JPH10104808A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide color photographic sensitive material processable with an activator soln. which practically does not contain any developing agent, ensuring high coloring density and preventing the occurrence of stain during preservation over a long period of time after processing. SOLUTION: This silver halide color photographic sensitive material has at least one photosensitive silver halide emulsion layer and at least one nonphotosensitive layer as photographic constituent layers on the substrate and contains at least one kind of dye forming a coupler in either of the constituent layers and further contains at least one kind of reducing agent for coloring represented by the formula (L)n -D and at least one kind of nonphotosensitive inorg. compd. having a negatively charged surface. In the formula, L is an electron attracting group capable of being eliminated in the process of developing, D is a residual group of compd. obtd. by removing (n) H atoms from a compd. Hn D having development activity and (n) is an integer of 1-3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color photographic light-sensitive material, and more particularly, to a silver halide color photographic light-sensitive material capable of rapidly forming an image by processing in an alkali bath substantially containing no developing agent. More particularly, the present invention relates to a silver halide color photographic light-sensitive material excellent in color developing property and storage stability of the light-sensitive material.

[0002]

2. Description of the Related Art In general, a color photographic light-sensitive material undergoes color development after exposure, whereby an oxidized p-phenylenediamine derivative and a coupler react to form a color image. In this method, a color reproduction method using a subtractive color method is used, and in order to reproduce blue, green, and red, yellow, magenta, and cyan color images having complementary colors are formed. Conventional color development is achieved by immersing the exposed color photographic light-sensitive material in an aqueous alkali solution (color developer) in which a p-phenylenediamine derivative is dissolved. However, the p-phenylenediamine derivative in an alkaline aqueous solution is unstable and easily deteriorates with time, and it is necessary to frequently replenish the color developing solution to maintain stable developing performance. Further, the used color developer containing the p-phenylenediamine derivative is complicated in disposal processing,
Processing of a large amount of used color developing solution discharged is a problem. In order to simplify the handling of such a color developing solution and the waste liquid treatment, it is desired to form an image by processing with an alkaline solution (hereinafter referred to as an activator solution) not containing an unstable compound such as a p-phenylenediamine derivative. Have been.

In order to realize image formation with an activator solution not containing an unstable compound such as a p-phenylenediamine derivative, a method of incorporating an aromatic primary amine developing agent or a precursor thereof into a hydrophilic colloid is known. The aromatic primary amine developing agent or its precursor that can be incorporated is described in, for example, US Pat. No. 2,507,114.
Nos. 3,764,328 and 4,060,418
And compounds described in JP-A-56-6235 and JP-A-58-192031. However, since these aromatic primary amine developing agents and their precursors are unstable, they have a drawback that stain occurs during storage of unprocessed photographic materials or during color development. In other words, a developing agent used in normal photographic material processing cannot be used as it is (in terms of storage stability), and a developer designed to increase the oxidation potential in order to satisfy storage stability is not available. Sufficient development activity cannot be exhibited during processing.
As a method for solving this problem, it is conceivable to use, as a developing agent, a compound in which a group capable of leaving in a color developing process is introduced into a compound having development activity. For example, European Patent 0.5
Nos. 45,491A1 and 0,565,165A1, and the like, in which a sulfonylhydrazine-type compound is incorporated in a hydrophilic colloid layer. The sulfonylhydrazine-type compound mentioned here reacts with the dye-forming coupler during the color-forming process, and the sulfonyl group is released to form a dye. Examples of the developing agent in which a group capable of leaving during the color forming process is introduced into a compound having a developing activity include carbamoylhydrazine type compounds in addition to the above compounds (EP 0,727,708 A1). However, in any of the above compounds, when the processed photosensitive material is stored for a long period of time, stain is generated in an unexposed portion, and particularly in a sulfonyl hydrazine type compound, stain is significantly generated, and the level is sufficient for practical use. Did not.

[0004]

The method of incorporating a color-forming reducing agent having a group capable of leaving during the color-forming process in a light-sensitive material is effective to some extent in achieving both development activity and stain. The generation of stain during subsequent long-term storage cannot be sufficiently prevented, and further improvement has been demanded.
Accordingly, a first object of the present invention is to provide a silver halide color photographic light-sensitive material which can be processed with an activator solution containing substantially no developing agent. A second object of the present invention is to provide a silver halide color photographic light-sensitive material having a high color density and preventing the occurrence of stain during long-term storage after processing.

[0005]

It has been found that the object of the present invention can be attained by using the following light-sensitive materials. (1) A silver halide photosensitive material having a photographic component layer comprising at least one photosensitive silver halide emulsion layer and at least one non-photosensitive layer on a support, wherein a dye is contained in any of the photographic components. It contains at least one kind of a coupler formed, contains at least one kind of a color-forming reducing agent represented by the following general formula (D-1) and at least one kind of a non-photosensitive inorganic compound whose surface is negatively charged. A silver halide color photographic light-sensitive material, characterized in that: General formula (D-1)

[0006]

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(Wherein L is an electron-withdrawing group capable of leaving during the development process, and D is a compound HnD having development activity)
Is a compound residue excluding n hydrogen atoms, and n is 1
-3. (2) The silver halide color photographic material as described in (1), wherein the non-photosensitive inorganic compound is a swellable inorganic layered compound. (3) The silver halide color photographic material as described in the above item (1) or (2), wherein the color-forming reducing agent is a compound represented by the following general formula (D-8). Formula (D-8) R ¹¹ CONNHHR ¹² (wherein, R ¹¹ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, or an amino group, and R ¹² represents an aryl group or an aromatic group. (4) wherein the non-photosensitive inorganic compound is contained in a photographic component layer different from the layer containing the dye-forming coupler. 3. The silver halide color photographic light-sensitive material described in 1. above. (5) The weight ratio of the layer containing the non-photosensitive inorganic compound to the binder of the non-photosensitive inorganic compound is 1/10 to 10 /
Item 1. The silver halide color photographic light-sensitive material according to any one of Items (1) to (4). (6) The non-photosensitive inorganic compound has an average aspect ratio of 10
The silver halide color photographic light-sensitive material according to any one of (1) to (4), which is 0 or more. (7) The silver halide color photographic material as described in any of (1) to (6) above, wherein the non-photosensitive inorganic compound is a swellable synthetic mica. (8) The silver halide color photographic material as described in any of (1) to (5) above, wherein the non-photosensitive inorganic compound is bentonite.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a specific configuration of the present invention will be described in detail. The non-photosensitive inorganic compound having a negatively charged surface (hereinafter, abbreviated as an anionic inorganic compound) used in the present invention is a compound composed of an anionic inorganic ion or an inorganic complex ion, and is processed from a photosensitive material. There is no particular limitation as long as it does not substantially elute in the liquid. The anionic inorganic compound may be either a non-swellable inorganic layered compound or a swellable inorganic layered compound, but preferably a swellable inorganic layered compound. Examples of the swellable inorganic layered compound include swellable clay minerals such as bentonite, hectonite and montmorillonite, swellable synthetic mica, and swellable synthetic smectite. These swellable inorganic layered compounds have a laminated structure composed of unit crystal lattice layers having a thickness of 10 to 15 °, and the substitution of metal atoms in public and private areas is remarkably larger than that of other clay minerals. As a result, the lattice layer suffers from a lack of positive charge, and N.sub.
Cations such as a ⁺ , Ca ²⁺ , and Mg ²⁺ are adsorbed. The cations interposed between these layers are called exchangeable cations and exchange with various cations. In particular, when the cations between the layers are Li ⁺ and Na ⁺ , the bond between the layered crystal lattices is weak because the ionic radius is small, and the swells greatly with water. In this state, if it is strongly stirred or a strong local pressure is applied, it will be easily cleaved and form a stable sol in water. Bentonite and swellable synthetic mica have a strong tendency and are preferred for the purpose of the present invention. In particular, swellable synthetic mica is preferably used.

As the swellable synthetic mica, Na tetrathick mica NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ , Na or L
i Teniolite (NaLi) Mg ₂ Li (Si ₄ O ₁₀ )
F ₂ , Na or Li hectorite (NaLi) _1/3 Mg
_2/3 Li _1/3 (Si ₄ O ₁₀ ) F _{2 and the} like. The swellable synthetic mica preferably used in the present invention has a thickness of 1 to 50 nm and a plane size of 1 to 20 μm. For diffusion control, the thinner the better, the better the flatness is, and the better the planar size is, as long as the smoothness and transparency of the coated surface are not deteriorated. Therefore, the average aspect ratio is 1
00 or more, preferably 200 or more, particularly preferably 50
0 or more. On the other hand, specific examples of the non-swellable inorganic layer compound include fluorophlogopite KMg ₃ (AlSi ₃ O ₁₀ ) F
₂ and potassium tetrasilicic mica KMg _2.5 (Si ₄ O ₁₀ ) F ₂ are preferred.

The amount of the anionic inorganic compound added to the photographic constituent layer is generally 50 to 10 in order to control the diffusion of additives such as couplers in the intermediate layer or the protective layer.
A 00mg / m ^2, preferably from 100 to 500 mg / m ^2, more preferably from 100 to 300 mg / m ^2. As a binder used in the layer containing the anionic inorganic compound, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; Various kinds of synthetic hydrophilic high-molecular substances such as homo- or copolymers such as alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, and polyacrylamide can be used.

As the gelatin, besides lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme dispersion can also be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides, epoxy compounds and the like are added to gelatin. What is obtained by reacting is used. The swellable synthetic mica preferably used in the present invention has a refractive index of about 1.
Since it is 53, the binder used in combination is preferably a polymer having the same refractive index. Since the refractive index of gelatin is 1.53 to 1.54, it is particularly preferable as a dispersed polymer or binder of swellable synthetic mica. The binder amount of the anionic inorganic compound-added layer is preferably from 1 to 2,000 parts by weight, more preferably from 10 to 1,000 parts by weight, particularly preferably from 20 to 500 parts by weight, based on 100 parts by weight of the anionic inorganic compound.

Next, a method for dispersing the anionic inorganic compound will be described. Anionic inorganic compound 5 in 100 parts by weight of water
Add 10 to 10 parts by weight, mix well with water, swell, and disperse in an acid splitter. Examples of the acid dispersing machine used to carry out the present invention include a method using various kinds of mills that directly apply mechanical force to disperse, a high-speed stirring type acid dispersing machine having a large shearing force, and applying high-intensity ultrasonic energy. There is a deacidifier. Specifically, a ball mill, a sand grinder mill, a biscomil, a colloid mill, a homogenizer, a dissolver, a polytron, a homomixer, a homoblender, a kedi mill, a jet agitator, a capillary emulsifier, a liquid siren, an electromagnetic strain type ultrasonic generator, There is an emulsifying device having a Paulman whistle. The dispersion of 5 to 10% by weight dispersed in water by the above method has a high viscosity or a gel state, and has extremely good storage stability. When adding to the coating solution, add it after diluting with water and sufficiently stirring.

Since the surface of the anionic inorganic compound is negatively charged, the surface becomes hydrophobic when a cationic surfactant or the like is adsorbed on the surface. When using an inorganic compound whose surface is hydrophobized in this way, after swelling with a solvent having a sufficient affinity for the hydrophobic part of the surfactant adsorbed on the surface, disperse and add a binder solution, A coating solution can be prepared.

The layer incorporating the anionic inorganic compound used in the present invention is not particularly limited as long as it is at least one layer of a photographic element. For example, a surface protective layer, a silver halide emulsion layer, an intermediate layer, an undercoat layer, a back layer, Other auxiliary layers and the like can be mentioned, but a surface protective layer, an undercoat layer and an intermediate layer are preferred. In a further preferred embodiment, the layer containing the dye-forming coupler, the layer containing the color-forming reducing agent, and / or the layer holding the generated coupler dye are sandwiched between the two layers, respectively. It is contained in at least two photographic constituent layers.

The color-forming reducing agent (color-forming developer) used in the present invention will be described. Generally, a developing agent used for a silver halide color photographic light-sensitive material reduces silver halide imagewise, directly or via another electron transfer agent, to produce an oxidized developing agent according to the exposure amount. The oxidized developing agent further reacts with a color forming agent (coupler) to form a dye. In this ordinary color photographic system, a developer is contained in a developer, and the developer permeates a photosensitive material during a development process, and development proceeds. In other words, it has high reactivity (it is easily decomposed by air oxidation because it is a reducing agent)
The developer is always supplied in a fresh form during the development process. However, since the developing agent used in the present invention is contained in the light-sensitive material, it must have excellent storage stability before and after the developing process, and have a seemingly contradictory feature of exhibiting high developing activity in the developing process. There is.
In other words, a developer used for ordinary processing of a photographic material cannot be used as it is (in terms of storage stability), and a developer designed to increase the oxidation potential in order to satisfy storage stability is not available. Sufficient development activity cannot be exhibited during processing. As one method for solving this problem, there is a method in which a compound capable of being released in a color developing process is introduced into a compound having a developing activity and used as a developing agent (reducing agent for color forming). This color-forming reducing agent has the following general formula (D-
It can be represented by 1). General formula (D-1)

[0016]

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In the general formula (D-1), L is an electron-withdrawing group which can be eliminated in the course of development processing, and D is a compound residue obtained by removing n hydrogen atoms from a compound HnD having development activity. , N is an integer of 1 to 3. The general formula (D-
The color-forming reducing agent represented by 1) preferably has a structure represented by the following general formula (D-2). General formula (D-2) L ¹ L ² N- (NH) _p- (X = Y) _q- Z In the general formula (D-2), L ¹ and L ² are hydrogen atoms or can be separated during the color developing process. A monovalent electron-withdrawing group, L ¹ and L ² are not hydrogen atoms at the same time, X and Y each independently represent methine or azomethine, and Z is a hydrogen atom, a hydroxyl group, an amino group or-.
NH ³ , L ³ represents an electron-withdrawing group, p represents an integer of 0 or 1, q represents an integer of 1 to 3, L ¹ ,
Any two of L ² , X, Y and Z may be linked to form a ring.

The preferred range of the color-forming reducing agent represented by formula (D-2) will be described in detail. In the formula (D-2), the electron-withdrawing groups represented by L ¹ and L ² are preferably an acyl group, a sulfinyl group, a sulfonyl group and a phosphoryl group, and particularly preferably an acyl group and a sulfonyl group. L ¹ and L ² are released during the color development process, but may be released after the color-forming reducing agent represented by the general formula (D-2) is oxidized, or may be released before being oxidized. Good. However, from the viewpoint that it is preferable that development does not proceed in the unexposed area (fog suppression), it is also considered that the developmentally active species generated in the development process remain unreacted in the photosensitive material, and this produces a colored substance. From the viewpoint of prevention (stain suppression), the color-forming reducing agent used in the present invention develops silver halide imagewise under basic conditions, and the oxidized developer formed at that time couples the coupler. A mechanism in which L ¹ and L ² are separated to form a dye is preferable. The form of elimination of L ¹ and L ² may be eliminated as an anion or a radical,
It may be released by the action of a nucleophilic species or a base (water, hydroxide ion, hydrogen peroxide, sulfite ion, hydroxylamine, etc.) in the developing solution. In the latter case, the nucleophilic species is positively added to the developing solution. L ¹ or L ² by adding
When a compound (especially preferably hydrogen peroxide) that promotes the release of silver or silver development is added, the nucleophilicity of the compound can be used to promote the release of L ¹ or L ² .

In the general formula (D-2), (X = Y) _q represents a π-electron conjugated system by a carbon atom or a nitrogen atom, and it is particularly preferable that X and Y are connected to form a ring,
q is preferably 2 or 3, and the number of nitrogen atoms contained therein is 0.
To 3 are preferred. (X = Y) When _q forms a ring, the number of ring members is preferably 5 or 6, and a hetero atom may be contained as a constituent atom of the ring. In this case, a preferable hetero atom is a nitrogen atom or an oxygen atom. And a sulfur atom, and particularly preferably a nitrogen atom. And (X = Y)
_q may have a condensed ring, and the condensed ring is preferably a benzene ring. X that binds to L ¹ L ² N when p is 0
May be any of a carbon atom or a nitrogen atom,
When p is 1, X bonded to NH is preferably a carbon atom.

In the general formula (D-2), when p is 0, Z
Is preferably a hydroxyl group, an amino group or NHL ³ , and when p is 1, Z is a hydrogen atom or NHL
³ is preferred. When Z is represented by NHL ³ , L ³ is preferably an acyl group, a sulfinyl group, a sulfonyl group and a phosphoryl group, and particularly preferably an acyl group and a sulfonyl group.

The color-forming reducing agent represented by the general formula (D-2) is preferably introduced into the light-sensitive material by a method of dispersing and coating in a high-boiling organic solvent, that is, a so-called oil protection method. Therefore, it is easily dissolved in high boiling organic solvents,
In order to stably maintain the developer in the photosensitive material, the developer preferably has a relatively large lipophilic group generally called a ballast group. Therefore, this ballast group preferably contains one or more linear or branched alkyl groups of a certain size, and the total number of carbon atoms of these alkyl groups is preferably from 3 to 32, more preferably 6-22, particularly preferably 8-18. The substitution position of the ballast group may be on L ¹ , L ² , (X = Y) or Z, but is preferably on L ¹ or L ² .

The color-forming reducing agent represented by the general formula (D-2) has a preferable pKa corresponding to the pH of the developing solution used.
(Acid dissociation constant), the absorption wavelength of the formed dye,
It may have a substituent in order to adjust the rate of desorption of L ¹ or L ^2, the rate of coupling with the coupler, or the oxidation potential to a desired range. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an amino group, a carboxyl group,
Examples include a sulfo group, an acyl group, an acylamino group, a carbamoyl group, a sulfonyl group, a sulfonylamino group, a sulfamoyl group, an alkyl group, an aryl group, an alkoxy group, a heterocyclic residue, and an aryloxy group.

Among the color-forming reducing agents represented by formula (D-2), more preferred are the following formulas (D-3) to (D-3).
It is a color-forming reducing agent represented by (D-10).

Formula (D-3) R ¹ SO ₂ NH-φ ¹ -NR ² R ³ Formula (D-4) R ⁴ SO ₂ NH-φ ² -OH Formula (D-5) R ⁵ CONH -Φ ³ -NR ⁶ R ⁷ General formula (D-6) R ⁸ CONH-φ ⁴ -OH General formula (D-7) R ⁹ SO ₂ NHNHR ¹⁰ General formula (D-8) R ¹¹ CONNHHR ¹² General formula ( _{^{D-9) R 13 SO 2}} NHN = φ 5 formula ^{(D-10) R 14 CONHN} = φ 6

In the general formulas (D-3) to (D-10), R ² , R ³ , R ⁶ and R ⁷ represent an alkyl group, an aryl group or a heterocyclic group, and R ¹⁰ and R ¹² represent an aryl group Or a heteroaryl group, R ¹ , R ⁴ , R
⁵ , R ⁸ , R ⁹ , R ¹¹ , R ¹³ and R ¹⁴ represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group or an amino group, and φ ^{1 to} φ ⁴ represent an arylene group or an heteroarylene group, phi ⁵ and phi ⁶ is a hydrocarbon ring group or a heterocyclic group bonded to the nitrogen atom by a double bond.

In general formulas (D-3) to (D-10), preferred as the alkyl group represented by R ^{1 to} R ¹⁴ is a linear or branched, chain or cyclic alkyl group having 1 to 30 carbon atoms. Among them, preferred are those having 1 to 22 carbon atoms.
Linear or branched alkyl groups such as methyl, ethyl, isopropyl, n-butyl, 2-ethylhexyl, n-dodecyl, t-octyl, n
-Tetradecyl group, n-hexadecyl group and n-octadecyl group.

In formulas (D-3) to (D-10), the aryl group represented by R ^{1 to} R ¹⁴ is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 20 carbon atoms. Are preferable, and examples thereof include a phenyl group, a naphthyl group, and an anthracenyl group. Among them, a preferable one is a phenyl group.

In the general formulas (D-3) to (D-10), preferred as the heterocyclic ring represented by R ^{1 to} R ¹⁴ are 5
A 7-membered heterocyclic ring, wherein the hetero atom is nitrogen,
Oxygen and sulfur atoms are preferred, and the number of carbon atoms is preferably 1 to 10, and particularly preferred is a nitrogen-containing 5- or 6-membered heterocyclic ring such as 2-imidazolyl group, 1,3-oxazol-2-yl group, , 3-thiazol-2-yl group, 5-tetrazolyl group, 3-indolinyl group, 1,
3,4-thiadiazol-2-yl group, 1,2,4-thiadiazol-5-yl group, 1,3-benzoxazol-2-yl group, 1,3-benzothiazol-2-yl group, 1, A 3-benzimidazol-2-yl group, 1,
2,4-triazol-3-yl group, 3-pyrazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrimidyl group, 4-pyrimidyl group, 1,3,5
-Triazin-2-yl group, 1,2,4-triazine-
Examples thereof include a 3-yl group, a 4-quinazolyl group, and a 2-quinoxalyl group. Further, these rings may have a condensed ring, and a preferable condensed ring is a benzene ring.

In general formulas (D-3) to (D-10), those preferred as the alkoxy groups represented by R ¹ , R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ¹¹ , R ¹³ and R ¹⁴ Is a linear or branched, chain or cyclic alkoxy group having 1 to 30 carbon atoms, and among them, preferred are those having 1 to 22 carbon atoms.
Linear or branched alkoxy groups such as methoxy, ethoxy, isopropoxy, n-butoxy, 2-ethylhexyloxy, n-dodecyloxy, n-tetradecyloxy, n-hexadecyl An oxy group and an n-octadecyloxy group.

In the general formulas (D-3) to (D-10), R ¹ , R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ¹¹ , R ¹³ and R ¹⁴
Preferred as the aryloxy group represented by are aryloxy groups having 6 to 20 carbon atoms, more preferably those having 6 to 10 carbon atoms, such as phenoxy, naphthoxy, and anthracenoxy groups. Among them, preferred is a phenoxy group.

In the general formulas (D-3) to (D-10)
R¹ , R^Four , R^Five , R⁸ , R⁹ , R ¹¹, R¹³And R¹⁴
Preferred as the amino group represented by
40 alkylamino groups, dialkylamino groups, aryl
Ruamino group, diarylamino group, heteroarylamido
Group, diheteroarylamino group, alkylaryl group
Amino group, alkylheteroamino group and arylhetero
An arylamino group, and an alkyl group having 1 to 20 carbon atoms.
Killamino, dialkylamino and arylamido
And a methyl group, e.g., methylamino group, ethylamino
Group, propylamino group, diethylamino group, di-n-o
Octylamino group, phenylamino group, dodecylamino
And a hexadecylamino group.

In the general formulas (D-3) to (D-6), φ
¹ Preferred arylene group represented by to [phi] ⁴ is an arylene group having 6 to 20 carbon atoms, further having 6
To 10 are preferable, and examples thereof include a phenylene group, a naphthylene group, and an anthracenylene group. Among them, a particularly preferable one is a phenylene group. These may have a condensed ring, and a preferable condensed ring is a benzene ring.

In the general formulas (D-3) to (D-6), φ
¹ preferably nitrogen, oxygen and sulfur atoms as the hetero atom constituting the hetero arylene group represented by to [phi] ^4, the number of hetero atoms, preferably 1 to 4, more preferably from 1 to 3, 1 or 2 Is particularly preferred. The number of carbon atoms is preferably 2 to 8, more preferably 3 to 5, and the number of ring members is preferably 5 or 6, may have a condensed ring, and a preferred condensed ring is a benzene ring. . Examples of the heteroarylene group represented by φ ^{1 to} φ ⁴ include the following, and particularly preferable ones are (HA-1), (HA-6), (HA-22) and (HA-23). It is. As φ ^{1 to} φ ⁴ , a benzene ring is most preferable.

[0034]

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In the general formulas (HA-1) to (HA-24), * represents a position bonding to NH in the general formulas (D-3) to (D-6), and ** represents NR ² R ³ , OH or NR
⁶ represents a position bonding to R ⁷ , R ^{15 to} R ¹⁹ represent an alkyl or aryl group, and these alkyl and aryl groups are represented by R ^{1 in the} general formulas (D-3) to (D-10).
It is synonymous with the alkyl group and the aryl group represented by to R ^14.

The general formula (D-9) and (D-10) preferred as the "hydrocarbon residue or heterocyclic group bonded to the nitrogen atom by a double bond" represented by phi ⁵ and phi ⁶ In 5 A 7-membered hydrocarbon ring group or a heterocyclic group, wherein the heteroatoms are preferably nitrogen, oxygen and sulfur atoms, and the number of heteroatoms contained is preferably 0 to 3, more preferably 0 to 2. And preferably has 2 to 8 carbon atoms, more preferably 3 to 6 carbon atoms, and particularly preferably a 5- or 6-membered nitrogen-containing unsaturated heterocyclic ring having the general formulas (D-9) and (D-9). -10)
These hydrocarbon rings and heterocycles have R at the carbon atom in the ring.
^It is preferable to form a double bond with ¹³ SO ₂ NHN or R ¹⁴ CONNHN, and it may have a condensed ring,
A preferred fused ring is a benzene ring. φ ⁵
And a “hydrocarbon ring group or heterocyclic group bonded to a nitrogen atom by a double bond” represented by φ ⁶ and (CH-
1) to (CH-19), and among them, preferred are (CH-5), (CH-6), (CH-9),
(CH-10), (CH-11), (CH-16) and (CH-18).

[0037]

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[0038]

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In the general formulas (CH-1) to (CH-18), R ^{21 to} R ³⁷ represent an alkyl group or an aryl group.
3) to (D-10) have the same meanings as the alkyl group and aryl group represented by R ^{1 to} R ¹⁴ .

In the general formulas (D-3) and (D-5), R ² and R ³ , φ ¹ and R ² , φ ¹ and R ³ , R ⁶ and R
⁷ , φ ³ and R ⁶ , and φ ³ and R ⁷ may be linked to form a ring. In this case, the number of ring members is preferably 5 or 6, and even if a hetero atom is contained as a ring-forming atom. Often, preferred as the hetero atom is an oxygen atom. Next, preferred ranges of the developing agents represented by formulas (D-3) to (D-10) will be described in more detail.

In formulas (D-3) to (D-10), preferred as R ¹ , R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ¹¹ , R ¹³ and R ¹⁴ are an aryl group and a heteroaryl Groups, an alkoxy group, an aryloxy group, an amino group and an anilino group, and those having a hydrogen atom bonded to a nitrogen atom are particularly preferable for the amino group and the anilino group. Preferred as R ¹ and R ^{4 in} formulas (D-3) and (D-4) are an aryl group, an alkyl group, an amino group and an anilino group, and particularly preferred are an alkyl group and an aryl group. Preferred as R ⁵ and R ^{8 in} formulas (D-5) and (D-6) are an aryl group, an alkyl group, an amino group and an anilino group, and particularly preferred are an amino group and an anilino group. R of the general formula (D-7)
Preferred as ⁹ are an aryl group, an alkyl group, an amino group and an anilino group, and particularly preferred are an aryl group and an alkyl group. Preferred as R ^{11 in} formula (D-8) are an aryl group, an alkyl group, an amino group and an anilino group, and particularly preferred are an amino group and an anilino group. Preferred as R ^{13 in} formula (D-9) are an aryl group, an alkyl group, an amino group and an anilino group, and particularly preferred are an aryl group and an alkyl group. Preferred as R ^{14 in} formula (D-10) are an aryl group, an alkyl group, an amino group and an anilino group, and particularly preferred are an amino group and an anilino group. Among the general formulas (D-3) to (D-10), preferred are (D-3), (D-4), (D-6) and (D-6).
-7), (D-8), (D-9), and (D-10), and more preferable ones are (D-4), (D-6), and (D-10).
-7), (D-8) and (D-10), more preferred are (D-4) and (D-8), and the most preferred is (D-8).

In the general formulas (D-7) and (D-8), R
¹⁰ and R ¹² represent an aryl group or a heteroaryl group, and a preferable aryl group is an aryl group having 6 to 10 carbon atoms, which may further have a condensed ring. Preferred aryl groups include phenyl groups, and those having at least one or more electron-withdrawing groups are preferred. Here, the electron withdrawing group means a group having a positive Hammett's sigma para value (σp value). More preferably, the sum of the σp values of all the substituents is 0.7 or more and 3.5 or less, more preferably 1.2 or more.
0 or less, and most preferably 1.5 or more and 2.5 or less. Preferred examples of the electron-withdrawing group include a halogen atom (a fluorine atom, a chlorine atom, and a bromine atom), an acyl group, a carbamoyl group, an alkoxycarbonyl group, a cyano group, a sulfonyl group, a sulfamoyl group, a nitrogen-containing heterocyclic group, and a polyfluoro group. Examples thereof include an alkyl group and a nitro group, and particularly preferable examples include a halogen atom, a carbamoyl group, a sulfamoyl group, a sulfonyl group, a cyano group, a nitrogen-containing heterocyclic group, and a polyfluoroalkyl group. Preferred as the heteroaryl group is a heteroaryl group having 5 or 6 ring members, which may have a condensed ring. As the hetero atom, a nitrogen atom, an oxygen atom and a sulfur atom are preferable, and when the ring does not contain a nitrogen atom, 2
It is preferable to have one or more electron-withdrawing groups,
More preferably, it contains one or more nitrogen atoms,
It is a heteroaryl group having one or more electron-withdrawing groups. Preferred examples of R ¹⁰ and R ¹² are shown below. * Represents a site bonded to NH in the general formula.

R ¹ , R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ¹⁰ , R
¹¹ , R ¹² , R ¹³ and R ¹⁴ may further have a substituent, and preferred substituents include a halogen atom (a fluorine atom, a chlorine atom, and a bromine atom) and an alkyl group (having 1 to 22 carbon atoms). ), An acyl group (C1-18), a sulfonyl group (C1-18), an alkoxy group (C1-1)
22), an aryloxy group (6 to 23 carbon atoms), an alkoxycarbonyl group (2 to 23 carbon atoms), an aryloxycarbonyl group (7 to 23 carbon atoms), a carbamoyl group (2 to 23 carbon atoms), and a sulfamoyl group ( Carbon number 0-2
2) an acylamino group (C1-22), a sulfonylamino group (C1-22), an acyloxy group (C1-22), a carboxyl group, a sulfo group, an amino group (C0-22), A hydroxyl group, a cyano group, a polyfluoroalkyl group, and a nitro group.

In the general formulas (D-3) and (D-5), R ² , R ³ , R ⁶ and R ⁷ are preferably an alkyl group having 1 to 8 carbon atoms. Hydroxyl group, alkoxy group (1 to 1 carbon atoms)
12), an acylamino group (1 to 12 carbon atoms), a sulfonylamino group (1 to 12 carbon atoms), and a cyano group.

The following are specific examples of the color-forming reducing agent used in the present invention, but the present invention is not limited thereto.

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The method of developing the light-sensitive material containing the color-forming reducing agent of the present invention after exposure is as follows: an activator processing method of developing with an alkaline processing solution not containing a color-developing agent; and an auxiliary developing agent / base. There is a method of processing with a processing solution containing, a method of developing the alkaline processing solution on a photosensitive material by a diffusion transfer method, and a method of processing by thermal development.

The activator processing is a processing method in which a color-forming reducing agent is incorporated in a light-sensitive material and is developed with a processing solution containing no color-forming developing agent. In the present invention, the `` activator solution '' is substantially free of a p-phenylenediamine-based color developing agent and a reducing agent for color development as conventionally used, but contains an alkali for increasing the pH of the solution. It is characterized by containing, and may contain other components (buffering agent, halogen, chelating agent, etc.). In some cases, it is preferable that a reducing agent is not contained in order to maintain processing stability. In this case, it is preferable that an auxiliary developing agent, hydroxyamines, sulfites, and the like are not substantially contained. Here, "substantially not contained" means preferably 0.5 mmol / liter or less, more preferably 0.1 mmol / liter or less. In particular, it is preferable not to contain at all. P of alkaline processing solution (aqueous solution) as activator solution
H is preferably from 9 to 14, particularly preferably 10
~ 13. For the sensitizer material for activator processing and its processing, see, for example, Japanese Patent Application Nos. 7-63572 and 7-3.
No. 34190, No. 7-334192, No. 7-3341
No. 97 and No. 7-344396.

The process of developing an alkaline processing solution in a diffusion transfer system is known in the art as an instant processing system, and includes at least one photosensitive layer / dye-forming layer (the photosensitive layer and the dye-forming layer are composed of the same layer). The photosensitive material having a mordant layer for capturing and mordanting the diffusible dye formed from the photosensitive layer / dye-forming layer on the same support or on a separate support is subjected to alkaline treatment. This means that the liquid is developed with a thickness of about 500 μm or less, preferably 50 to 200 μm. When an auxiliary developing agent is incorporated, it is preferable that the alkaline processing liquid does not contain the auxiliary developing agent for production and storage of the processing solution. In the case of the diffusion transfer method, the pH of the alkaline treatment liquid is preferably from 10 to 14, and particularly preferably from 12 to 14. For the process of the instant photosensitive material, see The Theory of P.
Photographic Process 4th Edition (1
977, Macmillan) and the specific structure of the film unit is disclosed in JP-A-63-22664.
No. 9 is described. Examples of the materials included in the film unit and various layers including the same are described below. The dye receiving layer and the mordant contained therein are described in JP-A-61-252551.
U.S. Pat. Nos. 2,548,564 and 3,756,8
No. 14, No. 4,124,386, No. 3,625
694. A neutralizing layer for lowering the pH of a photosensitive material after developing an alkaline processing solution is described in JP-B-7-122753, U.S. Pat.
No. 9,383, RD-No. 16102. The timing layer used in combination with this neutralizing layer is described in JP-A-54-136328, U.S. Pat.
267,262, 4,009,030 and 4,268,604. As the emulsion, any emulsion can be used. A preferred auto-positive emulsion for photographic light-sensitive materials is described in JP-A-7-333770.
And No. 7-3333771.
In addition, if necessary, a light shielding layer, a reflection layer, an intermediate layer, an isolation layer, an ultraviolet absorption layer, a filter layer, an overcoat layer,
An adhesion improving layer or the like can be provided. The processing solution for processing the above-mentioned light-sensitive material contains processing components necessary for development, and usually contains a thickening agent and spreads uniformly on the light-sensitive material. Thickening agents such as carboxymethylcellulose and hydroxyethylcellulose are preferable as the thickener. Details of the photosensitive layer and the processing solution are described in JP-A-7-337377.

The heat treatment in the heat development of the light-sensitive material is known in the art and can be applied to the light-sensitive material of the present invention. The photothermographic material and its process are described, for example, in Photo Industry Fundamentals (1979, published by Corona Co., Ltd.).
53-555 pages, 40 pages of video information issued in April 1978,
Nebbetts Handbook of Photo
OGRAPHY AND REPROGRAPHY 7
th Ed. (Van Nostrand and R
enihold Company), pages 32-33, U.S. Patent Nos. 3,152,904 and 3,301,67.
No. 8, No. 3,392,020, No. 3,457,0
No. 75, British Patent Nos. 1,131,108 and 1,1
67,777 and Research Disclosure Magazine 1
It is described in June 978, pages 9 to 15 (RD-17029).

The light-sensitive material of the present invention is prepared in accordance with US Pat. No. 4,514,49 for the purpose of accelerating silver development and a dye-forming reaction.
Nos. 4,657,848 and 5 (published by Aztec Co., Ltd. on March 22, 1991), pages 55 to 86, etc. No. 660, U.S. Pat.
It is preferable to apply the base generation method described in No. 0,445. To the light-sensitive material of the present invention, a heat solvent described in U.S. Pat. Nos. 3,347,675 and 3,667,959 may be added for the purpose of accelerating thermal development. When the light-sensitive material of the present invention is subjected to heat treatment, in order to promote development and / or diffusion transfer of the processing material,
Water, an aqueous solution containing an inorganic alkali metal salt or an organic base,
It is also preferable to include a low-boiling solvent or a mixed solvent of a low-boiling solvent and water or the above-mentioned basic aqueous solution in a light-sensitive material or a processing sheet and heat-treat it. Examples of the method using water include JP-A-63-144354 and JP-A-63-144.
355, 62-38460, JP-A-3-2105
No. 55, JP-A-62-253159 and 63-855
44, EP 210,660 and U.S. Pat. No. 4,740,445. The present invention relates to JP-A-7-261336 and JP-A-7-268045.
, JP-A-8-30103, JP-A-8-46822, JP-A-8-97344 and the like. The heating temperature in the thermal development step is from about 50 ° C. to 200 ° C., and particularly from 60 ° C. to 150 ° C. is useful.

The couplers preferably used in the present invention include compounds having structures represented by the following general formulas (1) to (12). These are compounds generally referred to as active methylene, pyrazolone, pyrazoloazole, phenol, naphthol, and pyrrolotriazole, respectively, and are compounds known in the art.

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Formulas (1) to (4) represent couplers referred to as active methylene couplers, wherein R ¹⁴ represents an optionally substituted acyl group, cyano group, nitro group, aryl group, A heterocyclic residue, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, and an arylsulfonyl group.

In the general formulas (1) to (3), R ¹⁵ is an optionally substituted alkyl group, aryl group or heterocyclic residue. In the general formula (4), R ¹⁶ is an aryl group or a heterocyclic residue which may have a substituent. R
^14, as the R ^15, the substituent that may be R ¹⁶ has, include those mentioned as examples of X ¹ to X ⁵ as described above.

In the general formulas (1) to (4), Y is a hydrogen atom or a group which can be eliminated by a coupling reaction with an oxidized form of a color-forming reducing agent. Examples of Y include a heterocyclic group (a heterocyclic atom is a saturated or unsaturated monocyclic or condensed 5- to 7-membered ring containing at least one nitrogen, oxygen, sulfur or the like, and examples thereof include succinimide and maleic Imide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole, imidazoline-2,4-dione, oxazolidin-2,4-dione , Thiazolidine-2,4-dione, imidazolidine-2-one, oxazolin-2-one, thiazoline-2
-One, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-
Pyrrolin-5-one, 2-imidazolin-5-one, indoline-2,3-dione, 2,6-dioxypurine,
Parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone,
6-pyridazone, 2-pyrazone, 2-amino-1,3,
4-thiazolidine, 2-imino-1,3,4-thiazolidine-4-one, etc.), halogen atom (eg, chlorine atom, bromine atom, etc.), aryloxy group (eg, phenoxy, 1-naphthoxy, etc.), hetero A ring oxy group (eg, pyridyloxy, pyrazolyloxy, etc.), an acyloxy group (eg, acetoxy, benzoyloxy, etc.),
Alkoxy group (eg, methoxy, dodecyloxy, etc.), carbamoyloxy group (eg, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, etc.), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy, etc.), alkoxycarbonyloxy group (Eg, methoxycarbonyloxy, ethoxycarbonyloxy, etc.), arylthio groups (eg, phenylthio, naphthylthio, etc.), heterocyclic thio groups (eg, tetrazolylthio, 1,3,4-thiadiazolylthio, 1,3,4- Oxadiazolylthio, benzimidazolylthio, etc.), alkylthio group (eg, methylthio, octylthio, hexadecylthio, etc.), alkylsulfonyloxy group (eg, methanesulfonyloxy, etc.), arylsulfonyloxy Groups (eg, benzenesulfonyloxy, toluenesulfonyloxy, etc.), carbonamide groups (eg, acetamide, trifluoroacetamide, etc.), sulfonamide groups (eg, methanesulfonamide, benzenesulfonamide, etc.), alkylsulfonyl groups (eg, , Methanesulfonyl, etc.), arylsulfonyl group (eg, benzenesulfonyl, etc.), alkylsulfinyl group (eg, methanesulfinyl, etc.), arylsulfinyl group (eg, benzenesulfinyl, etc.), arylazo group (eg, phenylazo, naphthylazo, etc.), A carbamoylamino group (for example, N-methylcarbamoylamino and the like);

Y may be substituted by a substituent,
Examples of the substituent for substituting Y include those described for X ^{1 to} X ⁵ . Y is preferably a halogen atom, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an aryloxycarbonyloxy group, an alkoxycarbonyloxy group, or a carbamoyloxy group. General formula (1)
In (4), R ¹⁴ and R ¹⁵ , and R ¹⁴ and R ¹⁶ may be bonded to each other to form a ring. Formula (5) represents a coupler called a 5-pyrazolone-based coupler, wherein R ¹⁷ represents an alkyl group, an aryl group, an acyl group, or a carbamoyl group. R ¹⁸ represents a phenyl group or a phenyl group substituted with one or more halogen atoms, alkyl groups, cyano groups, alkoxy groups, alkoxycarbonyl groups, or acylamino groups.

In the 5-pyrazolone coupler represented by the general formula (5), R ¹⁷ is an aryl group or an acyl group,
A phenyl group in which ¹⁸ is substituted with one or more halogen atoms is preferred. To describe these preferred groups in detail, R ¹⁷ is a phenyl group, a 2-chlorophenyl group, a 2-
Methoxyphenyl group, 2-chloro-5-tetradecanamidophenyl group, 2-chloro-5- (3-octadecenyl-1-succinimido) phenyl group, 2-chloro-5
An aryl group such as -octadecylsulfonamidophenyl group or 2-chloro-5- [2- (4-hydroxy-3-t-butylphenoxy) tetradecanamido] phenyl group or an acetyl group, 2- (2,4-di- t-pentylphenoxy) butanoyl group, benzoyl group, 3-
(2,4-di-t-amylphenoxyacetamido) is an acyl group such as a benzoyl group, and these groups may further have a substituent, and these groups may be a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. It is a connecting organic substituent or a halogen atom. Y has the same meaning as described above.

R ¹⁸ is preferably a substituted phenyl group such as a 2,4,6-trichlorophenyl group, a 2,5-dichlorophenyl group and a 2-chlorophenyl group. The general formula (6) represents a coupler called a pyrazoloazole coupler, wherein R ¹⁹ represents a hydrogen atom or a substituent. Q ³ represents a group of nonmetallic atoms necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). Among the pyrazoloazole couplers represented by the general formula (6), imidazo [1,2-b] pyrazoles described in U.S. Pat. U.S. Patent No. 4,
No. 500,654, pyrazolo [1,5-b]-
1,2,4-triazoles, U.S. Pat.
No. 067, pyrazolo [5,1-c] -1,2,4
-Triazoles are preferred.

For details of the azole ring substituents represented by the substituents R ¹⁹ and Q ³ , see, for example, US Pat.
No. 0,654, column 2, line 41 to column 8, line 27. Preferably, JP-A-61-
No. 65245, a pyrazoloazole coupler having a branched alkyl group directly bonded to the 2, 3 or 6-position of the pyrazolotriazole group, and a sulfonamide group in the molecule described in JP-A-61-65245. A pyrazoloazole coupler having an alkoxyphenylsulfonamide ballast group described in JP-A-61-147254;
Pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position described in JP-A-209457 or JP-A-63-307453;
No. 201443 is a pyrazolotriazole coupler having a carboxamide group in the molecule. Y has the same meaning as described above.

Formulas (7) and (8) are couplers called phenol couplers and naphthol couplers, respectively, wherein R ²⁰ is a hydrogen atom or —CONR ²² R
_{^{23, -SO 2 NR 22 R 23}} , -NHCOR 22, -NHCO
NR ²² R ^23, represents a group selected from -NHSO ₂ NR ²² R ^23. R ²² and R ²³ represent a hydrogen atom or a substituent. In the general formulas (7) and (8), R ²¹ represents a substituent, 1 represents an integer selected from 0 to 2, and m represents an integer selected from 0 to 4. When l and m are 2 or more, R ²¹ may be different from each other. Examples of the substituent of R ^{21 to} R ²³ include those described as examples of X ^{1 to} X ^{5 in} the general formulas (II) and (IV). Y has the same meaning as described above.

Preferred examples of the phenolic coupler represented by the general formula (7) include US Pat. No. 2,369,9.
No. 29, No. 2,801,171, No. 2,772
No. 162, No. 2,895,826, No. 3,77
2,002 and the like, 2-acylamino-5-alkylphenols, U.S. Pat. Nos. 2,772,162, 3,758,308, 4,126,396;
Nos. 4,334,011, 4,327,173
No. 3,329,729, West German Patent Publication No.
Nos. 2,166-9656, 2,5-diacylaminophenols, U.S. Pat. Nos. 3,446,622, 4,333,999, 4,451,559, and 4,427, No. 767, etc., and 2-phenylureido-5-acylaminophenols. Y is the same as described above.

A naphthol coupler represented by the general formula (8)
Preferable examples of US Pat. No. 2,474,29
No. 3, 4,052, 212 and 4,146, 3
No. 96, No. 4,282,233, No. 4,296,
2-carbamoyl-1-naphthol described in No. 200, etc.
And 2 described in U.S. Pat. No. 4,690,889.
-Carbamoyl-5-amido-1-naphthols and the like.
I can do it. Y is the same as above
is there. General formulas (9) to (12) represent pyrrolotriazole
Is a coupler called R ³², R³³, R³⁴Is a hydrogen atom
Or a substituent. Y is as described above.
You. R³², R³³, R³⁴Is a substituent of the aforementioned X¹~ X
^FiveAre mentioned as examples. General formula (9)
Preferred are pyrrolotriazole couplers represented by (12).
A good example is EP 488,248 A1,
No. 491,197A1 and No. 545,300
R³², R³³At least one is an electron-withdrawing group
Couplers. Same as above for Y
The same. In addition, fused phenol, imidazole,
Roll, 3-hydroxypyridine, other active methyl
Ren, active methine, 5,5-fused heterocycle, 5,6-fused ring
A coupler having a structure such as a heterocyclic ring can be used.

Examples of fused phenol couplers include US Pat. Nos. 4,327,173 and 4,564,586.
And the couplers described in JP-A Nos. 4,904,575 and the like can be used. As the imidazole coupler, couplers described in U.S. Pat. Nos. 4,818,672 and 5,051,347 can be used. As the 3-hydroxypyridine-based coupler, couplers described in JP-A-1-315736 and the like can be used.

As active methylene and active methine couplers, US Pat. Nos. 5,104,783 and 5,16
The couplers described in 2,196 and the like can be used. 5,5
-As a fused heterocyclic coupler, US Pat.
Pyrrolopyrazole couplers described in JP-A-4,289, and pyrroleimidazole couplers described in JP-A-4-174429 can be used. Examples of 5,6-fused heterocyclic couplers include pyrazolopyrimidine couplers described in U.S. Pat. No. 4,950,585 and JP-A-4-20473.
No. 0, pyrrolotriazine couplers described in EP-A-556700, and the like can be used.

In the present invention, in addition to the above-mentioned couplers, West German Patent Nos. 3,819,051A and 3,823,049.
No. 4,840,883, US Pat.
No. 4,930, No. 5,051,347, No. 4,4
No. 81,268, European Patent Nos. 304,856A2, 329,036, 354,549A2, 374,781A2, 379,110A2, 386,930A1, 63-141055
Nos. 64-32260, 64-32261, JP-A-2-29747, JP-A-2-44340, and 2-
No. 110555, No. 3-7938, No. 3-16044
No. 0, No. 3-172839, No. 4-17247,
4-179949, 4-182645, 4-
Nos. 184437, 4-188138, 4-188
No. 139, No. 4-194847, No. 4-204532
And the couplers described in JP-A Nos. 4-207473 and 4-204732 can also be used. Specific examples of the coupler that can be used in the present invention are shown below, but the present invention is of course not limited thereto.

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In the present invention, the color-forming reducing agent is used in an amount of 0.01 mmol per color-forming layer in order to obtain a sufficient color-forming density.
/ M ^{2 to} 10 mmol / m ² are preferably used.
A more preferred amount is 0.05 mmol / m ^{2 to} 5 m.
mol / m ² , and a particularly preferable usage amount is 0.1 mm.
ol / m ^{2 to 1} mmol. This range is preferred in that a sufficient color density can be obtained. The preferred amount of the coupler in the color-forming layer in which the color-forming reducing agent is used in the invention is from 0.05 to less than the molar amount of the color-forming reducing agent.
It is 20 times, more preferably 0.1 times to 10 times, particularly preferably 0.2 times to 5 times. This range is preferred in that a sufficient color density can be obtained.

The color light-sensitive material of the present invention is basically obtained by coating a support with a photographic constituent layer comprising at least one hydrophilic colloid layer. One of the photographic constituent layers is a light-sensitive silver halide. , A coupler for forming a dye, and a reducing agent for forming a color. The most typical embodiment is to add the dye-forming coupler and the color-forming reducing agent used in the present invention to the same layer, but they can be separately added to another layer if they can react. These components are preferably added to a silver halide emulsion layer or a layer adjacent to the silver halide emulsion layer in the light-sensitive material, and particularly preferably added together to a silver halide emulsion layer.

Further, the color-forming reducing agent of the present invention can be introduced into a photographic material by various known dispersion methods, dissolved in a high-boiling organic solvent (optionally using a low-boiling organic solvent in combination), and added to an aqueous gelatin solution. An oil-in-water dispersion method in which the emulsion is dispersed and added to the silver halide emulsion is preferred. The high boiling organic solvent that can be used in the present invention has a melting point of 100 ° C. or less and a boiling point of 140 ° C.
Any compound that is immiscible with water at a temperature of not less than ° C and is a good solvent for the color-forming reducing agent and coupler can be used. The melting point of the high boiling organic solvent is preferably 80 ° C. or lower. The boiling point of the high boiling organic solvent is preferably 160 ° C. or higher, more preferably 170 ° C. or higher. Details of these high-boiling organic solvents are described in JP-A-62-215272, page 137, lower right column to page 144, upper right column. In the present invention, when a high-boiling organic solvent is used, the amount of the high-boiling organic solvent used may be any amount,
Preferably, the ratio of the high-boiling organic solvent / color-forming reducing agent to the color-forming reducing agent is 20 or less by weight, preferably 0.02 or less.
To 5 are more preferable, and 0.2 to 4 are particularly preferable.

The average particle size of the lipophilic fine particles containing the color-forming reducing agent of the present invention is not particularly limited, but is preferably from 0.05 to 0.3 μm from the viewpoint of color-forming properties. Further, the thickness is more preferably 0.05 to 0.2 μm.

In general, in order to reduce the average particle size of the lipophilic fine particles, it is necessary to select the type of the surfactant, increase the amount of the surfactant used, increase the viscosity of the hydrophilic colloid solution, This can be achieved by lowering the viscosity of the organic layer by using a low-boiling point organic solvent in combination, or by increasing the shearing force such as increasing the rotation of the stirring blade of the emulsifier, or by lengthening the emulsification time. The particle size of the lipophilic fine particles can be measured by, for example, a device such as Nanosizer manufactured by Coulter, UK. When the dye formed from the color-forming reducing agent and the dye-forming coupler in the present invention is a diffusible dye, it is preferable to add a mordant to the light-sensitive material. When the present invention is applied to such a form, it is not necessary to immerse in an alkali to form a color, and therefore, the image stability after the processing is remarkably improved. The mordant may be used in any of the layers, but when added to a layer containing the color-forming reducing agent of the present invention, the stability of the color-forming reducing agent deteriorates. It is preferably used for a layer that does not contain. Furthermore, the dye formed from the color-forming reducing agent and the coupler diffuses through the swollen gelatin film during the treatment and dyes the mordant. Therefore, it is preferable that the diffusion distance is short in order to obtain good sharpness. Also, the color-forming reducing agent of the present invention,
When the dye formed from the coupler of the present invention is a water-soluble dye, it may flow out into the processing solution. Therefore, the layer to which the mordant is added to prevent this is preferably on the side opposite to the support with respect to the layer containing the color-forming reducing agent. However, JP-A-7-16833
When the barrier layer as described in No. 5 is provided on the side opposite to the support with respect to the layer to which the mordant is added, the layer to which the mordant is added is the same as the layer containing the color-forming reducing agent. It is also preferred that they are on the same side as the support.

The mordant used in the present invention may be added to a plurality of layers. In particular, when a plurality of layers contain a color-forming reducing agent, the mordant is added to each adjacent layer. It is also preferable to do so. The coupler forming the diffusible dye may be any coupler as long as the diffusible dye formed by coupling with the color-forming reducing agent of the present invention reaches the mordant, but the diffusible dye formed is pKa (Acid dissociation constant) It is preferable to have one or more dissociating groups of 12 or less, more preferably one or more dissociating groups of pKa 8 or less, and particularly preferably a dissociating group of pKa 6 or less. The molecular weight of the formed diffusible dye is preferably 200 or more and 2000 or less. Further, (the molecular weight of the formed dye / the number of dissociating groups having a pKa of 12 or less) is 10
It is preferably from 0 to 2,000, more preferably from 100 to 1,000. Here, as the value of pKa, a value measured using dimethylformamide: water = 1: 1 as a solvent is used.

The coupler forming the diffusible dye may be used in combination with the reducing agent for color formation of the present invention.
^-6 mol / liter or more is preferable, and 1 × 10
^-5 mol / liter or more preferably 1 ×
It is particularly preferred that the dissolution is 10 ^-4 mol / l or more.
The coupler forming the diffusible dye is dissolved in an alkaline solution having a diffusion constant of 25 ° C. and a pH of 11 at a concentration of 10 ⁻⁴ mol / liter in an alkaline solution having a diffusible dye formed by coupling with the color-forming reducing agent of the present invention. In this case, it is preferably 1 × 10 ⁻⁸ m ² / s ⁻¹ or more, more preferably 1 × 10 ⁻⁷ m ² / s ⁻¹ or more, and 1 × 10 ⁻⁶ m ² / s ^−. It is particularly preferred that it is ¹ or more.

The mordant which can be used in the present invention can be arbitrarily selected from mordants usually used.
Among them, a polymer mordant is particularly preferable. Here, the polymer mordant is a polymer having a tertiary amino group,
Examples of the polymer include a polymer having a nitrogen-containing heterocyclic moiety, and a polymer including a quaternary cation group.

Specific examples of homopolymers and copolymers containing a vinyl monomer unit having a tertiary imidazole group include US Pat. Nos. 4,282,305 and 4,11.
No. 5,124, No. 3,148,061, JP-A-60
No. 118834, No. 60-122941, No. 62-
The following may be mentioned, including the mordant layers described in Nos. 240443 and 62-244036.

Preferred specific examples of homopolymers and copolymers containing a vinyl monomer unit having a quaternary imidazolium salt include British Patent Nos. 2,056,101, 2,093,041, and 1,594. U.S. Pat. Nos. 4,124,386 and 4,115,12.
4, No. 4,450,224, JP-A-48-283.
The following may be mentioned, including the mordants described in No. 25 and the like.

Other preferred examples of homopolymers and copolymers having a vinyl monomer unit having a quaternary ammonium salt include US Pat. No. 3,709,690.
No. 3,898,088, No. 3,958,99
No. 5, JP-A-60-57836 and JP-A-60-60643.
No. 60-122940, No. 60-122942
And mordants described in JP-A-60-235134 and the like.

In addition, US Pat. No. 2,548,564
No. 2,484,430 and 3,148,16
No. 3,756,814 and the like, vinylpyridine polymer and vinylpyridinium cationic polymer; US Pat. No. 3,625,694
No. 3,859,096, No. 4,128,53
8, polymer mordants crosslinkable with gelatin and the like disclosed in GB 1,277,453 and the like; US Pat. Nos. 3,958,995 and 2,721,852
No. 2,798,063, JP-A-54-1152.
No. 28, No. 54-145529, No. 54-26027
Aqueous sol-type mordant disclosed in US Pat. No. 3,898,088; water-insoluble mordant disclosed in US Pat. No. 3,898,088; US Pat. No. 4,168,976 (Japanese Patent Laid-Open No. 54-137333) No. 3,709,690, 3,788,855, and 3,642,482; reactive mordants capable of forming a covalent bond with the dyes disclosed in the specification. No. 3,488,706,
No. 3,557,066, No. 3,271,147
No., JP-A-50-71332 and JP-A-53-30328.
Nos. 52-155528, 53-125, 5
Examples include mordants disclosed in the specification of JP-A-3-1024. Other US Pat. No. 2,675,316
And the mordants described in JP-A-2,882,156.

The polymer mordant of the present invention has a molecular weight of 1,0.
100 to 1,000,000 is suitable, and especially 10,000
00 to 200,000 is preferred. The above-mentioned polymer mordant is usually used by being mixed with a hydrophilic colloid. As the hydrophilic colloid, a hydrophilic colloid, a highly hygroscopic polymer or both of them can be used, and gelatin is most typical. The mixing ratio between the polymer mordant and the hydrophilic colloid, and the amount of the polymer mordant applied, are easily determined by those skilled in the art according to the amount of the dye to be morded, the type and composition of the polymer mordant, and the image forming process used. But the mordant / hydrophilic colloid ratio is 20/80
~ 80/20 (weight ratio), mordant applied amount is 0.2 ~ 15
g / m ² is suitable, preferably for use in the 0.5 to 8 g / m ^2. In the present invention, it is preferable to use an auxiliary developing agent and its precursor in the light-sensitive material, and these compounds will be described below. The auxiliary developing agent used in the present invention is a compound having an action of promoting electron transfer from a color-forming reducing agent to silver halide in the course of developing silver halide grains, and preferably, an exposed silver halide. It is a compound which develops particles and whose oxidized form can oxidize a color-forming reducing agent (hereinafter referred to as cross-oxidation). As the auxiliary developing agent usable in the present invention, pyrazolidones, dihydroxybenzenes, reductones or aminophenols are preferably used, and pyrazolidones are particularly preferably used. The diffusivity of these compounds in the hydrophilic colloid layer is preferably low,
For example, the solubility in water (25 ° C.) is preferably 0.1%
The content is more preferably 0.05% or less, particularly preferably 0.01% or less. The precursor of the auxiliary developing agent used in the present invention is a compound which is stably present in the light-sensitive material, but which releases the above-mentioned auxiliary developing agent quickly once it is processed with a processing solution. In this case, it is preferable that the diffusivity in the hydrophilic colloid layer is low. For example, the solubility in water (25 ° C.) is preferably 0.1% or less, more preferably 0.05% or less, and particularly preferably 0.01% or less.
It is as follows. The solubility of the auxiliary developing agent released from the precursor is not particularly limited, but the auxiliary developing agent itself preferably has low solubility. The auxiliary developing agent precursor that can be used in the present invention is preferably represented by the general formula (A).

Formula (A) A- (L) _n -PUG A represents a block group in which the bond to (L) _n -PUG is cleaved during development processing. Represents a linking group in which the bond between L and PUG is cleaved after the bond is cleaved, n represents an integer of 0 to 3, and PUG represents an auxiliary developing agent. As the auxiliary developing agent, an electron-emitting compound according to the Kendall-Peltz rule other than the p-phenylenediamine compounds is used, and the above-mentioned pyrazolidones are preferably used. As the blocking group represented by A, the following known ones can be applied. That is, a blocking group such as an acyl group or a sulfonyl group described in U.S. Pat. No. 3,311,476, a blocking group utilizing a reverse Michael reaction described in JP-A-59-105542 or the like;
No. 280140, a blocking group utilizing quinone methide or a compound similar to quinone methide by intramolecular electron transfer, JP-A-63-318555 (European Patent Publication 0)
No. 295729), a blocking group utilizing an intramolecular nucleophilic substitution reaction, a blocking group utilizing an addition reaction of a nucleophile to a conjugated unsaturated bond described in JP-A-4-186344, and the like. 62-163051, a blocking group utilizing a β-elimination reaction, JP-A-61-188540, a blocking group utilizing a nucleophilic substitution reaction of diarylmethanes, and JP-A-62-187850. Group utilizing the Rossen rearrangement reaction of
No. 7457, a blocking group utilizing the reaction between an N-acyl compound of thiazolidine-2-thione and an amine, and a di-reactive compound having two electrophilic groups described in WO 93/03419. Blocking groups that react with a nucleating agent can be exemplified. The group represented by L is a linking group capable of cleaving (L) _n-1 -PUG after leaving from the group represented by A during development processing. Absent. Specific examples of the auxiliary developing agent or its precursor are shown below, but the compounds used in the present invention are not limited to these specific examples.

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These compounds may be added to any of the photosensitive layer, the intermediate layer, the undercoat layer and the protective layer. When the compound contains an auxiliary developing agent, it is preferably used by adding it to a non-photosensitive layer. As a method of incorporating these compounds into the photosensitive material, a method of dissolving in a water-miscible organic solvent such as methanol and directly adding the compound to the hydrophilic colloid layer, and coexisting with a surfactant to form an aqueous solution or a colloidal dispersion. The method of addition, after dissolving in a solvent or oil that is substantially immiscible with water,
A method of adding a substance dispersed in water or a hydrophilic colloid, a method of adding a dispersion in the form of a solid fine particle dispersion, and the like can be used, and a conventionally known method can be applied alone or in combination. The method for preparing the solid fine particle dispersion is described in detail in page 20 of JP-A-2-23544. The amount added to the light-sensitive material is from 1 mole% to the color-forming reducing agent.
It is 200 mole%, preferably 5 mole% to 100 mole%, more preferably 10 mole% to 50 mole%.

Absorb light of a specific wavelength for the purpose of adjusting sensitivity, improving safelight safety, adjusting light color temperature, preventing halation, preventing irradiation, or adjusting the sensitivity balance of a multilayer color photosensitive material. For this purpose, it is also preferable to include a light absorbing compound in the silver halide emulsion layer or another hydrophilic colloid layer.

As the light absorbing compound, there can be mentioned a method of dyeing a specific layer using a solid fine particle dispersion of a water-insoluble dye in addition to using a water-soluble dye. Nos. 120030, 56-12639, 55-155350, 55-155351, 6
3-27838, 63-197943, 52-
Nos. 92716 and 64-40827, JP-A-2-28
2244, European Patent Publication Nos. EP015601 and 32
3729, 274723, 276566, 299435, WO 88/04794, JP-A-5-216166, JP-A-5-313307,
The compounds and addition methods described in European Patent EP 0549486 and the like can be used. A solid fine particle dispersion of this type of dye has dissociable hydrogen in the molecule of the dye, and controls the fixation and decolorization in the hydrophilic colloid layer by the pH dependence of the dissociation. Further, in order to control the absorption spectrum of the coating film of the solid fine particle dispersion of the dye to a waveform suitable for the purpose, the dye represented by the following general formula (I) is first dispersed in the form of solid fine particles, and then the other than hydrogen ion
A method of preparing the dye solid fine particle dispersion by heat treatment in the presence of a valent cation and a base can also be used.

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In the formula (I), D represents a compound residue having a chromophore, X represents a dissociable hydrogen or a group having a dissociable hydrogen, and y represents an integer of 1 to 7. The preferred range of y is 1-5, and the particularly preferred range is 1-3. The solid dye that can be used in the present invention refers to a dye that is solid at room temperature (25 ° C.), and preferably has a melting point of 60 ° C. or higher. X
And between D may be separated by a divalent linking group, the divalent linking group include an alkylene group, an arylene group, a heterocyclic _{residue, -CO -, - SO n (} n = 0,1, 2), -NR
-(R represents a hydrogen atom, an alkyl group, an aryl group),
—O— and a divalent group obtained by combining these linking groups, and further include an alkyl group, an aryl group, an alkoxy group, an amino group, an acylamino group, a halogen atom,
It may have a substituent such as a hydroxyl group, a carboxyl group, a sulfamoyl group, a carbamoyl group and a sulfonamide group. Preferred examples _{- (CH 2) n - (} n: 1,
_{2,3), - CH 2 CH (} CH 3) CH 2 -, 1,2-
Phenylene, 5-carboxy-1,3-phenylene,
1,4-phenylene, 6-methoxy-1,3-phenylene, -CONHC ₆ H ₄ -, and the like can be given. The dye represented by the general formula (I) is characterized by having dissociable hydrogen and the like in its molecular structure.

The compound having a chromophore at D can be selected from a number of well-known dyes. These compounds include oxonol dyes, merocyanine dyes, cyanine dyes, arylidene dyes, azomethine dyes, triphenylmethane dyes, azo dyes, anthraquinone dyes,
Indoaniline dyes can be mentioned.

The dissociable hydrogen or the group having a dissociable hydrogen represented by X is non-dissociable when the dye represented by the formula (I) is added to the silver halide photographic light-sensitive material of the present invention. It has the property of rendering the dye of formula (I) substantially insoluble in water, and in the step of developing the light-sensitive material, dissociates to render the compound of formula (I) substantially water-soluble. Has characteristics. Examples of the group having a dissociable hydrogen represented by X include a group having a carboxylic acid group, a sulfonamide group, a sulfamoyl group, a sulfonylcarbamoyl group, an acylsulfamoyl group, a phenolic hydroxyl group, and the like. Examples of the dissociable hydrogen represented by X include hydrogen of an enol group of an oxonol dye.

Among the compounds represented by the formula (I), preferred are those wherein the group having a dissociable hydrogen in X is a group having a carboxylic acid group, particularly an aryl group substituted with a carboxyl group. Are preferred. less than,
Specific examples of the compound represented by formula (I) that can be used in the present invention will be described, but the present invention is not limited thereto.

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The above dyes are described in International Patent WO 88/047.
No. 94, EP 274,723 A1, EP 2
76,566 and 299,435, JP-A-52-9
No. 2716, No. 55-155350, No. 55-155
No. 351, 61-205934, 48-6862
No. 3, U.S. Pat. Nos. 2,527,583 and 3,48
Nos. 6,897, 3,746,539, 3,93
No. 3,798, No. 4,130,429, No. 4,04
0,841, JP-A-3-282244 and 3-79
No. 31, No. 3-167546, etc., or a method described in the gazette or a method according to the method.

At the time of and / or after the preparation of the solid fine particle dispersion, a hydrophilic colloid such as polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polysaccharide, and gelatin is coexistent for the purpose of stabilizing the dispersion and reducing the viscosity. It can also be done. It is particularly preferable to use polyvinyl alcohol and polyvinyl pyrrolidone for preventing aggregation.

The dye-forming coupler and the color-forming reducing agent used in the present invention are most typically added to the same layer. However, if they can react, they are separately added to different layers. be able to. These components are preferably added to a silver halide emulsion layer in a light-sensitive material or an adjacent layer thereof, and particularly preferably to the same silver halide emulsion layer together. In this embodiment, both compounds are preferably co-emulsified in a high boiling organic solvent.

In the silver halide photographic light-sensitive material of the present invention,
Conventionally known photographic materials and additives can be used. For example, a transmissive support or a reflective support can be used as a photographic support. Examples of the transmissive support include transparent films such as cellulose nitrate film and polyethylene terephthalate, and polyesters of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG) and polyesters of NDCA, terephthalic acid and EG. And the like provided with an information recording layer such as a magnetic layer are preferably used. As the reflective support, a reflective support laminated with a plurality of polyethylene layers or polyester layers, and containing a white pigment such as titanium oxide in at least one of such water-resistant resin layers (laminated layers) is preferable. Further, it is preferable that the water-resistant resin layer contains a fluorescent whitening agent. The fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the fluorescent whitening agent, preferably, a benzoxazole-based, coumarin-based, or pyrazoline-based fluorescent whitening agent can be used, and more preferably, a benzoxazolylnaphthalene-based or benzooxazolylstilbene-based fluorescent whitening agent is used. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . The mixing ratio when mixed with the water-resistant resin is preferably 0.0005 to 3% by weight based on the resin, more preferably 0.05 to 3% by weight.
01 to 0.5% by weight.

The reflective support may be a transmissive support or a reflective support as described above, on which a hydrophilic colloid layer containing a white pigment is applied. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface. Examples of the silver halide emulsion used in the present invention include silver chloride, silver bromide, silver iodobromide and silver chlorobromide emulsions. From the viewpoint of rapid processing, a silver chloride emulsion having a silver chloride content of 95 mol% or more is used. Silver or silver chlorobromide emulsions are preferred, and silver halide emulsions having a silver chloride content of at least 98 mol% are preferred. Among such silver halide emulsions, those having a silver bromide localized phase on the surface of silver chloride grains are particularly preferable because high sensitivity can be obtained and photographic performance can be stabilized.

The above-mentioned reflective supports and silver halide emulsions,
Further, different metal ion species doped in silver halide grains, storage stabilizers or antifoggants for silver halide emulsions, chemical sensitization (sensitizer), spectral sensitization (spectral sensitizer), Cyan, magenta, yellow couplers and their emulsifying and dispersing methods, color image preservability improvers (anti-stain and anti-fading agents), dyes (colored layers), gelatin species, layer composition of photosensitive material, coating pH of photosensitive material, etc. As described above, those described in the patents of Tables 1 and 2 can be preferably applied to the present invention.

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[Table 1]

[0144]

[Table 2]

As the antibacterial and antifungal agents usable in the present invention, those described in JP-A-63-271247 are useful.
The light-sensitive material of the present invention can be used in a cathode ray tube (CRT) in addition to being used in a printing system using a normal negative printer.
Also, it is suitable for a scanning exposure method using. A cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser. Further, adjustment of the optical axis and color is also easy. Various light emitters that emit light in a spectral region are used as necessary for a cathode ray tube used for image exposure. For example, any one of a red light emitter, a green light emitter, and a blue light emitter, or a mixture of two or more thereof is used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in a yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube which emits white light by mixing these light emitters is often used.

When the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions and the cathode ray tube also has a phosphor which emits light in a plurality of spectral regions, a plurality of colors are exposed at a time, ie, the cathode ray tube is exposed. The image signal of a plurality of colors may be input to the display unit to emit light from the display screen. A method of sequentially inputting image signals for each color, sequentially emitting light of each color, and exposing through a film that cuts a color other than that color (plane sequential exposure)
However, in general, field-sequential exposure is preferable for improving image quality because a cathode ray tube with high resolution can be used. The light-sensitive material of the present invention may be a monochromatic high light source such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a second harmonic generation light source (SHG) combining a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal. It is preferably used for a digital scanning exposure system using density light. The system is compact,
In order to reduce the cost, it is preferable to use a semiconductor laser, or a second harmonic generation light source (SHG) in which a semiconductor laser or a solid-state laser is combined with a nonlinear optical crystal. Particularly, in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When such a scanning exposure light source is used,
The spectral sensitivity maximum wavelength of the light-sensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source used. In a solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the laser oscillation wavelength can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be provided in the usual three wavelength ranges of blue, green and red. If the exposure time in such scanning exposure is defined as the exposure time for the pixel size when the pixel density is 400 dpi, the preferred exposure time is 10 ^-4 seconds or less, more preferably 10 ^-6 seconds or less. Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the above table.

[0148]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but it should be understood that the present invention is not limited to these Examples.

Example 1 A surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, followed by providing a gelatin subbing layer containing sodium dodecylbenzenesulfonate, and further coating six types of photographic constituent layers. (100) was produced. The coating solution was prepared as follows. First layer coating solution 17 g of coupler (C-78), color developing agent (42) 2
0 g and a solvent (Solv-1) 80 g were dissolved in ethyl acetate, and this solution was added to 400 g of a 16% gelatin solution containing 10% sodium dodecylbenzenesulfonate and citric acid.
To prepare an emulsified dispersion A. On the other hand, silver chlorobromide emulsion A (cubic, a large-sized emulsion A having an average grain size of 0.88 μm and a small-sized emulsion A having an average grain size of 0.70 μm:
7 mixtures (silver molar ratio). The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion). did. This emulsion contains the following blue-sensitive sensitizing dyes A, B, and C in an amount of 7.0 × 10 ^-4 mol per mol of silver per mol of silver, and 7.0 × 10 ^-4 mol per mol of silver. , 8.5 × 10 ^-4 mol each. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion A and the silver chlorobromide emulsion A were mixed and dissolved to prepare a first layer coating solution having the following composition. The emulsion coating amount indicates a silver equivalent coating amount.

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The coating solutions for the second to sixth layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Cpd-2, Cpd-
3, the total amount of each of Cpd-4 and Cpd-5 was 15.0.
^{mg / m 2, 60.0mg / m} 2, 50.0mg / m 2
And 10.0 mg / m ² .

Also, 1- (5-methylureidophenyl)
-5-mercaptotetrazole was added to each silver halide emulsion layer at 3.0 × 10 ^-3 mol per mol of silver halide. (Layer Structure) The composition of each layer is shown below. The number is the coating amount (g
/ M ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [The first layer side polyethylene contains white pigment (TiO ₂ 15% by weight) and bluish dye (ultramarine)]

First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A 0.20 Gelatin 1.50 Yellow coupler (C-78) 0.17 Color developing agent (42) 0.20 Solvent (Solv-2) ) 0.80

Second layer (color mixture prevention layer) Gelatin 1.09 Color mixture prevention agent (Cpd-6) 0.11 Solvent (Solv-1) 0.19 Solvent (Solv-3) 0.07 Solvent (Solv-4) 0.25 Solvent (Solv-5) 0.09 1,5-diphenyl-3-pyrazolidone 0.06 (fine particle solid dispersion state)

Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion B 0.20 Gelatin 1.50 Magenta coupler (C-58) 0.24 Color developing agent (42) 0.20 Solvent (Solv-2) ) 0.80

Fourth layer (color mixture prevention layer) Gelatin 0.77 Color mixture prevention agent (Cpd-6) 0.08 Solvent (Solv-1) 0.14 Solvent (Solv-3) 0.05 Solvent (Solv-4) 0.14 Solvent (Solv-5) 0.06 1,5-diphenyl-3-pyrazolidone 0.04 (fine particle solid dispersion state)

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C 0.20 Gelatin 0.15 Cyan coupler (C-44) 0.21 Color developer (42) 0.20 Solvent (Solv-2) ) 0.80

Sixth layer (protective layer) Gelatin 1.01 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-1) 0.01

Silver chlorobromide emulsion B: cubic, 1: 3 mixture of large-size emulsion B having an average grain size of 0.55 μm and small-size emulsion B having an average grain size of 0.39 μm (Ag molar ratio). The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain surface containing silver chloride as a base in each size emulsion.

In the silver chlorobromide emulsion B, green sensitizing dyes D, E,
F was used in the amount shown below.

(The sensitizing dye D was used in an amount of 1.5 × 10 ⁻³ mol for a large-sized emulsion, 1.8 × 10 ⁻³ mol for a small-sized emulsion, and Sensitizing dye E was used in an amount of 2.0 × 10 ^-4 mol per mol of silver halide and 3.5 mol per mol of silver halide.
× 10 ^-4 mol of sensitizing dye F per mol of silver halide, 1.0 × 10 ^-3 mol for large-size emulsion, and 1.4 × 10 ^-3 mol for small-size emulsion. Added)

Silver chlorobromide emulsion C: cubic, 1: 4 mixture of large-sized emulsion C having an average grain size of 0.10 μm and small-sized emulsion 0.08 μm (Ag molar ratio). The coefficient of variation of the grain size distribution was 0.09 and 0.11, and 0.8 mol% of AgBr was locally contained in a part of the grain surface having silver chloride as a base in each size emulsion.

The red sensitizing dyes G and H were used in the silver chlorobromide emulsion C in the following amounts.

(Per mol of silver halide, 2.5 × 10 ^-4 mol was added to the large-size emulsion, and 4.0 × 10 ^-4 mol was added to the small-size emulsion.)

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In the fifth layer (red-sensitive layer), the following compounds were further added in an amount of 2.6 × 10 ^-2 mol per mol of silver halide.

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For the purpose of preventing irradiation, the following dyes were added to the emulsion layer (the coating amount is shown in parentheses).

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The color developing agents in the coating solutions of the first, third and fifth layers were replaced with the color developing agents and couplers shown in Table 3 in equimolar amounts, or the swellable inorganic layered compound of the present invention was used. Were added to each photographic constituent layer, and samples (101) to (114) were produced in exactly the same manner as the production of the sample (100).

[0177]

[Table 3]

Samples (100) to (100) prepared as described above
(114) was subjected to gradation exposure with a three-color separation filter for sensitometry using an FWH type photometer (color temperature of light source: 3200 ° K) manufactured by Fuji Photo Film Co., Ltd.

The sample after exposure was processed in the following processing steps. Processing process temperature Time development 40 ° C 20 seconds Bleaching and fixing 40 ° C 45 seconds Rinse Room temperature 45 seconds

Developing solution (alkali activating solution) Water 600 ml Potassium phosphate 40 g KCl 5 g Hydroxyethylidene-1,1-diphosphonic acid (30%) 4 ml UVX 2 g Add water 1000 ml 1N potassium hydroxide Was adjusted to pH = 12 (25 ° C.).

Bleaching-fixing solution Water 600 ml Ammonium thiosulfate (700 g / liter) 93 ml Ammonium sulfite 40 g Ammonium iron (III) ethylenediaminetetraacetate 55 g 2 g ethylenediaminetetraacetic acid 2 g Nitric acid (67%) 30 g Water is added to 1000 ml PH = 5.8 (25 ° C) with acetic acid and aqueous ammonia
Was adjusted.

Rinse solution Chlorinated sodium isocyanurate 0.02 g Deionized water (conductivity 5 μS / cm or less) 1000 ml pH 6.5

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In the obtained sample, the yellow colored portion was measured with blue light, the magenta colored portion was measured with green light, and the cyan colored portion was measured with red light. Furthermore, each of the above samples was subjected to 60 ° C.
After storing at 70% RH for 20 days, the density of each colored portion was measured to obtain a residual ratio. Table 4 shows the results of the above concentration measurement.

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[Table 4]

In Table 4, a comparative sample (1) containing the color-forming reducing agent of the present invention and not containing the swellable inorganic layered compound was used.
00, 105, and 110), the stain at the unexposed portion after storage under high temperature and high humidity significantly increases. By using the swellable inorganic layered compound of the present invention in combination, it was possible to suppress the stain under high temperature and high humidity while maintaining the coloring property equal to or higher than that of the comparative sample (101 to 10).
4, 106-109, 111-114). In Table 4, the sample of the present invention suppressed the stain without deteriorating the stability of the dye image with respect to the comparative sample. By using the color-forming reducing agent and the swellable inorganic layered compound of the present invention, a high color-developing density can be obtained by a development process using an activator solution containing substantially no developing agent, and the stain in storage after the process is improved. Was. In addition, the effect of the present invention can be obtained also for non-photosensitive inorganic compounds whose surface is negatively charged, other than the swellable inorganic layered compound.

Example 2 The procedure of Example 1 was repeated, except that a layer containing a mordant was applied using the color developing agent, coupler and solvent in the first, third and fifth layers as shown below. Thus, a silver halide color photographic light-sensitive material (115) was produced. The emulsions, compounds and the like used are the same as those used in Example 1. (Layer Structure) The composition of each layer is shown below. The number is the coating amount (g
/ M ² ). The silver halide emulsion represents a coating amount in terms of silver. Support Polyethylene laminated paper [The first layer of polyethylene contains white pigment (TiO ₂ 15% by weight) and bluish dye (ultramarine)]

First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A 0.20 Gelatin 1.50 Yellow coupler (C-84) 0.17 Color developing agent (28) 0.20 Solvent (Solv-1) ) 0.80

Second layer (color mixture preventing layer) Gelatin 1.09 Color mixture inhibitor (Cpd-6) 0.11 Solvent (Solv-1) 0.19 Solvent (Solv-3) 0.07 Solvent (Solv-4) 0.25 Solvent (Solv-5) 0.09 1,5-diphenyl-3-pyrazolidone 0.03 (fine particle solid dispersion state)

Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion B 0.20 Gelatin 1.50 Magenta coupler (C-104) 0.24 Color developing agent (28) 0.20 Solvent (Solv-1) ) 0.80

Fourth layer (color mixture prevention layer) Gelatin 0.77 Color mixture prevention agent (Cpd-6) 0.08 Solvent (Solv-1) 0.14 Solvent (Solv-3) 0.05 Solvent (Solv-4) 0.14 Solvent (Solv-5) 0.06 1,5-diphenyl-3-pyrazolidone 0.02 (fine particle solid dispersion state)

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C 0.20 Gelatin 0.15 Cyan coupler (C-112) 0.21 Color developing agent (28) 0.20 Solvent (Solv) -1) 0.80

Sixth layer (mordant layer) Gelatin 1.00 Mordant (ExP) 2.33 Seventh layer (protective layer) Gelatin 1.01 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Fluid Paraffin 0.02 Surfactant (Cpd-1) 0.01

[0194]

Embedded image

The color developing agents in the coating solutions of the first, third and fifth layers were replaced with the color developing agents and couplers shown in Table 5 in equimolar amounts, or the swellable inorganic layered compound of the present invention was used. Were added to each photographic constituent layer, and samples (116) to (124) were produced in exactly the same manner as the production of the sample (115). The sample was exposed and processed in exactly the same manner as in Example 1. In the obtained sample, the yellow coloring portion was measured with blue light, the magenta coloring portion was measured with green light, and the cyan coloring portion was measured with red light. Further, each of the above samples was subjected to
After storage at 20% RH for 20 days, the density of each color-developed portion was measured and the results are shown in Table 6 as residual rates. From the results in Table 6, by using the color-forming reducing agent and the swellable inorganic layered compound of the present invention, a high color-forming density can be obtained by development with an activator solution substantially free of a developing agent, and after processing. It can be seen that the stain during storage is suppressed.

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[Table 5]

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[Table 6]

[0198]

According to the present invention, a light-sensitive material having a high color density and an improved stain in storage after processing by an activator solution substantially free of a developing agent can be obtained.

Claims (8)

[Claims] 1. A silver halide light-sensitive material comprising a support having a photographic component layer comprising at least one photosensitive silver halide emulsion layer and at least one non-photosensitive layer. Containing at least one dye-forming coupler, at least one color-forming reducing agent represented by the following formula (D-1), and at least one non-photosensitive inorganic compound having a negatively charged surface. A silver halide color photographic light-sensitive material comprising: General formula (D-1) (Wherein L is an electron-withdrawing group that can be removed in the course of development, D is a compound residue obtained by removing n hydrogen atoms from a compound HnD having development activity, and n is an integer of 1 to 3) Is.) 2. The silver halide color photographic material according to claim 1, wherein said non-photosensitive inorganic compound is a swellable inorganic layered compound. 3. The color-forming reducing agent represented by the following general formula (D-8)
3. The silver halide color photographic light-sensitive material according to claim 1, which is a compound represented by the formula: Formula (D-8) R ¹¹ CONNHHR ¹² (wherein, R ¹¹ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, or an amino group, and R ¹² represents an aryl group or an aromatic group. Represents a heterocyclic group.) 4. The silver halide color photographic light-sensitive material according to claim 1, wherein said non-photosensitive inorganic compound is contained in a photographic component layer different from a layer containing a dye-forming coupler. material. 5. The weight ratio of the layer containing the non-photosensitive inorganic compound to the binder of the layer containing the non-photosensitive inorganic compound is 1/10.
The silver halide color photographic light-sensitive material according to any one of claims 1 to 4, wherein the ratio is from 10/1 to 10/1. 6. The silver halide color photographic material according to claim 1, wherein said non-photosensitive inorganic compound has an average aspect ratio of 100 or more. 7. A silver halide color photographic light-sensitive material according to claim 1, wherein said non-photosensitive inorganic compound is a swellable synthetic mica. 8. The silver halide color photographic material according to claim 1, wherein said non-photosensitive inorganic compound is bentonite.