JPH0685073B2 - Processing method of silver halide photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method of processing a photographic light-sensitive material containing a light-sensitive silver halide emulsion layer combined with a blocked photographic reagent releasing a photographically useful reagent. .

(Prior Art) By adding a photographically useful photographic reagent to a photographic light-sensitive material in advance and exerting its effect, a characteristic different from that obtained when a photographic reagent is contained in a processing solution is achieved. To be Its features are: 1) For example, photographic reagents that can be easily decomposed under acid / alkali or oxidation / reduction conditions and can withstand long-term storage in a processing bath can be effectively used. 2) Processing liquid composition is simplified and adjustment is easy. 3) It is possible to activate the required photographic reagent at the required time during processing, or 4) Only at the required place, that is, only in a specific layer of the multi-layer photosensitive material and / or a layer in the vicinity thereof. 5) The action amount of the photographic reagent can be changed as a function of the silver halide development. However, if the photographic reagent is added to the photographic light-sensitive material in an active form, it may react with other components in the photographic light-sensitive material during storage before processing or decompose under the influence of heat or oxygen. As a result, the expected performance cannot be achieved during processing.

As one method of solving such a problem, the active groups of the photographic reagent are blocked, and the photographic reagent is added in the form substantially inactive in the photographic material, that is, as a photographic reagent precursor in the photographic material, and is added at the time of development processing. There is a method to generate a photographic reagent for the first time.

According to this method, when a useful photographic reagent is a dye, for example, by blocking a functional group that greatly affects the spectral absorption of the dye and shifting the spectral absorption to the short wavelength side or the long wavelength side, the desired Even if the silver halide emulsion layer having a light-sensitive spectrum region is made to coexist in the same layer, there is an advantage that the so-called filter effect does not cause reduction in light-sensitivity. Further, if the useful photographic reagent is an antifoggant or a development inhibitor, blocking the active group can suppress the desensitization effect due to the adsorption to the photosensitive silver halide during storage and the formation of a silver salt. By releasing these photographic reagents at the necessary timing during development processing,
There are advantages that fog can be reduced without deteriorating sensitivity, overdevelopment fog can be suppressed, or development can be stopped at a necessary time. When useful photographic reagents are developing agents, auxiliary developing agents, development accelerators, or nucleating agents, blocking active groups or adsorbing groups can cause various photographic effects due to the formation of semiquinones or oxidants by air oxidation during storage. There is an advantage in that the generation of fog nuclei during storage is prevented by preventing adverse effects or by injecting electrons into silver halide, and as a result, stable processing can be realized. Even when the photographic reagent is a bleaching accelerator or a bleaching / fixing accelerator, by blocking those active groups, the reaction with other coexisting components is suppressed during storage, and the protective group is removed during processing,
It has an advantage that desired performance can be exhibited at a required time.

As described above, the use of photographic reagent precursors can be a very effective means for sufficiently exhibiting the performance of photographic reagents, but on the other hand, those precursors satisfy very strict reciprocal requirements. Must. That is, it must be able to satisfy the contradictory requirements that it stably exists under storage conditions, and that during processing, the blocking group is released at the required timing to release the photographic reagent quickly and efficiently. .

Several techniques are already known as a block technology for photographic reagents. For example, those utilizing a blocking group such as an acyl group and a sulfonyl group described in JP-B-47-44805, JP-B-54-39727, JP-B-55-9696, and JP-B-55-3492.
Utilizing a blocking group that releases a photographic reagent by the so-called reverse Michael reaction described in Japanese Patent No. 7-54, Japanese Patent Publication No. 54-3
9727, JP-A-57-135944, 57-135945, 57-136
JP-A-55-533, which utilizes a blocking group which releases a photographic reagent with the formation of a quinone methide or a quinone methide-like compound by intramolecular electron transfer described in JP-A-640-533.
Those utilizing the intramolecular ring closure reaction described in JP-A-30, or JP-A-57-76541, JP-A-57-135949, and JP-A-57-1798.
Those utilizing the 5-membered or 6-membered cleavage described in the specification No. 42 are known as known techniques.

Furthermore, a means for accelerating the release of the photographic reagent during processing by adding a compound that promotes the cleavage of the photographic reagent precursor to the processing solution or the exposure is also known.
A combination of a hydroxylamine compound and a ring-opening type precursor described in JP-A-59-197037, JP-A-59-1
A combination of hydroxamic acids and a ring-cleaving precursor described in 98453, a combination of oximes and a ring-cleaving precursor described in JP-A-60-35729, and JP-A-59-218439. A combination of sulfites and levulinic acid type precursors described in the specification, JP-A-59-20105
There is a combination of sulfites described in No. 7 with an α, β-unsaturated carbonyl type precursor.

(Problems to be solved by the invention) However, in the conventional photographic reagent blocking technology, when a photographic reagent that is stable under storage conditions is processed, the release rate of the photographic reagent is too small and a high alkaline treatment of pH 12 or higher is required. However, it also has a drawback that it gradually decomposes under storage conditions even if the release rate is sufficient with a treatment solution having a pH of 9 to 12, impairing its function as a precursor. Further, it cannot be said that the accelerating effect is still insufficient in combination with the accelerator.

Therefore, an object of the present invention is to provide a novel means for releasing a photographic reagent at a desired timing during development processing, which is completely stable under the storage conditions of a light-sensitive material, and particularly pH 9
(EN) Provided are a photographic reagent precursor and a processing method therefor capable of realizing a timely release of a photographic reagent even when it is processed with a processing solution having a relatively low pH of -12.

(Means for Solving Problems) As a result of various investigations conducted by the present inventors to overcome the above problems, as a result, a photographic reagent precursor in which a protecting group having a specific structure is bonded to a photographically useful group is used as an amine. It was found that the object can be achieved by treating in the presence of the above, and the present invention has been completed based on this finding.

That is, the present invention relates to at least one By a nucleophilic attack of a nucleophile on the carbonyl group At least one layer of a photosensitive silver halide containing at least one blocked photographic reagent capable of releasing a photographically useful reagent by bond cleavage and subsequent intramolecular electron transfer reaction or intramolecular nucleophilic reaction It is intended to provide a silver halide photographic light-sensitive material characterized by processing a photographic light-sensitive material having an emulsion layer in the presence of amines.

The blocked photographic reagent capable of releasing the photographically useful reagent of the present invention, that is, the photographic reagent precursor is represented by the following general formulas (I) to (IV).

In the general formulas (I) to (IV), PUG is an antifoggant,
Development inhibitor, auxiliary developer, dye, DIR hydroquinone,
Represents a photographically useful group consisting of a photographic reagent selected from a coupler, a nucleating agent, a bleaching accelerator or a developing agent; L ₁ , L ₂ and
L ₃ represents a timing group; l ₁ , l ₂ and l ₃ each represent 1 or 0; R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or a substituent; Z ₁ , Z ₂ And Z ₃ represent a non-metal atom group forming a 5-membered to 7-membered ring and may form a condensed ring.

The amines used in the present invention are preferably represented by the following general formula (V).

In the general formula (V), R ₇ and R ₈ each represent a hydrogen atom or a substituent.

In the general formula (I), Z ₁ is preferably alkylene, cycloalkylene, alkenylene, arylene, cararalkylene, acylalkylene, acylaralkylene, thioalkylene, thioalkenylene, thioarylene, thioaralkylene, oxyalkylene, oxyalkenylene,
It represents oxyarylene, oxyaralkylene, aminoalkylene, aminoalkenylene, aminoarylene, aminoaralkylene, heterocyclene and the like.

The 5-membered to 7-membered ring represented by Z ₁ may have a hetero atom or may form a condensed ring, and preferable rings include thiosuccinimide, thiomaleimide and imidazoline-2-thio- 5-one, imidazolidin-2-thio-4-one, oxazoline-2-thio-4-one, thiazoline-2-thio-4-one, thiophthalimide, puperidine-6-thio-2-one, dihydrooxazine −
2-thio-4-one, tetrahydrooxazin-2-thio-4-one, dihydrothiazin-2-thio-4-one, terrahydrothiazin-2-thio-4-one, tetrahydropyrimidin-2-thio -4-one, hexahydropyrimidin-2-thio-4-one, dihydroazepine-7-thio-2-one, tetrahydroazepine-7-thio-2-one, hexahydroazepine-7-thio-2
These rings may have a substituent, and preferable substituents include the following. Halogen atom (eg fluorine atom, chlorine atom, bromine atom, etc.), alkyl group (eg methyl group, butyl group,
Hexadecyl group etc.), aryl group (eg phenyl group, naphthyl group, 4-t-octylphenyl group, 4-hexadecyloxyphenyl group etc.), alkenyl group (eg isopripyridene group, benzylidene group etc.), alkoxy group (eg ethoxy). Group, butoxy group, decyloxy group, etc.), aryloxy group (for example, phenoxy group,
4-dodecyloxycarbonylphenoxy group, etc.), alkylthio group (for example, ethylthio group, octylthio group,
Dodecylthio group), amino group (eg dimethylamino group, N-methyl-N-octylamino group, anilino group, morpholino group etc.), acyl group (eg acetyl group, octanoyl group, palmitoyl group, benzoyl group etc.), carbamoyl A group (for example, a methylcarbamoyl group,
Butylcarbamoyl group, dodecylcarbamoyl group, 4-
Hexadecyloxyphenylcarbamoyl group, etc.), carbonamide group (eg, butyramide group, octanamide group, benzamide group, etc.), ureido group (eg, ethylureido group, decylureido group, tetradecylureido group, phenylureido group, etc.), sulfamoyl group ( For example, methyloctylsulfamoyl group, dioctylsulfamoyl group, methylhexadecylsulfamoyl group,
Phenylsulfamoyl group), sulfonamide group,
(For example, octylsulfonamide group, hexadecylsulfonamide group, 4-t-octylphenylsulfonamide group, etc.), sulfonyl group (for example, ethylsulfonyl group, hexylsulfonyl group, 4-decaneamidophenylsulfonyl group, etc.), carboxyl group, Sulfo group, oxycarbonyl group (eg, octyloxycarbonyl group,
Tetradecyloxycarbonyl group, phenyloxycarbonyl group, etc.), carbonyloxy group (eg, acetyloxy group, palmitoyloxy group, benzoyloxy group, etc.), cyano group, nitro group, 2-pyridyl group and 1
-Represents a benzotriazole group and the like.

The photographically useful group represented by PUG in the general formula (I) is a known photographic reagent having a hetero atom bonded thereto, for example, mercaptotetrazoles, mercaptotriazoles, mercaptopyrimidines, mercaptobenzimidazoles, mercaptothiazoles. , Antifoggants and development inhibitors represented by benzotriazoles and imidazoles; developers such as p-phenylenediamines, hydroquinones and p-aminophenols; auxiliary developing agents represented by pyrazolidones, hydrazine And nucleating agents such as hydrazides; silver halide solvents such as sodium thiosulfate; bleaching accelerators such as aminoalkylthiols; and azo dyes and azomethine dyes. Further, a photographic reagent further having a redox function for releasing the above-mentioned photographic reagent as a function of development, for example, a color material for color diffusion transfer sensitizing material or DIR-hydroquinones can be mentioned as a useful photographic reagent. .

In addition, the timing group L ₁ in the above general formula (I) is a group known per se and has a function of shifting the state in which the residue represented by PUG can be used in time (taking timing). That is, the bond is cleaved and L ₁ -PU
After the G residue is generated, L ₁ has a function such that the bond between PUG and L ₁ takes some suitable time to be cleaved.
Therefore, if L ₁ -PUG has diffusibility, it is possible to design such that the PUG generated at a position distant from the point where the precursor of the present invention is incorporated functions.

As the timing group represented by L ₁ , for example, a photographically useful group (the above PUG) is released by an intramolecular ring closure reaction of a p-nitrophenoxy derivative described in US Pat. No. 4,248,962 (JP-A-54-145135). What to do; U.S. Pat. No. 4,310,6
12 (JP-A-55-53330) and 4,358,525 which release PUG by an intramolecular ring closure reaction after ring cleavage; US Pat. Nos. 4,330,617, 4,446,216, and 4,4
Nos. 83,919 and JP-A-59-121328, which release PUG with formation of acid anhydride by intramolecular ring closure reaction of carboxyl group of succinic acid monoester or analog thereof; U.S. Pat. No. 4,409,323 , No. 4,421,845, Research Disclosure No. 21228 (December 1981), US Pat. Nos. 4,416,977 (JP-A-57-135944), JP-A-58-
Nos. 209736 and 58-209738, which release PUG by forming quinomonomethane or an analog thereof by electron transfer through a double bond conjugated with an aryloxy group or a heterocyclic oxy group; US Patent No. 4,420,554 (JP-A-57-136640), JP-A-57-135945, JP-A-57-188035
No. 58-98728 and No. 58-209737, which release PUG from the γ-position of an enamine by electron transfer of a portion having an enamine structure of a nitrogen-containing heterocycle described in JP-A-57-56.
PUG is released by an intramolecular ring-closing reaction of an oxy group produced by electron transfer to a carbonyl group conjugated with a nitrogen atom of a nitrogen-containing heterocycle described in 837; US Pat. No. 4,146,3
96 (JP-A-52-90932), JP-A-59-93442, JP-A-SHO
With the formation of aldehydes described in 59-75475, etc., PUG
Those which emit the following: JP-A-51-146828, JP-A-57-179842,
No. 59-104641, which releases PUG with decarboxylation of the carboxyl group; has a structure of -O-COOCR ₁₁ R ₁₂ -PUG, and produces PUG with decarboxylation and subsequent formation of aldehydes. Releasing agent; Releasing PUG with formation of isoianatate described in JP-A-60-7429; U.S. Pat. No. 4,438,1
Examples thereof include those that release PUG by a coupling reaction with an oxidized product of a color developing agent described in No. 93 and the like.

In the general formula (I), l ₁ represents 1 or 0. In the general formula (II), Z ₂ represents a nonmetallic atom group capable of forming a 5-membered ring to a 7-membered ring having-(L ₂ ) l ₂ -PUG as a substituent, and Z ₂ has another substituent. Good. The preferred substituents are
It is the same as those listed as the substituent of Z _{1 in} the general formula (I).

L ₂ , l ₂ and PUG in the general formula (II) have the same meanings as L ₁ , l ₁ and PUG in the general formula (I), respectively. General formula (II)
R ₁ is preferably a substituted or unsubstituted alkyl group (eg, ethyl group, cyclohexyl group, decyl group, α-di-t
-Amylphenoxypropyl group, etc.), aryl group (for example, 4-chlorophenyl group, 4-tetradecyloxyphenyl group, 3-pentadecylphenoxymethyl group, etc.), aralkyl group (for example, benzyl group, 4-octanamidobenzyl group, 4-dodecyloxyphenylethyl group, etc., alkoxy group (eg, methoxy group, decyloxy group, 2- (2,4-di-t-amylphenoxy))
Ethoxy group), aryloxy group (for example, 2,4-
Di-t-octylphenoxy group, 3-dodecylsulfonamidophenoxy group, 4-hexadecylphenoxy group and the like).

In formula _{(II), - (L 2} ) substitution position of l ₂ -PUG by electron transfer of an anion generated on the nitrogen - (L ₂₎ l ₂ -PU
It is a position capable of leaving G, and is preferably on the atom adjacent to the nitrogen atom or at the allyl position or the benzyl position.

In formula (III), Z ₃ represents an atomic group necessary for forming a 5- to 7-membered ring, and specifically, alkylene,
Examples thereof include cycloalkylene, alkenylene, arylene, aralkylene, oxyalkylene, thioalkylene, aminoalkylene and heterocyclene.

R ₂ and R ₃ may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an acyl group, a sulfonyl group, a heterocyclic residue or the like.

R ₄ represents an alkyl group, an alkenyl group, a cycloalkyl group, a heterocyclic residue, an aryl group, an aralkyl group or the like.

In the general formula (III), the electrophilic bond represented by X means a bond having an electrophilic reactivity to a reaction site having a high electron density, because the bond center is electron-deficient. Preferably a carbonyl group, a thiocarbonyl group,
A sulfonyl group, a sulfinyl group, etc. are mentioned, Especially preferably, a carbonyl group is mentioned.

When R ₂ , R ₃ , R ₄ and Z _{3 above} are carbon-containing groups,
The preferred range of carbon number is 1 to 18 in each case. Further, it is preferable to make a combination such that these groups have such a size as to impart immobility or semi-immobility to the whole molecule. Furthermore, these groups more preferably render the entire molecule resistant to diffusion. Further, when the groups allowed for R ₂ , R ₃ , R ₄ and Z ₃ are substitutable, carbon or nitrogen in the group or a substitutable atom such as oxygen may have a substituent. There may be a plurality of substituents, and these substituents may have one or more substituents. Typical examples of these permissible substituents are halogen atom, cyano group, nitro group, hydroxyl group, carboxyl group, sulfo group and G group.
−, GO−, GS−, GCO−, GCOO−, −CONH ₂ −, −OCON
_{H 2, -SO 2 NH 2,} -NHCONH 2 -, - NHSO 2 NH 2, -SO 2 G, -S
OG, —COOG, —NHSO ₂ G and the like, where G represents a resin group hydrocarbon group, an aryl group or a heterocyclic group.

In the general formula (III), m represents an integer of 0 to 3, n represents 0 or 1, and m + n represents an integer of 1 to 3.

In the general formula (III), L ₃ , l ₃ and PUG have the same meanings as L ₁ , l ₁ and PUG in the general formula (I), respectively.

In the general formula (IV), Z ₄ , L ₄ , l ₄ and PUG have the same meanings as Z ₁ , L ₁ , l ₁ and PUG in the general formula, respectively. R ₅ and R _{6 in the} general formula (IV) are preferably each a hydrogen atom,
Represents an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, a halogen atom, an acyl group, etc., and R ₅ and R ₆ combine to form a cycloalkyl group, a carbonyl group, a thiocarbonyl group, or an imino group. Alternatively, the above-mentioned groups may have a substituent, and as these substituents, those exemplified as the substituent of Z ₁ in the general formula (I) are preferable.

In the general formula (V), R ₇ and R ₈ may be the same or different, preferably a hydrogen atom, an alkyl group,
Aryl group, alkenyl group, aralkyl group, amino group,
It represents an imino group, a hydroxy group, an alkoxy group, an aryloxy group or the like, and may have a substituent other than a hydrogen atom or a hydroxy group, or R ₇ and R ₈ are bonded to each other to form a ring. May be formed.

R ₇ and R ₈ more preferably represent an alkyl group or an aryl group, one of which may be a hydrogen atom and the other may be substituted; or an alkyl group or an aryl group, both of which may be substituted.

Particularly preferably, R ₇ and R ₈ each represent a substituted or unsubstituted alkyl group, or R ₇ represents a hydrogen atom and R ₈ represents a substituted or unsubstituted alkyl group.

The amine represented by the general formula (V) may be contained in the processing solution or may be added to the photosensitive material, in which case it is contained as an amine precursor represented by a salt with an acid. You may.

The precursor compounds of the present invention represented by the general formulas [I] to [IV] have excellent storage stability, and at the same time, during development processing (for example, conventional monochrome / color photographic processing, diffusion transfer method monochrome / color photographic processing, heat development color). The reason for the rapid release of the photographically useful reagent in the presence of the amines represented by the general formula [V] is not yet clear, but with reference to the literature on thiazolidinethione derivatives by Eiichi Fujita et al. Can be thought of as.

Fujita et al., Proceedings of the 22nd Natural Organic Compounds Conference, 55
Page 4 (1979); Tetrahedron Letters
Letters), Vol. 21, pp. 841 (1980).
The reactivity of the N-acyl derivative [VI] of 2-thione (wherein R represents an alkyl group) is reported in detail. According to it, compound [VI] It is extremely stable in water and does not undergo any hydrolysis. It is also described that it has low reactivity with alcohols or hydroxide ions, but reacts rapidly with amines. It is considered that the precursor compounds [I] to [IV] of the present invention also undergo the same reaction as above,
It stably exists without being affected by water present during storage, and upon development, reacts with various amines represented by the general formula [V] to cause rapid cleavage of a bond to form a photographically useful group. Since it is released, it can be presumed that both stability during storage and high reactivity during development are compatible.

The preferred addition amount of the precursor compound of the present invention exemplified by the general formulas [I] to [IV] depends on the kind of the photographic reagent to be released, but the antifoggant and the development inhibitor are 10 ^-8 per mol of silver. -10 to 10 ^-1 mol, preferably 10 ^-6 to 10 ^-1 mol for a mercapto-based antifoggant, 10 ^-5 to 10 ^-1 mol for an azole-based antifoggant such as benzotriazole, and silver 1 for a developing agent.
10 ^-2 to 10 mol per mol, preferably 0.1 to 5 mol, the pyrazolidone-based auxiliary developing agent is 10 ^-4 to 10 mol, preferably 10 ^{-2 to} 5 mol, per 1 mol of silver, and the development accelerator or nucleating agent is 10 ^-2 to 10 ^-6 mol, and preferably 10 ^-3 to 1 mol of silver
A silver halide solvent such as 10 ^-5 mol and sodium thiosulfate is 10 ^-3 to 10 mol, preferably 10 ^-2 to 1 mol per mol of silver, and a dye or a color material for color diffusion transfer photographic is 10 per mol of silver. ^-3 to 1 mol, preferably 5 x 10 to 0.5 mol.

When the amines represented by the general formula [V] are added to the treatment liquid, the addition amount thereof is 10 ⁻³ to 1 mol / l, preferably 10 ^{−3.
It is −2 to} 5 × 10 ⁻¹ mol / l. When it is added to the light-sensitive material, it is 10 ^-7 mol to 10 mol, preferably 10 ^-5 mol, per mol of silver.
Mol to 1 mol. Since amines show a reducing property although they are very weak, fog tends to occur when the upper limit of the above range is exceeded.

Next, the precursor compound [I] used in the present invention
Specific examples of [IV] and amines [V] are shown below, but the invention is not limited thereto.

(Exemplified compound) The photographic reagents in the above compounds are as follows.

(1) Antifoggant, development inhibitor (Compound examples: [I]-(1) to (4), (7),
(8), (10), (13), (14), (16), (17),
(22), (23), (25), (28) to (30), (32),
(33), (40), (41), (44), (45), [II]-
(1) to (4), (9), (13), (15), (16),
(19), (20), [III]-(1) to (10), (13),
(14), (26), (30), [IV]-(1) to (3),
(8)-(10), (13), (15), (16), (18)-
(20), (22) to (24)) (2) Auxiliary developer ([I]-(5), (12), (15), (18), (20),
(24), (42), [II]-(5) to (7), (17),
[III] (17) to (20), [IV]-(4), (5), (1
2), (14)) (3) Dye ([I]-(6), (34), (35), [II]-(10),
[III]-(24), (27), [IV]-(7), (17),
(25)) (4) DIR hydroquinone ([I]-(9), (36) to (39), (43), [II]-
(8), (18), [III]-(22), (23), (25),
(28)) (5) Coupler ([I]-(11)) (6) Nucleating agent ([I]-(19), (21), (27), [II]-(12),
(14), [III]-(15), (16), [IV]-(11)) (7) Bleaching accelerator ([I]-(26), (31), [II]-(11) , [III]
-(11), (12), (29), [IV]-(21)) (8) Developer ([III]-(21), [IV]-(6)) [V]-(1)ⁿ C_FourH₉NH₂ [V]-(2) HOCH₂CH₂NH₂  [V]-(9)ⁿ C₈H₁₇NH₂ [V]-(10) CH₃OCH₂CH₂NH₂ [V]-(11) (ⁿC_TenH_{twenty one}NH₂)₂・ H₂SO_Four [V]-(12)ⁿ C₁₆H₃₃NH₂ [V]-(14) C₃H₇OCH₂CH₂OCH₂CH₂NH₂ [V]-(15) (HOCH₂CH₂)₂NH [V]-(16) (CH₃OCH₂CH₂)₂NH [V]-(17) (C₂H_Five)₂NH [V]-(25) NH₃ CH₂CH₂SO₃   Represented by the general formula [I] and the general formula [II] of the present invention
The synthetic method of the compound is described in Japanese Patent Application No. 60-221295, in which
II] is a compound described in Japanese Patent Application No. 60-200751.
The compound represented by the general formula [IV] is described in Japanese Patent Application No. 60-221296.
It is described in detail in each detailed document.

Amines represented by the general formula [V] are, for example, RB Wagner, HD Zock, Synthetec Organic Chemistry, Item 653, Zon Willie End Sands, 1953 (RBWagner, HDZook, Synthetic Organic
Chemistry, P.653, John Wiley and Sons Inc., 1953), but it can be easily obtained from domestic and overseas reagent manufacturers. (For example, it is described in the reagent maker catalogs of Tokyo Kasei Kogyo, Wako Pure Chemical Industries, Kanto Kagaku Kogyo, Koei Kagaku Kogyo, Aldrich, Merck, etc.) Precursor of the photographically useful reagent used in the present invention [I]
To [IV] may be used in combination of two or more kinds, and the amines represented by the general formula [V] may be used in combination of two or more kinds.

The blocked photographic reagent (precursor) of the present invention
[I] to [IV] are images of a silver halide emulsion layer, a color material layer, an undercoat layer, a protective layer, an intermediate layer, a filter layer, an antihalation layer, a black and white or color diffusion transfer method of a silver halide photographic light-sensitive material. It may be added to any of the layers or cover sheet layers and other auxiliary layers.

In order to add the placursors used in the present invention to these layers, the precursor is left in the coating liquid for forming the layers, or a solvent that does not adversely affect the photographic light-sensitive material, such as water or alcohol. It can be added after being dissolved in an appropriate concentration. Further, the precursor may be dissolved in a high boiling point organic solvent and / or a low boiling point solvent and then emulsified and dispersed in an aqueous solution and added. Also, JP-A-51-39853, JP-A-51-59942, JP-A-54-32552, U.S. Pat.
It may be added by impregnating the polymer latex by the method described in JP-A-199,363.

The precursor of the present invention may be added at any time during the process for producing a light-sensitive material, but it is generally preferable to add it immediately before coating. The amines represented by the general formula [V] are used by adding them to the developer, but they may be added in the light-sensitive material. In that case, it is preferable to add them to a layer different from the precursors represented by the general formulas [I] to [IV] so that they react with each other during processing. In addition, it is particularly preferable to form an ammonium salt with a strong acid to add it.

The compound of the present invention can be used, for example, in a coupler type color photographic light-sensitive material.

As a general method for forming a color image from a color photographic light-sensitive material, a subtractive color method is used, and yellow, magenta, and cyan, which have a complementary color relationship with silver halide emulsions selectively sensitive to blue, green, and red, respectively. Color image forming agents are used. For example, acylacetanilide or dibenzoylmethane type couplers are used for forming yellow color images, and pyrazolone, pyrazolobenzimidazole, cyanoacetophenone or indazolone type couplers are mainly used for forming magenta color images. For forming cyan images, phenolic couplers such as phenols and naphthols are mainly used.

Generally, color photographic light-sensitive materials are roughly classified into an external type in which a coupler is put in a developing solution and an internal type in which a coupler is contained in each photosensitive layer of the photosensitive material so as to maintain an independent function. It In the latter, dye image-forming couplers are incorporated in the silver halide emulsion. The coupler added to the emulsion must be non-diffused (diffused resistant) in the emulsion binder matrix.

In the internal method, the process of processing a color photographic light-sensitive material basically consists of the following three processes.

(1) Color development step (2) Bleach step (3) Fixing step The bleaching step and the fixing step can be performed simultaneously. That is, it is a bleach-fixing step (so-called brix), in which developed silver and undeveloped silver halide are desilvered. In addition to the two basic steps of color development and desilvering described above, the actual development process includes auxiliary steps such as maintaining the photographic and physical quality of the image or improving the storability of the image. Accompany it. For example, a hardening bath to prevent excessive softening of the photosensitive film during processing, a stop bath to effectively stop the development reaction, an image stabilizing bath to stabilize the image, or a desorption to remove the backing tank of the support. A process such as a membrane bath may be mentioned.

In order to introduce the coupler into the silver halide photographic light-sensitive material of the present invention, the conventionally known method for adding or dispersing the coupler to the emulsion and its addition method to the gelatin / silver halide emulsion or hydrophilic colloid are known. Is applied. For example, a high boiling organic solvent-dibutyl phthalate, tricresyl phosphate, wax, a method of mixing and dispersing a coupler with a higher resin acid and its ester, for example, U.S. Pat.
304,939, No. 2,322,027, etc. Also, a method in which a coupler having a low boiling point organic solvent or a water-soluble organic solvent is mixed and dispersed. A method of dispersing the coupler in combination with a high boiling point organic solvent. For example, U.S. Pat.
No. 0, No. 2,801,171, No. 2,949,360, etc., the coupler itself is sufficiently low melting point (for example, 75 ℃
In the case of the following), a method of dispersing them alone or in combination with other couplers to be used in combination, such as colored couplers or uncolored couplers. For example German Patent No. 1,14
Descriptions such as 3,707 apply.

As the dispersion aid, a commonly used anionic surfactant (for example, alkylbenzene sodium sulfonate,
Sodium dioctyl sulfosuccinate, sodium dodecyl sulphate, sodium alkylnaphthalene sulfonate, Fischer type couplers, etc. Zwitterionic surfactants (eg N-tetradecyl N, N dipolyethylene α betaine etc.) and nonionic surfactants (For example, sorbitan, monolaurate, etc.) is used.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, a color-forming coupler, that is, a color formed by oxidative coupling with an aromatic primary amine developing agent (for example, a phenylenediamine derivative or an aminophenol derivative) in the color development processing is formed. It may also contain a compound. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and the like, and yellow couplers include acylacetamide couplers (for example, benzoylacetanilides, pivaloylacetanilides). , Etc., and cyan couplers include naphthol couplers, phenol couplers, and the like. These couplers are preferably non-diffusible ones having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ion. Further, it may be a colored coupler having a color correcting effect, or a coupler releasing a development inhibitor with development (so-called DIR coupler). In addition to the DIR coupler, a colorless DIR coupling compound which is colorless in the product of the coupling reaction and releases a development inhibitor may be contained.

When the photographic element of the present invention is applied to color diffusion transfer photographic method, it is a peeling (beer apartment) type or Japanese Patent Publication No. 46-1.
6356, 48-33697, JP-A-50-13040, and integrated type as described in British Patent 1,330,524, peeling as described in JP-A-57-119345 The unnecessary film unit can be configured.

The compounds of the present invention can also be used in black-and-white light-sensitive materials. Examples of the black-and-white light-sensitive material include X-ray film for direct medical use, black-and-white film for general photography, lith film, scanner film and the like.

Other constitutions of the silver halide photographic light-sensitive material of the present invention, for example, a method for producing a silver halide emulsion, halogen composition, crystal habit, grain size, chemical sensitizer, antifoggant, stabilizer, surfactant, gelatin. Hardened silver, hydrophilic colloid binder, matting agent, dye, sensitizing dye, anti-fading agent, anti-color mixing agent, polymer latex, whitening agent, antistatic agent, etc. are not particularly limited. For example, Research Disclosure (Research Disclosure) Volume 176, 22-31
The description on page (December 1978) can be referred to.

The compounds of the present invention are also suitable for activator processing in which a color developing agent or its precursor is incorporated in a light-sensitive material and processed in an alkaline bath. Further, even when the activator treatment is carried out at a high temperature of 50 ° C. or higher, a precursor which is advantageous in terms of storability can be selected, and the compound of the present invention can be used for such purpose.

Further, a method of exposing the silver halide photographic light-sensitive material of the present invention,
The developing method and the like are not particularly limited, and any of known methods and known processing solutions described in Research and Disclosure, pages 28 to 30 can be applied. This photographic processing may be either photographic processing for forming a silver image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing) depending on the purpose. The treatment temperature is usually selected between 18 ° C and 50 ° C, but it may be lower than 18 ° C or higher than 50 ° C. Especially when treated at a high temperature of 50 ° C or higher, the reaction between the precursor and the amines is accelerated, and the release rate of the photographically useful reagent from the precursor is increased, so it is possible to select a precursor that is advantageous in terms of storage stability. Becomes

The developing solution used for black-and-white photographic processing may contain a known developing agent. As developing agents, dihydroxybenzenes (for example, hydroquinone), 3-
Pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p)
-Aminophenol) and the like can be used alone or in combination. The developer generally contains other known preservatives, alkali agents, pH buffers, antifoggants, etc.,
Further, if necessary, a dissolution aid, a color toning agent, a development accelerator, a surfactant, a defoaming agent, a water softener, a film hardener, a viscosity imparting agent, etc. may be contained.

A so-called "lith type" development process can be applied to the photographic emulsion of the present invention. What is "lith type" development processing? For the photographic reproduction of line images or the photographic reproduction of halftone images with halftone images, dihydroxybenzenes are usually used as the developing agent, and the development process is performed under a low sulfite ion concentration. It is a development process that makes the process contagious.

Also, U.S. Pat.Nos. 4,166,742, 4,168,977, and 4,22.
1,857, 4,224,401, 4,243,739, 4,272,60
No. 6, 4,311,781 and the like, the method of the present invention is applied to the reproduction of halftone images and line drawings when the surface latent image type emulsion is developed in the presence of a hydrazine compound to obtain a hard photographic property. Photographic properties that are effective, have extremely high sensitivity and high contrast, and are free from the occurrence of non-imagewise fine dot-like blackening phenomenon called black spots can be obtained.

The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. Color developing agents are known general aromatic amine developers such as phenylenediamines (e.g. 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-). N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4
-Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-
Methanesulfoamidoethylaniline, 4-amino-3-
Methyl-N-ethyl-N-β-methoxyethylaniline and the like) can be used.

LFA Mason's "Photo Processing Chemistry" (published by Focal Press) [LFAMason, Photographic Processing Ch
emistry (Focal Press)], pp. 226-229, U.S. Pat. Nos. 2,193,015 and 2,592,364, JP-A-48-64933.
No., etc. may be used.

(Effects of the Invention) The silver halide photographic light-sensitive material of the present invention has an excellent effect that it exists stably under storage conditions and promptly and efficiently releases photographic reagents at the timing required during processing. . In particular, the silver halide photographic light-sensitive material of the present invention can realize a timely release of the photographic reagent even when it is processed with a processing solution having a relatively low pH of 9 to 12.
Further, in the present invention, there is an excellent effect that desensitization due to addition of the photographic reagent precursor can be prevented and the function of the released photographic reagent can be exhibited.

(Example) The present invention will be described in more detail with reference to the following examples.

Example 1 The effectiveness of processing the development inhibitor precursor of the present invention in the presence of amines was evaluated.

[Emulsion I]

4 x 10 ^-7 per Ag / mol in gelatin aqueous solution kept at 50 ℃
In the presence of a molar amount of potassium iridium (III) hexachloride and ammonia, an aqueous solution of silver nitrate, an aqueous solution of potassium iodide and an aqueous solution of potassium bromide were added simultaneously for 60 minutes, and the pAg was kept at 7.8 during that period to obtain an average particle size of 0.28μ, A cubic monodisperse emulsion having a silver iodide content of 1 mol% was prepared. Further, this emulsion was washed with water according to a conventional method to remove soluble salts, gelatin was added, and chemical sensitization was performed with sodium thiosulfate. Subsequently, an emulsion I was prepared by adding 0.1 mol% aqueous potassium iodide solution per mol of silver to convert the grain surface.

Emulsion I contained 5,5'-dichloro-9-ethyl-3,3'-bis (3-sulfopropyl) oxacarbocyanine sodium salt as a sensitizing dye and 4-hydroxy-6-methyl-1 as a stabilizer. , 3,3a, 7 Tetrazaindene, polyethyl acrylate dispersion, polyethylene glycol, 1,3
-Vinylsulfonyl-2-propanol and the compounds of the invention as shown in Table 1 and compound A: 2- [4- [2- (2,4
-Di-tert-pentylphenoxy) butyroamido] phenyl] -1-formylhydrazine was added, and coating was performed on a polyethylene terephthalate film so that the silver amount was 3.5 g / m ² . As a comparison, a sample containing no compound of the present invention and an unblocked development inhibitor was prepared. In this way, Sample Nos. 1 to 22 as shown in Table 1 were prepared, and each sample was exposed and developed using the developing solution I or II shown below to measure the characteristics. The results are shown in Table 1.

Developer Formulation I Hydroquinone 35.0 g N-methyl-p-aminophenol 1/2 sulfate 0.8 g Sodium hydroxide 9.0 g Potassium triphosphate 74.0 g Potassium sulfite 90.0 g Ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium bromide 3.0 g 5-Methylbenzotriazole 0.5g 3-Diethylamino-1-propanol 15.0g Diethanolamine ([V] to (15)) 15.0g Add water 1 (pH = 11.6) Developer formulation II Hydroquinone 35.0g N-methyl- p-Amino phenol 1/2 sulfate 0.8g Sodium hydroxide 9.0g Potassium triphosphate 74.0g Potassium sulfite 90.0g Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium bromide 3.0g 5-Methylbenzotriazole 0.5g 2-Butyl Aminoethanol ([V]-(8)) 17.0g Add water 1 (pH = 11.6) The results are shown in Table 1. As is clear from Table 1,
The samples 2 to 7 and 13 to 20 of the present invention have a remarkable effect of improving the black spots while maintaining the characteristics of high sensitivity and high contrast as compared with the comparative samples 8 to 11 and 19 to 22.

The relative sensitivity is the relative value of the reciprocal of the exposure amount that gives a turbidity of 1.5 at 38 ° C. for 30 seconds, and the value of Sample 1 is set to 100.

○ Black spots are evaluated on a scale of 5 by microscopic observation, with "5" being the best and "1" being the worst.
"5" or "4" is practical, "3" is poor but practically usable, and "2" or "1" is not practical. "3"
The one between "4" and "4" was evaluated as "3.5", and the one between "4" and "5" was evaluated as "4.5".

○ Black spots are evaluated when the pH of the developer rises to 11.8.
38 ° C., 30 ″ development result.

Example 2 An antifoggant precursor and a magenta coupler (C-1) shown in Table 2 were dissolved in tricresyl phosphate and ethyl acetate on a cellulose triacetate film support provided with an undercoat layer to form a gelatin. Samples 1 to 11 were prepared by coating the following emulsion layers which were emulsified and dispersed in an aqueous solution. The coating amount of each substance is shown in parentheses as g / m ² .

(1) Emulsion layer Negative type silver iodobromide emulsion (grain size 1.5μ silver 1.6 × 10 ^-2 mo
l / m ² ) Antifoggant precursor or DIR compound (8.0 × 10 ^-5
mol / m ² magenta coupler C-1 (1.33 × 10 ^-3 mol / m ² ) tricresyl phosphate (0.959g / m ² ) gelatin (2.5g / m ² ) (2) protective layer 2,4-dichloro -6-Hydroxy-s-triazine sodium salt (0.05g / m ² ) Gelatin (1.30g / m ² ) After leaving these films at 40 ° C and 70% relative humidity for 14 hours, they are sensitized with white light. After exposure for totometry, the following color development processing (A processing) was performed. The processed sample was subjected to density measurement with green light to obtain photographic data.

Color development process time Temperature 1. Color development 3'15 "38 ℃ 2. Bleach 6'30" 〃 3. Wash with water 2'〃 4. Fixing 4'〃 5. Wash with water 4'〃 6. Safety 1 '= Here, the composition of each processing solution in the color development processing step is as follows.

Color developer water 800 ml 4- (N-ethyl-N-hydroxyethyl) amino-2
-Methylaniline / sulfate 5g Sodium sulfite 5g Potassium carbonate 30g Potassium hydrogen carbonate 1.2g Potassium bromide 1.2g Sodium chloride 0.2g Trisodium nitrilotriacetic acid 1.2g Add water 1 (pH10.1) Bleach solution Water 800ml Ethylenediaminetetraacetic acid Ferric ammonium salt 100 g Ethylenediaminetetraacetic acid disodium 10 g Potassium bromide 150 g Nitric acid 10 g Water added 1 (pH 6.0) Fixer water 800 ml Ammonium thiosulfate 150 g Sodium sulfite 10 g Sodium bisulfite 2.5 g Water added 1 (pH 6 .0) Stabilizer Water 800 ml Formalin (37%) 5 ml Dry well 3 ml Water was added 1 Next, except that 5 × 10 ^-2 mol of amines shown in Table 2 was added to the color developer 1 of A treatment. The completely same process as the A process was performed. These processes are called B to E processes. In addition,
The pH of the developer for the B to E processing is 10.1.

Table 2 shows the values of the maximum color densities of Samples 1 to 11 by the respective treatments.

From Table 2, in the case of the treatment with the treatment liquid A containing no amine acid, the samples 2 containing the antifoggant precursor compound
11, the decrease in color density was small. On the other hand, when the treatment liquids B to E containing amines were used, a large decrease in color density was observed in all of Samples 2 to 11 containing the antifoggant precursor.

From the above facts, it is clear that the amines promote the release of the antifoggant from the precursor compound in Samples 2 to 9 during the treatment.

The couplers used here are as follows.

Example 3 The emulsion layer shown in Example 2 was further modified with a salt of amines (4 × 10 6
^-3 mol / m ² ), coating samples 12 to 15 were prepared. These film samples were exposed in the same manner as in Example 2 to give A of Example 2.
The photographic properties obtained after the treatment and the C treatment are shown in Table 3.

From Table 3, in all cases, the A treatment of the sample containing no salt of amines did not reduce the fog, but the C treatment did not substantially reduce the relative sensitivity, but the fog was reduced. On the other hand, it is clear that in Samples 12 to 15 in which amines were applied as salts to the light-sensitive material in advance, the A treatment significantly reduced the fog while maintaining the relative sensitivity. Therefore, it is apparent that the effect of accelerating the deprotection reaction of the precursor by the amines of the present invention is similarly exerted even when the processing liquid is added or when it is preliminarily applied to the photosensitive material.

Claims (1)

[Claims] 1. At least one photographic reagent precursor represented by the following general formula, and at least 1
A method for processing a silver halide photographic light-sensitive material, which comprises processing a photographic light-sensitive material having a light-sensitive silver halide emulsion layer as a layer in the presence of amines. (In the general formulas (I) to (IV), PUG is a photographic reagent selected from an antifoggant, a development inhibitor, an auxiliary developing agent, a dye, a DIR hydroquinone, a coupler, a nucleating agent, a bleaching accelerator or a developing agent. Represents a photographically useful group consisting of L ₁ , L ₂ and L ₃ represent a timing group, respectively, l ₁ , l ₂ and
l ₃ represents 1 or 0 respectively; R ₁ , R ₂ , R ₃ and R ₄
Represents a hydrogen atom or a substituent; Z ₁ , Z ₂ and Z ₃ are 5
Represents a nonmetallic atom group forming a member ring to a 7-membered ring, and the ring may form a condensed ring. )