least one of a sulfo group, a carboxyl group, a hydroxyl group and an amino group in the molecule in order to increase the water solubility. Among these groups, a sulfo group, a carboxyl group, and a hydroxyl group are alkali metal salts (lithium,
Sodium, potassium salts, etc.), ammonium salts, organic base salts (pyridinium, guanidium, piperidinium,
Triethylammonium, triethanolamine salt, etc.)
And the like.

The amino group may form a salt with any inorganic or organic acid (eg, hydrochloric acid, sulfuric acid, sulfurous acid, carboxylic acids, phosphoric acids, p-toluenesulfonic acid, etc.).

It is preferred that the water-soluble coupler and the reaction product of the water-soluble coupler and the oxidized color developing agent according to the present invention do not remain in the finally formed photosensitive material. Therefore, the reaction product of the water-soluble coupler and the oxidized color developing agent may have any spectral absorption and may be colorless.

The molecular weight of the water-soluble coupler is preferably 10
It is less than 00, more preferably less than 500. Among the water-soluble couplers, those having the above-mentioned solubility not only under alkaline conditions but also under neutral conditions are particularly preferably used.

Of the water-soluble couplers used in the present invention,
A water-soluble coupler having a structure represented by the following general formula (1) or (2) has high effects of the present invention and is preferred.

[0110]

Embedded image

Formula (2) A ₂ —CH (X ₀ ) —B _{2 In the} formula, X ₀ represents a hydrogen atom, an alkyl group or a group capable of leaving by reaction with an oxidized form of a color developing agent. A ₁ and B ₁
Each represents a nitrogen atom or a carbon atom, and Z ₁ represents A ₁ -C (X
₀ ) = B ₁ represents an atom group necessary to form a ring.
A ₂ and B ₂ are each —COR ¹¹ , —CN, —C (R ¹² )
^{= NR 11, -CSR 11, -NO} 2, -N (R 11)
(R ¹² ), -N ⁺ (R ¹¹ ) (R ¹² ) (R ¹³ ), -SO ₂ R
¹¹ or an aryl group. A ₂ and B ₂ may be bonded to each other to form a ring. R ¹¹ , R ¹² and R ¹³ each represent a hydrogen atom or a monovalent organic group.

In the above general formulas (1) and (2), X
The alkyl group represented by ₀ preferably has 1 to 10 carbon atoms, may be linear or branched, and may have a substituent.

Examples of the group capable of leaving by reaction with an oxidized form of the color developing agent represented by X ₀ include, for example, a halogen atom (chlorine, bromine, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy ,
Alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythio, carbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring linked by N atom, alkyloxy Carbonylamino, aryloxycarbonylamino, carboxyl,

[0114]

Embedded image

(Wherein A ₁₁ and B ₁₁ each represent the above-mentioned A
₁ and B ₁ have the same meanings as above, and each of R ₁₀₁ and R ₁₀₂ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group), but preferably X ₀ is a hydrogen atom .

The general formula (1) is specifically represented by the following general formulas (1-1) to (1-6).

[0117]

Embedded image

In the formula, X ₂₁ and Z ₂₁ have the same meanings as X ₀ and Z ₁ in formula (1), respectively, and R ₂₁ , R ₂₂ ,
R ₂₃ , R ₂₄ and R ₂₇ each represent a hydrogen atom or a monovalent organic group. 1 represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₇
The organic group having no valence is not particularly limited. For example, a halogen atom and alkyl, cycloalkyl, alkenyl,
Cycloalkenyl, alkynyl, aryl, heterocyclic, acyl, sulfonyl, sulfinyl, phosphonyl, carbamoyl, sulfamoyl, cyano, spiro compound residue,
Bridged hydrocarbon compound residue, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, acylamino, sulfonamide,
Imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino,
Examples include groups such as alkoxycarbonyl, aryloxycarbonyl, alkylthio, arylthio, heterocyclic thio, sulfo, nitro, carboxyl, and hydroxyl.

R ₂₅ and R ₂₆ each represent a divalent organic group substituted through an oxygen atom, a sulfur atom or a carbon atom or a nitrogen atom. The structures represented by the general formulas (1-2), (1-3), and (1-5) may have a conjugate relationship with each other. The same applies to the structure represented.

In the general formulas (1-1) to (1-6),
X ₂₁ is = NC (X ₀ ) = N −, = NC (X ₀ ) = C
_{(R 21) -, = C} (R 22) -C (X 0) = N -, = C
_{(R 23) -C (X 0} ) = C (R 24) -, - C - (=
_{R 25) -C (X 0)} = N- , or -C (= R ₂₆₎ -C
(X ₀ ) = A group of atoms necessary to form a ring together with C (R ₂₇ ), preferably a group of carbon, hydrogen, oxygen and nitrogen atoms.

The ring formed is preferably a 5- to 6-membered ring, and may have a substituent. As the substituent, R ₂₁ described above,
Group represented by R _22, R _23, R ₂₄ and R ₂₇ can be mentioned.
Z ₂₁ may combine with R _{21 to} R ₂₇ to form a ring.

[0122] In the general formula (2), X ₀ has the same meaning as X ₀ in formula (1).

A ₂ and B _{2 in} the general formula (2) each represent —CO
^{R 11, -CN, -C (R} 12) = NR 11, -CSR 11, -
NO ₂ , -N (R ¹¹ ) (R ¹² ), -N ⁺ (R ¹¹ ) (R ¹² )
(R ^13), - it represents a SO ₂ R ¹¹ or an aryl group, A ₂ and B ₂ Among this, T. H. James: The Theory of Photographic Process (TheT
heavy of the Photographic
Process, 3rd edition, p. 388, FIG. 17.6, a combination which becomes active couplers is preferable.

Examples of the monovalent organic group represented by R ¹¹ , R ¹² and R ¹³ include the groups represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₇ . R ¹¹ and R ¹² may be bonded to each other to form a ring. A ₂ and B ₂ may also be bonded to each other to form a ring, and the formed ring is preferably a 5- to 6-membered ring.

In formula (2), when A ₂ and B ₂ are bonded to each other to form a ring, the structure may be conjugated to the structure represented by formula (1).

Among the water-soluble couplers, more preferable ones are represented by the following formulas (3) to (11).

[0127]

Embedded image

In the general formulas (3) to (11), X ₀ has the same meaning as X ₀ in the general formula (1), and R _{31 to} R
₄₅ and R _{48 each} represent a hydrogen atom or a monovalent organic group, and examples of the monovalent organic group include R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R _27.
And the group represented by

R ₄₆ and R ₄₇ each represent —CN, —C
(R ¹² ) = NR ¹¹ , −N ⁺ (R ¹¹ ) (R ¹² ) (R ¹³ )

[0130]

Embedded image

[0131] or represents a -COR ^11.

[0132] Here, R ^11, R ^12, R ^13, the have each the same meaning as R ^11, R ^12, R ¹³ in the general formula (2), R ¹¹ and R ^12, taken together form a ring May be.
R ₀ represents a hydrogen atom or a monovalent organic group, and p ₀ represents an integer of ₀ to 4. When p ₀ is 2 or more, a plurality of R ₀ may be the same or different.

One of Z _{31 to} Z ₃₂ is -N =, and the other is = N.
Represents C ( _R49 )-. Where R ₄₉ is synonymous with R ₃₅
Represents a hydrogen atom or a monovalent organic group.

[0134] m ₁₁ represents an integer of 0 to 2, when m ₁₁ is 2, the two R _35, may be the same or different. n ₁₁ is 0
4 of an integer, when n ₁₁ is 2 or more, plural R ₃₉ may be the same or different.

In the general formula (3), R ₃₁ and R ₃₂ and / or
Alternatively, R ₃₃ and R ₃₄ may combine with each other to form a ring.

In the general formula (3), R ₃₁ , R ₃₂ , R
Among the groups represented by ₃₃ or R ₃₄ , in the general formula (4), R
Among the groups represented by ₃₅ , in the general formula (5), R ₃₆ or R
Among the groups represented by ₃₇ , in the general formula (6), R ₃₈ or R
Among the groups represented by ₃₉ , in the general formula (7), R ₄₀ or R
Among the groups represented by ₄₁ , in the general formula (8), R ₄₂ or R
Among the groups represented by ₄₃ , in the general formula (9), R ₄₄ or R
Among the groups represented by ₄₅ , in the general formula (10), among the groups represented by R ₄₆ , in the general formula (11), the groups represented by R ₄₇ or R ₄₈ include a sulfo group, a carboxyl group, and a hydroxyl group. Preferably, at least one of a group and an amino group is contained.

Among the water-soluble couplers represented by formulas (3) to (11), particularly preferred are the water-soluble couplers represented by formulas (3) and (3).
Water-soluble couplers represented by (4) and (5).

The specific examples of the water-soluble coupler used in the present invention are shown below, but the invention is not limited thereto.

[0139]

Embedded image

[0140]

Embedded image

[0141]

Embedded image

[0142]

Embedded image

[0143]

Embedded image

[0144]

Embedded image

[0145]

Embedded image

[0146]

Embedded image

[0147]

Embedded image

[0148]

Embedded image

[0149]

Embedded image

[0150]

Embedded image

These water-soluble couplers are already known compounds, and some are commercially available. Also, methods known in the art, for example, US Pat. No. 2,369,929
No. 2,434,272, No. 2,474,293
No. 2,521,908, JP-A-48-59838.
No. 51-26034, U.S. Pat. No. 2,875,05
7, 3,265,506, West German Patent 1,547,
868, West German Application Publication No. 2,219,917, U.S. Pat. No. 1,425,020, JP-A-51-10783,
U.S. Pat. Nos. 2,600,788 and 2,983,608
No., West German Patent 1,810,454, West German Patent Application (O
LS) 2,408,665, JP-B-40-6031
No., JP-A-51-20826, Journal of the Chemical Society, Perkin Transactions I (J. Chem. Soc., Perkin Tr.
ans. I), (1977), 2047-2052, U.S. Pat. No. 3,725,067, JP-A-59-99437.
Nos., 60-172982 and 60-190779
A person skilled in the art can easily synthesize the compound by referring to the methods described in the above items.

The amount of the water-soluble coupler according to the present invention is not particularly limited, but is preferably from 1 mmol to 150 mmol / l, more preferably from 5 mmol to 100 mmol / l.
In the case of liter, the effect of the present invention is remarkable and particularly preferable.

The water-soluble coupler according to the present invention may contain at least one kind, but two or more kinds may be used in combination.

The amplification developer according to the present invention may contain the above-mentioned water-soluble coupler in advance, or may be formed by being eluted from the photosensitive material during the amplification development. The effect of the present invention is particularly remarkable if it is previously contained in the amplification developer, which is preferable.

The mode in which the water-soluble coupler according to the present invention is contained in an amplification developer substantially free of a color developing agent described later is particularly preferred because the effects of the present invention are high. Here, the term "substantially not containing a color developing agent" means a state in which the color developing agent is not previously added to the amplification developer, and is incorporated in the photosensitive material or impregnated in the photosensitive material. The color developing agent brought in by the processing solution is not included.

Further, the water-soluble coupler according to the present invention is particularly preferably contained in an amplification developer containing at least one oxidizing agent for amplification development described later, because the effect of the present invention is high.

The invention according to claim 4 is characterized in that the amplification developer contains at least one kind of radical scavenger.

As described in JP-A-8-62768, “0018”, the radical scavenger in the present invention is obtained by adding galvinoxyl to 0.05 g at 25 ° C.
mmoldm ^-3 ethanol solution and 2.5 of test compound
An ethanol solution of mmoldm- ^{3 is} mixed by the stopped flow method, and the time change of the absorbance at 430 nm is measured, and a compound that substantially discolors galvinoxyl (decreases the absorbance at 430 nm) is used. May be measured at a lower concentration).

Preferably, the decoloration rate constant of galvinoxyl determined by the above method is 0.01 mmol ⁻¹ s ⁻¹ d.
m ³ or more, more preferably 0.1 mmol ⁻¹ s ⁻¹ dm ³ or more.

The method for determining the radical scavenging rate using galvinoxyl is described in Microchem. J., Vol. 31, pp. 18-21 (1985). The stopped flow method is described in, for example, No. 6, page 321 (1970).

A scavenger preferably used in the present invention is represented by the following general formula (B).

In the formula (B), R ³¹ -N (OH) -R ³² , wherein R ³¹ is an alkyl group (having preferably 1 to 36 carbon atoms, more preferably 1 to 26 carbon atoms, for example, methyl, Ethyl, i-propyl, cyclopropyl, i-
Butyl, cyclohexyl, t-octyl, decyl, dodecyl, hexadecyl, benzyl, etc.), alkenyl group (preferably having 2 to 36 carbon atoms, more preferably having 2 to 2 carbon atoms)
6, such as vinyl, allyl, i-propenyl, 2
-Butenyl, oleyl and the like), an aryl group (having preferably 6 to 40, more preferably 6 to 30 carbon atoms,
For example, phenyl, naphthyl and the like), a heterocyclic group (a group forming a 5- to 7-membered heterocyclic ring having at least one of a nitrogen atom, a sulfur atom, an oxygen atom and a phosphorus atom as a ring-constituting atom, preferably a nitrogen-containing heterocycle) Ring having from 1 to 4 nitrogen atoms, most preferably from 5 to 5 having from 1 to 3 nitrogen atoms
6-membered heterocyclic groups such as 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, pyridyl, pyrazinyl, pyrimidinyl, prenyl, quinolyl, imidazolyl, 1,2,4-triazole -3-yl, benzimidazol-2-yl, thienyl, furyl, imidazolidinyl, pyrrolinyl, tetrahydrofuranyl, morpholinyl, piperazinyl, etc.), acyl group (acetyl, benzoyl, pivaloyl, α- (2,4-di-t) -Pentylphenoxy) butyryl, myristoyl, stearoyl,
Naphthoyl, 2-pentadecylbenzoyl, isonicotinoyl and the like, a sulfonyl group (preferably an alkyl or arylsulfonyl group such as methanesulfonyl, butanesulfonyl, benzenesulfonyl, toluenesulfonyl and the like), a sulfinyl group (preferably an alkyl or arylsulfinyl group, for example, Methanesulfinyl, benzenesulfinyl, etc.), carbamoyl group (N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl, N-butyl-N-phenylcarbamoyl, etc.), sulfamoyl group (N-methylsulfamoyl, N -Phenylsulfamoyl, N, N-diethylsulfamoyl, N-ethyl-N-dodecylsulfamoyl, etc.), alkoxycarbonyl group (methoxycarbonyl, i-pentyloxy) It represents carbonyl, cyclohexyl oxycarbonyl, benzyloxycarbonyl, and octadecyloxycarbonyl) or an aryloxycarbonyl group (phenoxycarbonyl, naphthoxycarbonyl, etc.).

R ³² represents a hydrogen atom or the same group as represented by R ³¹ .

Examples of the 5- to 7-membered ring which may be formed by combining R ³¹ and R ³² include succinimide, phthalimide, triazole, urazole, hydantoin, 2-oxo-4-oxazolidinone ring and the like.

The groups represented by R ³¹ and R ³² may further have a substituent, such as an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, an alkoxy group, an aryloxy group, Alkylthio group, arylthio group, amino group (including substituted amino group), acylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group, halogen atom, cyano group, nitro group, sulfonyl group, acyl group, Examples thereof include an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and a hydroxyamino group.

Hereinafter, typical specific examples of the radical scavenger represented by the general formula (B) will be shown.

[0167]

Embedded image

[0168]

Embedded image

[0169]

Embedded image

[0170]

Embedded image

[0171]

Embedded image

The amount of the radical scavenger according to the present invention is not particularly limited, but is preferably from 1 mmol to 500 mmol / l, and more preferably from 5 mmol to 250 mmol / l, the effect of the present invention is remarkable. And particularly preferred.

The radical scavenger according to the present invention may contain at least one kind, but two or more kinds may be used in combination.

Next, a description common to the present invention according to claims 1 to 9 will be given.

Examples of the oxidizing agent for amplification and development according to the present invention include:
For example, compounds providing hydrogen peroxide such as hydrogen peroxide, salts of hydrogen peroxide, and adducts of hydrogen peroxide; peroxo compounds such as peroxoborates and peroxocarbonates; and cobalt (III) complexes such as cobalt hexaammine complexes. ,
Halogenous acids such as chlorous acid and periodic acid can be used. Among them, a method using a compound that gives hydrogen peroxide such as hydrogen peroxide, a salt of hydrogen peroxide, and an addition compound of hydrogen peroxide as an oxidizing agent is advantageous because the amplification effect is high and the load on the environment is reduced. It is.

As the color developing agent used in the amplification developer according to the present invention, an aromatic primary amine color developing agent is preferably used. For example, N, N-diethyl-p-phenylenediamine, 2-amino-5-diethylamino Toluene, 2-amino-5- (N-ethyl-N-laurylamino) toluene, 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline, 2-methyl-4- (N-
Ethyl-N- (β-hydroxyethyl) amino) aniline, 4-amino-3-methyl-N-ethyl-N- (β-
(Methanesulfonamido) ethyl) -aniline, N-
(2-amino-5-diethylaminophenylethyl) methanesulfonamide, N, N-dimethyl-p-phenylenediamine, 4-amino-3-methyl-N-ethyl-N
-Methoxyethylaniline, 4-amino-3-methyl-
N-ethyl-N- (β-ethoxyethyl) aniline, 4
-Amino-3-methyl-N-ethyl-N-([gamma] -hydroxypropyl) aniline and the like.

In addition to the aromatic primary amine color developing agents, for example, EP-A-565165 and EP-A-572054
And 593110, JP-A-8-202002, JP-A-8-227131, JP-A-8-234390 and the like can also preferably use the sulfonylhydrazide and carbonylhydrazide type color developing agents.

A black-and-white developing agent can be used in combination with the amplification developer according to the present invention. Examples of black-and-white developing agents include dihydroxybenzenes, 3-pyrazolidones, pyrogallols, glycines, hydroxylamines, hydrazines, aminophenols, reductones,
Aminopyrazolines and the like.

The mode in which the black-and-white developing agent is contained in the amplification processing solution containing the above-described color developing agent is preferable from the viewpoint of improving the color forming speed of the lowermost layer.

The ratio between the black-and-white developing agent and the color developing agent is arbitrary, but the molar ratio of the black-and-white developing agent to the color developing agent is preferably in the range of 0.02 to 2.0, particularly preferably 0.1 to 2.0. A range of from 1.0 to 1.0 is particularly preferable because it is easy to achieve both a low minimum density and a high maximum density.

The amplification developer according to the present invention may contain a known compound such as a pH buffer, an inhibitor, a preservative, and a sequestering agent.

Examples of the pH buffer include potassium or sodium carbonate, sodium or potassium hydrogen carbonate, potassium or sodium borate, potassium or sodium phosphate, disodium or potassium hydrogen phosphate, sodium or potassium dihydrogen phosphate, and water. Calcium oxide, sodium silicate, β-alanine diacetate, arginine, asparagine, ethylenediamine, ethylenediaminetetraacetic acid, ethylenediaminedisuccinate, glycine, histidine, imidazole, isoleucine, leucine, methyliminodiacetic acid, nicotinic acid, nitrilotriacetic acid, piperidine , Proline, purine, and pyrrolidine.

Examples of the inhibitor include halide ions such as chloride ion, bromide ion and iodide ion, or benzotriazole, 5-nitrobenzotriazole, 5-methylbenzotriazole, adenine, 1-
Known inhibitors such as phenyl-5 mercaptotetrazole can be mentioned.

Examples of the preservative include known preservatives such as sodium sulfite, potassium sulfite, hydroxylamine and diethylhydroxylamine.

Examples of the sequestering agent include ethylenediaminetetraacetic acid, 1,2-propylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, iminodiacetic acid, trimethylenetetraaminehexaacetic acid, ethylenediaminetetrapropionic acid, tr
ans-cyclohexane-1,2-diaminetetraacetic acid, ethylenediamine-N, N'-diacetate-N, N'-
Examples thereof include aminopolycarboxylic acids such as dipropionic acid and salts thereof, 1-hydroxy-ethylidene-1,1-diphosphonic acids and salts thereof, catechol disulfonic acids and salts thereof, and pyridine-2-carboxylic acids and salts thereof. In particular, when a sequestering agent having a stability constant with Fe ²⁺ or Ag ⁺ of 5.0 or more is used, the present invention is particularly effective against variations in processing temperature, processing solution supply timing, and the like. This is preferable because the effect of can be stably reproduced.

In the present invention, it is possible to supply a processing solution containing the above color developing agent and an oxidizing agent for amplification development to a photographic material, or a processing solution containing a developing agent and an oxidizing agent for amplification development. A liquid containing the agent is divided into a plurality and prepared,
It is also possible to supply to a photosensitive material.

The image forming method according to the present invention is described, for example, in JP-A-52-13335 and JP-A-55-127555.
As described in JP-A-61-77851 and the like, a developing agent and an oxidizing agent are present in the same processing bath (developing / amplifying solution) to produce developed silver as a catalyst and the subsequent amplification development processing. A method performed in the same bath, JP-A-5-216192,
As described in JP-A-5-346647 and the like, a method in which a developing bath containing a developing agent and an amplification bath containing an oxidizing agent are separated, silver is formed in the developing bath, and the developing agent is brought into the amplification bath and amplified and developed. Or JP-A-61-88259.
As described in JP-A No. 7-077788, etc., after processing in a developing bath containing a developing agent to form developed silver, and then performing amplification development in a processing bath containing a developing agent and an oxidizing agent. Can be As a processing method without using a processing bath, for example, a method of spraying a developing solution, an amplifying solution, or an amplifying developing solution in a mist onto a silver halide photosensitive material as described in JP-A-61-80150, etc. Can be used.

When the developing bath and the amplification bath are separated, the preferred amount of the developing agent in the developing solution is 0.2 to 20 g / l, particularly preferably 1 to 10 g / l. The amount of hydrogen peroxide (30% solution) in the amplification solution is 0.1 to 100 ml / l.

When processing is carried out in a single bath comprising a developing bath and an amplification bath, the preferred amount of the developing agent in the developing / amplifying solution is 0.5 to
15 g / l, more preferably 1 to 7 g / l, and the preferred amount of hydrogen peroxide (30% solution) is 0.1 to 30 m
1 / l, more preferably 1 to 5 ml / l.

In the present invention, the amplification developer (the above-described developer, amplification solution, and development / amplification solution) can be used in an arbitrary pH range.
It is preferably from 9.0 to 12.5, and more preferably used in the range of pH 10.5 to 12.0.

The processing temperature for amplification development according to the present invention is 20
The temperature is preferably at least 60 ° C and not more than 60 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, it is preferable that the temperature is not too high.

The amplification development time varies depending on the type of photosensitive material, the processing temperature, the activity of the processing solution, and the like.
It is preferably performed within 0 seconds, more preferably within 90 seconds.

Next, the photosensitive material according to the present invention will be described.

The composition of the silver halide emulsion used in the light-sensitive material of the present invention may have a silver chloride content of at least 80 mol%, and may include silver chlorobromide, silver chloroiodobromide, silver chloroiodide, and silver chloride. Any silver halide emulsion such as silver can be used alone or in combination of two or more.

As the silver halide emulsion used in the light-sensitive material according to the present invention, a silver halide emulsion having a portion containing silver bromide at a high concentration can be preferably used.
In this case, the portion containing a high concentration of silver bromide may be a so-called core / shell emulsion in which a complete layer is formed, or a region in which the complete layer is not formed and the composition is merely partially present. In this case, what is called an epitaxy junction may be used. Further, the composition may change continuously or discontinuously. It is particularly preferable that the portion where silver bromide is present at a high concentration is present at the top of silver halide grains.

The silver halide emulsion used in the light-sensitive material of the present invention may contain heavy metal ions for the purpose of improving various photographic characteristics. Such heavy metal ions include iron, iridium, platinum, palladium,
Group 8 to 10 metals such as nickel, rhodium, osmium, ruthenium, and cobalt; and cadmium, zinc, and group 12 transition metals such as mercury; lead, rhenium, molybdenum;
Examples include tungsten, gallium, and chromium ions. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferred.

These heavy metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt.

When the heavy metal ion forms a complex, the ligand may be a cyanide ion, thiocyanate ion, isothiocyanate ion, cyanate ion, or the like.
Examples include chloride ion, bromide ion, iodide ion, carbonyl, nitrosyl, and ammonia.
Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

In order to incorporate heavy metal ions into the silver halide emulsion used in the light-sensitive material according to the present invention, the heavy metal ion or a complex containing the heavy metal ion is added before silver halide grains are formed and during the formation of silver halide grains. May be added at any point in each step during physical ripening after the formation of silver halide grains. During the formation of silver halide grains, heavy metal ions or complexes containing them are dissolved together with halide salts. Can be continuously added over the whole or a part of the particle forming process.

When the heavy metal ion is added to the silver halide emulsion, the amount is 1 × 10 ^-9 per mol of silver halide.
Mol or more and 1 × 10 ^-2 mol or less, particularly 1 mol
It is preferably at least 10 ^-8 mol and not more than 5 10 ^-5 mol.

The shape of the silver halide grains used in the light-sensitive material according to the present invention is arbitrary. One preferred example is
It is a cube having a {100} plane as a crystal surface. U.S. Pat. Nos. 4,183,756 and 4,225,6
No. 66, JP-A-55-26589, JP-B-55-42
No. 737 and The Journal of Photographic Science (J. Photogr. Sci.) 2
1, 39 (1973), etc., particles having an octahedral, tetradecahedral, dodecahedral or the like shape can be prepared and used. Further, particles having a twin plane may be used.

As the silver halide grains according to the present invention, grains having a single shape are preferably used, but it is also preferable to add two or more monodispersed silver halide emulsions to the same layer.

As the apparatus and method for preparing a silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion used in the light-sensitive material according to the present invention may be obtained by any of an acidic method, a neutral method, and an ammonia method. The particles may be grown at a time, or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The form of reacting the soluble silver salt with the soluble halide salt may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Also, JP-A-57-92523 and JP-A-57-92523.
No.-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device disposed in a reaction mother liquor, and a water-soluble silver described in German Offenlegungsschrift 2,921,164, etc. A device for continuously adding a salt and an aqueous solution of a water-soluble halide salt while changing the concentration,
No. 501776, etc., a reaction mother liquor may be taken out of a reactor and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant. If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

As the silver halide grains used in the light-sensitive material of the present invention, so-called tabular silver halides are preferably used in order to control gradation balance. As tabular grains containing silver chloride at a high concentration, grains having a {111} major plane and grains having a {100} major plane are known. Particles having a flat surface are particularly preferably used.

The use of tabular silver halide grains in the light-sensitive material of the present invention has the advantage that the bleaching time of the peracid bleaching composition can be shortened, and is particularly preferred.

The silver halide emulsion used in the light-sensitive material of the present invention can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer.

As the chalcogen sensitizer applied to the silver halide emulsion used in the light-sensitive material according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, and the like can be used. Sensitizers are preferred.

The silver halide emulsion used in the light-sensitive material according to the present invention prevents fog generated during the preparation step of the light-sensitive material, reduces performance fluctuation during storage, and prevents fog generated during development. Known antifoggants and stabilizers can be used for the purpose. Examples of preferred compounds that can be used for such a purpose are described in
The compound represented by the general formula (II) described in the lower column of page 1 of JP-A-146036 can be exemplified. These compounds are added according to the purpose in a step of preparing a silver halide emulsion, a step of chemical sensitization, at the end of the step of chemical sensitization, a step of preparing a coating solution and the like.

In the light-sensitive material according to the present invention, the total amount of the light-sensitive silver halide contained in the light-sensitive material was 0.3 g / g.
m ² or less, and the amount of silver halide contained in each photosensitive layer is preferably 0.1 g / m ² or less. When the amount of silver halide is in the above range, the load on the desilvering treatment is small, and the ratio of the development reaction in the own layer to the influence of the development reaction in the other layer is small, and the stability of gradation reproduction is improved, which is preferable. The preferable amount of silver halide is 0.001 to 0.001 per each image forming layer.
0.1 g / m ² , more preferably 0.01 to
It is in the range of 0.08 g / m ² .

The coupler used in the light-sensitive material according to the present invention may be any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm by coupling reaction with an oxidized form of a color developing agent. Although it is also possible to use, particularly typical examples include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, A typical example is a cyan dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm.

The cyan coupler preferably usable in the light-sensitive material of the present invention is described in JP-A-4-11415.
The general formula (C-I) described in the lower left column of page 4, No. 5, page 5,
A coupler represented by formula (C-II):
The general formulas (Ia), (Ia) and
b) and cyan couplers represented by (Ic);
General formulas (IIα) to (VIIIα) described in the lower right column of page 6 to the upper left column of page 7 and the lower right column of page 7
The cyan couplers represented by the general formulas (IIβ) to (VIIIβ) described in the upper left column of page 8 can be mentioned. Especially,
Formulas (IIα) to (VIIIα) and (IIβ) to (VIII
The cyan coupler represented by β) is preferable because it has sharp image dye absorption and excellent color reproducibility.

The magenta coupler which can be preferably used in the light-sensitive material of the present invention is described in JP-A-4-1141.
General formula (MI) described in the upper right column on page 4 of JP-A No. 54,
The coupler represented by (M-II) can be mentioned.
More preferred among the above magenta couplers are the couplers represented by the general formula (MI) described in the upper right column on page 4 of the publication, and among them, the RM of the above general formula (MI)
Is a tertiary alkyl group, which is excellent in light resistance and particularly preferred.

The yellow coupler which can be preferably used in the light-sensitive material according to the present invention is described in JP-A No. 4-11 / 1990.
The general formula (Y-
The couplers represented by I) can be mentioned. Of these, couplers in which RY1 in the general formula [Y-1] is an alkoxy group or couplers represented by the general formula [I] described in JP-A-6-67388 can reproduce yellow having a preferable color tone and are preferable. The most preferred compounds are those represented by the general formula [Y-1] described in JP-A-4-81847, page 1 and pages 11 to 17 of the same.

When an oil-in-water emulsion dispersion method is used to add the couplers and other organic compounds used in the light-sensitive material according to the present invention, they are usually added to a high-boiling organic solvent and, if necessary, to a low-boiling organic solvent. And / or dissolved together with a water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. The high-boiling organic solvent that can be used for dissolving and dispersing the coupler preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

As a compound preferable as a surfactant used for dispersing a photographic additive or adjusting a surface tension at the time of coating, a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule are preferable. Containing. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time until the addition to the coating solution after the dispersion and the time from the addition to the coating solution to the coating are preferably as short as 10 hours each. Preferably within 3 hours, more preferably within 20 minutes.

The coupler includes light of the formed dye image,
In order to prevent discoloration due to heat, humidity and the like, it is preferable to use a discoloration inhibitor in combination. Particularly preferred compounds include phenyl ether compounds represented by general formulas I and II described on page 3 of JP-A-2-66541,
No. 174150, a phenolic compound represented by the general formula IIIB, JP-A-64-90445, an amine compound represented by the general formula A, and JP-A-62-18.
Metal complexes represented by the general formulas XII, XIII, XIV and XV described in JP-A-2741 are particularly preferable for magenta dyes. Further, compounds represented by the general formula I 'described in JP-A-1-19649 and compounds represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, the compound (d-11) described in the lower left column of page 9 of JP-A-4-114154 and the compound (A'-1) described in the lower left column of page 10 of the same publication are disclosed. And the like. In addition, the fluorescent dye releasing compounds described in U.S. Pat. No. 4,774,187 can also be used.

In the light-sensitive material according to the present invention, a compound which reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity or added to a silver halide emulsion layer. It is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone.

It is preferable to add an ultraviolet absorber to the light-sensitive material according to the present invention to prevent static fog or improve the light fastness of a dye image. Preferable ultraviolet absorbers include benzotriazoles. Particularly preferred compounds are compounds represented by the formula III-3 described in JP-A-1-250944, and JP-A-64-6664.
6, a compound represented by the general formula III,
UV-1L to UV-27 described in 3-187240
L, compounds represented by the general formula I described in JP-A-4-1633, and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

In the light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used. In particular, dyes having absorption in the visible region include those described in JP-A-3-2518.
The dyes of AI-1 to 11 described on page 308 of JP-A-40 and the dyes described in JP-A-6-3770 are preferably used.
General formula (I) described in the lower left column of page 2 of JP-A-750-750,
The compounds represented by (II) and (III) have preferable spectral characteristics, do not affect the photographic characteristics of the silver halide photographic emulsion, and do not cause contamination due to residual color.

In order to improve the sharpness, the amount of these dyes added was 680 nm for the unprocessed sample of the light-sensitive material.
Is preferable to make the spectral reflection density 0.7 or more, more preferably 0.8 or more.

It is preferable to add a fluorescent whitening agent to the light-sensitive material according to the present invention because whiteness can be improved. Preferred examples of the compound include a compound represented by the general formula II described in JP-A-2-232652.

When the light-sensitive material according to the present invention is used as a color photographic light-sensitive material, it is combined with a yellow dye-donating substance, a magenta dye-donating substance, and a cyan dye-donating substance and spectrally sensitized to a specific region in a wavelength region of 400 to 900 nm. And a layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

As the spectral sensitizing dye, any known compounds can be used. As the blue-sensitive sensitizing dye, BS-1 to 8 described in JP-A-3-251840, page 28, can be used alone. Or in combination. As the green photosensitive sensitizing dye, the same publication 2
GS-1 to GS-5 described on page 8 are preferably used.
As the red-sensitive sensitizing dye, R 29 described in
S-1 to S-8 are preferably used. In the case of performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye. The dyes of IRS-1 to 11 described in JP-A No. 6-8 are preferably used. These infrared, red, green, and blue light-sensitive sensitizing dyes include supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pp. 8-9, and JP-A-5-6.
Compound S-1 described in No. 6515, pages 15 to 17
It is preferable to use a combination of -S-17.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

As a method for adding the sensitizing dye, the sensitizing dye may be dissolved in water or a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone or dimethylformamide or water and added as a solution, or may be added as a solid dispersion. It may be added.

In the light-sensitive material according to the present invention, it is advantageous to use gelatin as a binder. If necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, A hydrophilic colloid such as a sugar derivative, a cellulose derivative, or a synthetic hydrophilic polymer such as a homopolymer or a copolymer can also be used.

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination.
It is preferable to use the compounds described in JP-A Nos. 9054 and 61-245153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the colloid layer in order to prevent the growth of mold and bacteria which adversely affect photographic performance and image storability. It is preferable to add a slipping agent or matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer in order to improve the physical properties of the surface of the photosensitive material or the processed sample.

As the support used in the light-sensitive material according to the present invention, any material may be used, such as paper coated with polyethylene or polyethylene terephthalate, a paper support made of natural pulp or synthetic pulp, a vinyl chloride sheet, For example, polypropylene, polyethylene terephthalate support, baryta paper, etc. which may contain a white pigment can be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable. As the water-resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

As the white pigment used for the support, inorganic and / or organic white pigments can be used, and preferably, inorganic white pigments are used.

Further, it is more preferable that the value of the center plane average roughness (SRa) of the support is 0.15 μm or less, and more preferably 0.12 μm or less, since the effect of good gloss can be obtained. In addition, trace amounts of ultramarine, oil-soluble dyes, etc. to adjust the spectral reflection density balance of the white background after treatment in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer to improve whiteness It is preferable to add a bluing agent or a reddish agent.

The light-sensitive material of the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface, if necessary, and then directly or undercoating (adhesion, antistatic property of the support surface, It may be applied via one or more undercoat layers for improving dimensional stability, friction resistance, hardness, antihalation properties, friction properties and / or other properties.

At the time of coating the light-sensitive material according to the present invention, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

In order to form a photographic image using the photosensitive material according to the present invention, the image recorded on the negative may be optically focused on the photosensitive material to be printed and printed. Also, the image may be once converted into digital information, then the image may be formed on a CRT (cathode ray tube), and this image may be formed on a photosensitive material to be printed and printed. The printing may be performed by scanning while changing the light intensity or the irradiation time.

The image forming method of the present invention is particularly preferably applied to a photosensitive material for forming an image for direct viewing. For example, color paper, color reversal paper, a photosensitive material for directly forming a positive image, a photosensitive material for a display, and a photosensitive material for a color proof can be used. It is particularly preferable to apply the invention to a photosensitive material having a reflective support.

In the image forming method of the present invention, after the amplification and development, bleaching and fixing may be performed as required. The bleaching process may be performed simultaneously with the fixing process.
After the fixing process, a water washing process is usually performed. Also,
As an alternative to the water washing treatment, a stabilization treatment may be performed.

As the processing apparatus used in the image forming method of the present invention, even if it is a roller transport type in which the photosensitive material is conveyed between rollers arranged in a processing bath, the photosensitive material is fixed on a belt and conveyed. An endless belt method may be used, but a processing bath is formed in a slit shape, and a processing method for supplying a processing liquid to the processing bath and transporting the photosensitive material, and a spray method for spraying the processing liquid,
A web method by contact with a carrier impregnated with the processing solution,
A method using a viscous treatment liquid can also be used.

[0241]

Next, the present invention will be described based on examples, but embodiments of the present invention are not limited to these examples.

Embodiment 1 Embodiment 1 is an embodiment of the image forming method according to the present invention.

(Blue-sensitive silver halide emulsion (Em-B
Preparation of 1) pAg = (A1 solution) and (B1 solution) below in 1 liter of a 2% aqueous gelatin solution kept at 40 ° C.
7.3, pH = 3.0 were added simultaneously while controlling, and the following (solution C1) and (solution D1) were further pAg = 8.0, pH =
Simultaneous addition was performed while controlling to 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437.
The pH was controlled using sulfuric acid or an aqueous sodium hydroxide solution.

(A1 solution) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B1) Silver nitrate 10 g Water was added to 200 ml (Solution C1) Sodium chloride 102.7 g Potassium hexachloroiridium (IV) ate 4 × 10 ⁻⁸ mol Potassium hexacyanoferrate (II) 2 × 10 ⁻⁵ mol Potassium bromide 1.0 g Add water 600 ml (Solution D1) Silver nitrate 300 g Add water 600 ml after completion of addition, Kao Atlas Demol After desalting using a 5% aqueous solution of N and a 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to obtain an average particle size of 0.57 μm.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1A was obtained. The above-mentioned EMP-1A was optimally subjected to chemical sensitization at 60 ° C. using the following compounds to give a blue-sensitive silver halide emulsion (Em-B).
1) was obtained.

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5
-Mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole (Preparation of green photosensitive silver halide emulsion (Em-G1)) In the preparation of silver halide emulsion EMP-1A,
Except that the addition time of (A1 solution) and (B1 solution) and the addition time of (C1 solution) and (D1 solution) were changed, the average particle diameter was 0.30 μm and the silver chloride content was 99.5 mol%. A monodispersed cubic emulsion EMP-11A was obtained. EMP-11 above
A was optimally subjected to chemical sensitization at 60 ° C. using the following compound to obtain a green photosensitive silver halide emulsion (Em-G1).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ^-4 mol / mol AgX Stabilizer STAB-3 3 × 10 ^-4 mol / mol AgX (Preparation of red-sensitive silver halide emulsion (Em-R1)) The above-mentioned silver halide emulsion In preparing EMP-1A,
Except that the addition time of (solution A1) and (solution B1) and the addition time of (solution C1) and (solution D1) were changed, the average particle diameter was 0.32 μm and the silver chloride content was 99.5 mol%. A monodispersed cubic emulsion EMP-21A was obtained. The above EMP-21
A was optimally subjected to chemical sensitization at 60 ° C. using the following compound to obtain a red-sensitive silver halide emulsion (Em-R1).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX SS-1 2.0 × 10 ⁻³ mol / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-3 3 × 10 ^-4 mol / mol AgX

[0248]

Embedded image

(Preparation of photosensitive materials (101) and (102)) High-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to prepare a paper support. However,
On the side on which the emulsion layer was coated, a molten polyethylene containing anatase-type titanium oxide having a surface treatment dispersed therein at a content of 15% by weight was laminated. After the reflective support was subjected to corona discharge treatment, a gelatin undercoat layer was provided thereon, and each layer having the following constitution was further provided thereon to prepare a silver halide photographic material (101). In the preparation of the photosensitive material, each coating solution was prepared so as to have the following coating amount, and (H-1) and (H-2) were added as hardening agents. Surfactants (SU-1), (SU-2), (S
U-3) was added to adjust the surface tension. Further, (F-1) was added to each layer so that the total amount became 0.04 g / m ² .

The coating amount of each layer is shown below.

Layer composition Addition amount (g / m ² ) 7th layer (protective layer) Gelatin 1.00 DIDP 0.002 DBP 0.002 Silicon dioxide 0.003 6th layer (UV absorbing layer) Gelatin 0.40 AI-1 0.01 UV absorber (UV-1) 0.12 UV absorber (UV-2) 0.04 UV absorber (UV-3) 0.16 Stain inhibitor (HQ-5) 0.04 PVP 0.03 Fifth layer (red-sensitive layer) Gelatin 1.30 Red-sensitive emulsion (Em-R1) 0.020 Cyan coupler (C-1) 0.28 Dye image stabilizer (ST-1) 0 .10 Anti-stain agent (HQ-1) 0.004 DBP 0.10 DOP 0.20 Fourth layer (ultraviolet absorbing layer) Gelatin 0.94 Ultraviolet absorbing agent (UV-1) 0.28 Ultraviolet absorbing agent (UV- 2) 0.09 UV absorption Collector (UV-3) 0.38 AI-1 0.02 Stain inhibitor (HQ-5) 0.10 Third layer (green-sensitive layer) Gelatin 1.30 AI-2 0.01 Green-sensitive emulsion (Em-G1) 0.025 Magenta coupler (M-1) 0.20 Dye image stabilizer (ST-3) 0.20 Dye image stabilizer (ST-4) 0.17 DIDP 0.13 DBP 0 .13 second layer (middle layer) gelatin 1.20 AI-3 0.01 anti-stain agent (HQ-2) 0.03 anti-stain agent (HQ-3) 0.03 anti-stain agent (HQ-4) 0 0.05 Stain inhibitor (HQ-5) 0.23 DIDP 0.04 DBP 0.02 Fluorescent brightener (W-1) 0.10 First layer (blue-sensitive layer) Gelatin 1.20 Blue-sensitive emulsion (Em-B1) 0.062 Yellow coupler (Y- ) 0.70 Dye image stabilizer (ST-1) 0.10 Dye image stabilizer (ST-2) 0.10 Dye image stabilizer (ST-5) 0.10 Stain inhibitor (HQ-1) ) 0.01 Image stabilizer A 0.15 DBP 0.10 DNP 0.05 Support Polyethylene laminated paper The amount of silver halide applied was shown in terms of silver.

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sulfosuccinate sodium salt SU-3: di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) sodium salt H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium DBP: dibutyl phthalate DIDP: diisodecyl phthalate DOP : Dioctyl phthalate DNP: dinonyl phthalate PVP: polyvinylpyrrolidone HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di- sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di (1,1-dimethyl-4-hexyloxycarbonyl) butylhydroquinone Image stabilizer A : Pt-octylpheno Rule

[0253]

Embedded image

[0254]

Embedded image

[0255]

Embedded image

[0256]

Embedded image

Further, a light-sensitive material (102) was prepared in the same manner as in the preparation of the light-sensitive material (101), except that the amounts of silver halide in the first, third and fifth layers were changed as follows. photosensitive material (102) fifth layer red-sensitive emulsion (Em-R1) 0.18 g / m 2 layer 3 green-sensitive emulsion (Em-G1) 0.15 g / m 2 first layer blue-sensitive emulsion (Em-B1) 0.26 g / m ² The photosensitive materials (101), (10)
2) was subjected to light wedge exposure for 0.5 seconds with green light, developed or amplified by the following processing steps, and then desilvered by desilvering step 1. In addition,
During processing with each photographic processing solution, excess photographic processing solution present on the surface of the photosensitive material was removed with a blade made of silicon rubber.

The obtained sample was subjected to a densitometer PDA-6.
5 (manufactured by Konica Corporation), and the reflection density was measured. Next, using a microdensitometer PDM-5AR (manufactured by Konica Corporation), the maximum reflection density when the step where the green light reflection density is closest to 0.5 was scanned and measured in a range of 3 mm with an aperture size of 10 μm × 50 μm. The density difference was used as an evaluation scale for granularity. The smaller this value is, the better the granularity is, and the smaller the roughness of the printed image is. The results are shown in Table 1.

Processing Step A Processing Temperature Temperature Color Developer (CDC-1) 38.0 ± 0.5 ° C. 45 seconds Amplification Processing Step 1 Processing Temperature Temperature Amplification Developer (CDA-1) 33. 0 ± 0.5 ° C. 50 seconds Amplification process step 2 Processing temperature Time 1st processing solution (CD-1) 36.0 ± 0.5 ° C. 20 seconds 2nd processing solution (OX-1) 36.0 ± 0.5 ° C. 20 seconds Desilvering process 1 Processing time Processing temperature Bleaching / fixing solution (BF-1) 30 seconds 35.0 ± 0.5 ° C. Stabilizing solution 60 seconds 30-34 ° C. Drying 30 seconds 60-80 ° C. The composition of the treatment liquid is shown below.

Color developer (CDC-1) Pure water 800 ml Triethylenediamine 2 g Potassium bromide 0.01 g Potassium chloride 1.0 g Potassium sulfite 0.25 g N-ethyl-N- (β methanesulfonamidoethyl) -3-methyl -4-aminoaniline sulfate 6.0 g N, N-diethylhydroxylamine 6.8 g triethanolamine 10.0 g diethylenetriaminepentaacetic acid sodium salt 2.0 g potassium carbonate 30 g water-soluble surfactant described in Table 1 The total volume is made up to 1 liter and adjusted to pH 10.1 with sulfuric acid or potassium hydroxide.

Amplification developer (CDA-1) Pure water 800 ml Potassium bromide 0.001 g Potassium chloride 0.35 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 4 0.0 g N, N-diethylhydroxylamine 4.7 g Diethylenetriaminepentaacetic acid sodium salt 2.0 g 1-hydroxyethylidene-1,1′-diphosphonic acid 0.35 g Potassium carbonate 20 g Water-soluble surfactant Hydrogen peroxide Water (30%) 5.0 ml Water was added to make the total volume 1 liter, and pH = 10 with sulfuric acid or potassium hydroxide. Adjust to 8.

First treatment liquid (CD-1) Pure water 800 ml Potassium bromide 0.001 g Potassium chloride 0.35 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 10.0 g L-ascorbic acid 3.0 g Water-soluble surfactant described in Table 1 Adjust the pH to 8.0 with potassium hydroxide or sulfuric acid, and add water to make the total amount 1 liter.

Second treatment liquid (OX-1) Pure water 800 ml Disodium hydrogenphosphate 10 g Potassium carbonate 20 g Diethylenetriaminepentaacetic acid sodium salt 2.0 g 1-Hydroxyethylidene-1,1'-diphosphonic acid 0.35 g Water-soluble interface Activator Described in Table 1 Hydrogen peroxide (30%) 5.0 ml Adjust the pH to 11.0 with potassium hydroxide or sulfuric acid, and add water to make the total amount 1 liter.

Bleaching-fixing solution (BF-1) Pure water 700 ml Diethylenetriaminepentaacetate ammonium ferric dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4 -Thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Add water to make the total volume 1 liter, and adjust the pH to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing liquid Pure water 800 ml o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g diethylene glycol 1 0.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP (polyvinylpyrrolidone) 1.0g Ammonia water (25% aqueous solution of ammonium hydroxide) 2.5g Nitrilotriacetic acid trisodium salt 1.5g Add water to make the total volume 1 liter, and adjust the pH to 7.5 with sulfuric acid or ammonia water. I do.

[0266]

[Table 1]

In Table 1, No. From the comparison of Nos. 101 and 102, in the normal processing without amplification development, the presence or absence of the water-soluble surfactant in the processing liquid composition hardly contributed to the granularity. It can be seen that in the amplification and development processing of 103 to 129, the granularity is improved when a water-soluble surfactant is present in the processing solution. In addition, No.
From the comparison of Nos. 104 to 120, the processing solution composition containing the water-soluble surfactant contained No. 10 containing the oxidizing agent for amplification development. 1
04 to 107; 110, 112, 114, 11
6, 118 and 120 show that the effects of the present invention are particularly remarkable, and are thus preferable. In addition, No. From the comparison of 104 to 129, it can be seen that the effect of the present invention is particularly remarkable when the water-soluble surfactant is a nonionic or anionic surfactant, which is preferable.

Embodiment 2 Embodiment 2 is an embodiment of the image forming method according to the second aspect.

The photosensitive materials (101) and (102) prepared in Example 1 were exposed to green wedges for 0.5 second with a light wedge, and developed or amplified by the same processing steps as in Example 1. After that, the desilvering process in the desilvering process 1 was performed. During processing with each photographic processing solution, excess photographic processing solution present on the surface of the photosensitive material was removed with a blade made of silicon rubber. The same evaluation as in Example 1 was performed on the sample thus obtained.

In Example 2, the color developer (CDC-1), the amplification developer (CDA-1),
In each of D-1) and (OX-1), a compound represented by the general formula (A) was added as shown in Table 2 instead of the water-soluble surfactant.

[0271]

[Table 2]

In Table 2, No. From the comparison between Nos. 201 and 202, in the normal processing without amplification development, the presence or absence of the compound represented by the general formula (A) in the processing solution composition hardly contributed to the granularity. It can be seen that in the amplification and development processes 203 to 220, the granularity is improved when the compound represented by the general formula (A) is present in the processing solution. In addition, No. From the comparison of 204 to 220,
When the processing solution composition containing the compound represented by the general formula (A) contains no. 204-207, N
o. 209, 211, 213, 215, 217 and 21
No. 9 shows that the effect of the present invention is particularly remarkable and is preferable. In addition, No. From the comparison of 204 to 216, the compound represented by the general formula (A) was 3.0 × 10 ⁻³ mol to 9.0.
It can be seen that the effect of the present invention is particularly remarkable when it is a particularly preferred embodiment of the present invention of × 10 ^-2 mol / l, which is preferable.

Embodiment 3 Embodiment 3 is an embodiment of the image forming method according to the third aspect.

The light-sensitive materials (101) and (102) prepared in Example 1 were exposed to green wedge light for 0.5 seconds using a light wedge, and developed or amplified by the same processing steps as in Example 1. After that, the desilvering process in the desilvering process 1 was performed. During processing with each photographic processing solution, excess photographic processing solution present on the surface of the photosensitive material was removed with a blade made of silicon rubber. The same evaluation as in Example 1 was performed on the obtained sample.

In Example 3, the color developer (CDC-1), the amplification developer (CDA-1),
In each of D-1) and (OX-1), a water-soluble coupler was added as shown in Table 3 in place of the water-soluble surfactant.

[0276]

[Table 3]

In Table 3, no. Compared with 301 and 302, in the normal processing without amplification development, when a water-soluble coupler is present in the processing solution composition, the granularity is rather deteriorated as the maximum concentration decreases.
o. It can be seen that in the amplification and development processes 303 to 320, the granularity is improved when a water-soluble coupler is present in the processing solution. In addition, No. From the comparison of Nos. 304 to 320, the processing solution composition containing the water-soluble coupler contained no color developing agent. 310, 312, 314, 3
16, 318 and 320 show that the effects of the present invention are particularly remarkable and are preferable. In addition, No. 304-316
It can be seen from the comparison that the effect of the present invention becomes particularly remarkable when the water-soluble coupler is a particularly preferred embodiment of 5 to 100 mmol / l, which is preferable.

Embodiment 4 Embodiment 4 is an embodiment of the image forming method according to claim 4.

The light-sensitive materials (101) and (102) prepared in Example 1 were exposed to green wedges for 0.5 seconds with green light, and developed or amplified by the same processing steps as in Example 1. After that, the desilvering process in the desilvering process 1 was performed. During processing with each photographic processing solution, excess photographic processing solution present on the surface of the photosensitive material was removed with a blade made of silicon rubber. The same evaluation as in Example 1 was performed on the obtained sample.

In Example 4, the color developer (CDC-1), the amplification developer (CDA-1),
In each of D-1) and (OX-1), a radical scavenger was added immediately before the treatment as shown in Table 4 instead of the water-soluble surfactant.

[0281]

[Table 4]

In Table 4, No. From the comparison between Nos. 401 and 402, in the normal processing without amplification development, the granularity is hardly affected by the presence or absence of the radical scavenger in the processing solution composition. It can be seen that in the amplification development processes of 403 to 420, the granularity is improved when a radical scavenger is present in the processing solution. In addition, No. From the comparison of Nos. 404 to 420, the processing solution composition containing the radical scavenger contained no color developing agent. 410, 412, 414, 416,
418 and 420 show that the effects of the present invention are particularly remarkable and are preferable. In addition, No. From the comparison of 404 to 416, it can be seen that the effect of the present invention becomes particularly remarkable when the radical scavenger is 5 mmol to 2500 mmol / liter, which is a particularly preferred embodiment of the present invention.

Example 5 The photosensitive material (101) prepared in Example 1 was subjected to image exposure through a Konica Color LV400 color negative film which had been photographed and developed, and then subjected to the amplification described in Examples 1 to 4. The print image obtained by performing the development processing was observed. As a result, it was confirmed that the printed image created by using the image forming method of the present invention can reduce the roughness of the image, particularly in the highlight portion, and obtain a beautiful printed image.

[0284]

According to the present invention, a processing solution composition for amplification and development having improved graininess and an image forming method can be provided.

Claims (9)

[Claims] 1. A processing solution composition for amplification development comprising at least one water-soluble surfactant. 2. A processing solution composition for amplification and development comprising at least one compound selected from the compounds represented by the following general formula (A). Embedded image [Wherein, L represents an alkylene group which may be substituted, and A represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, an amino group which may be alkyl-substituted, or an ammonium group which may be alkyl-substituted. R represents a hydrogen atom or an alkyl group which may be substituted, and a carbamoyl group which may be alkyl-substituted or a sulfamoyl group which may be alkyl-substituted. ] 3. A processing solution composition for amplification development comprising a water-soluble coupler capable of performing a coupling reaction with an oxidized form of at least one color developing agent. 4. A processing solution composition for amplification and development comprising at least one kind of radical scavenger. 5. The processing solution composition for amplification development according to claim 1, wherein the water-soluble surfactant is a nonionic or anionic surfactant. 6. The processing solution composition for amplification development according to claim 1, further comprising at least one oxidizing agent for amplification development. 7. The processing solution composition for amplification development according to claim 2, comprising at least one type of color developing agent. 8. The processing solution composition for amplification development according to claim 3, wherein the composition does not substantially contain a color developing agent. 9. A support comprising at least one layer of a dye-providing substance and a photosensitive silver halide having a silver chloride content of at least 80 mol% in terms of silver of 0.001 g / m ^{2 to} 0.1 g / m ^{2. Two}
After imagewise exposing a silver halide photographic material having a color image forming layer to be contained, amplification processing is carried out using the processing solution composition for amplification development according to any one of claims 1 to 8. An image forming method comprising: