JPS59140445A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To enable release of a photographic reagent kept perfect in storage conditions at a necessary timing in processing by using a specified photographic reagent for a photosensitive material contg. a photosensitive emulsion layer having a photographic reagent in combination. CONSTITUTION:A photographic reagent in a photographic material contg. a photosensitive silver halide emulsion combined with the photosensitive reagent is blocked with hetero atoms as shown in the formula in which when n is O, A is a photographic reagent, and combines through N or O with a phthalide ring and when n is 1, A combines through N, O, or S with Z, and Z is a divalent bonding group. As said blocked photographic reagent, a compd. directly combined with one of azole type antifoggants typified by benzotriazoles, or an assistant developing agent of one of pyrazolidones is especially desirable. As the addition amt. of said reagent, a desirable amt. of antifoggant is 10<-8>-10<-1> mole per mole of silver halide, and that of said assistant developer is 10<-4>-10<-1> mole per mole of silver halide, as shown in the table.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photographic material, and more particularly to a photographic material containing a precursor compound in which the active group of a photographically useful photographic reagent is blocked.

The fact that a photographically useful photographic reagent is added in advance to a photographic light-sensitive material and its effect is exhibited is different from the case where it is used by containing it in a processing solution. Its features include, for example, the ability to effectively utilize photographic reagents that are easily decomposed under acidic/alkali or oxidizing/reducing conditions and cannot withstand long-term storage in processing baths; It may be possible to use the necessary photographic reagents at the necessary timing during processing, or it may be possible to apply the necessary photographic reagents only in the necessary locations, that is, in a certain layer of a multilayer photosensitive material and in its neighboring layers. Examples include being able to work the reagents and vary the amount of photographic reagents present as a function of silver halide development. However, if a photographic reagent is added to a photographic light-sensitive material in an active form, it may react with other components in the photographic light-sensitive material or decompose due to the influence of heat, oxygen, etc. during storage before processing. As a result, the expected performance cannot be achieved during processing. As a method for solving such problems, there is a method of blocking the active groups of a photographic reagent and adding it to a photographic light-sensitive material in a substantially inactive form, that is, as a precursor for a photographic reagent. When a useful photographic reagent is a dye, it greatly affects the spectral absorption of the dye.
Blocking the functional group that is I'' and shifting its spectral absorption to the short wavelength side or to the long wavelength side (C=) It has the advantage that there is no reduction in sensitivity due to the so-called filter effect.If a useful photographic reagent is an antifoggant, currently an inhibitor, it blocks active groups and prevents adsorption of silver to photosensitive silver halide during storage. At the same time, it can suppress the desensitizing effect caused by salt formation.
These photographic reagents are released at the required timing (which has advantages such as reducing fog without impairing sensitivity, suppressing over-development fog, or being able to stop development at the required time. If the useful photographic reagent is a developer, auxiliary developer, or ζ4 fogging agent, by blocking the active or adsorbent groups, various photographic effects due to the formation of semiquinones and oxidants due to air oxidation during storage can be prevented. It has the advantage of preventing fog nucleation during storage by preventing adverse effects on the copper halide or preventing electron injection into the copper halide, and as a result, stable processing can be achieved. - In the case of fixation accelerators, by blocking their active groups, the reaction with other components contained therein is suppressed during storage, and by removing the blocking groups during processing, desired performance can be achieved. It has the advantage of being able to be used at the right time.

As mentioned above, the use of photographic mulberry precursors 1I can be an extremely effective means for maximizing the performance of '14xμs, but on the other hand, these precursors − must satisfy very strict requirements. In other words, it is stable under storage conditions, and during processing, the blocking group is released at the required timing, allowing the photographic reagent to be released quickly and efficiently. Must be.

Several blocking techniques for photographic reagents are already known. For example, those using the acyl group, sulfonyl group, etc. described in the specification of Tokko Sho 2-Gugu and J'Oj, Tokko Sho! Dar J 9, 7
．． 27th ridge, same 3. No. 945', No. 9.22 Akira J (L+ book), so-called j; f2, utilizing a blocking group that releases a photographic reagent by the Michael reaction, Tokko Sho, 4i&-1. No. 2.27, JP-A-Sho J-
7-73. t9 gugu issue, same J7-/,? Nata + t3,
JP-A No. 77-/3t&yO, which utilizes a blocking group that releases a photographic reagent for the production of a quinonemebdo or non-mebdo-like compound by intramolecular electron transfer, as described in JP-A No. 77-/3t&yO, JP-A No. 7330. Those that utilize the intramolecular ring-closing reaction described in IvlllltF, or those that utilize the intramolecular ring-closing reaction described in IvlllltF, or those that utilize the intramolecular ring-closing reaction described in
J9 & ri number, same j7-/7rit number listed in the specification blind
Techniques that utilize ring cleavage of members or g members are known as well-known techniques. These known techniques are used to store f'+
If 1 is stable, the release rate of the photographic reagent during processing is too low and requires high alkaline treatment with a pH of 2 or more, or the release rate is not sufficient in a processing solution with a pH of 2 or more. Even under storage conditions, it gradually decomposes and the precursor
This invention has drawbacks such as impairing the function of IJ- and the inability to widely control the release rate of photographic reagents, which limits the pH range in which it can be used. The blocked photographic agent is completely stable and releases the photographic reagent at the required timing during processing.
lc reagent, and furthermore, a wide range of pH ft.
The objective is to provide a blocked photographic reagent that exhibits a substantial function in the field.

An object of the present invention is to provide a photographic material containing a photosensitive halogenated emulsion layer in which a blocked photographic reagent is combined, in which the photographic reagent is expressed by the following general formula (1) via a heteroatom. This was achieved using a photosensitive material that is blacked out as shown in the photosensitive material L7.

General formula (1) (wherein, when A is n-θ, it represents a photographic reagent bonded via a nitrogen atom or an oxygen atom, and when n-/, it is a photographic reagent bonded via a nitrogen atom, an oxygen atom, or a sulfur atom. represents a photographic reagent with a Z knee bond.

2 represents a divalent linking group bonded to the phthalide nucleus via an oxygen atom, and n represents O or /.

X is a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxy group, a carbonate ester group, an amino group, a carbonamide group, a sulfonamide F group, a ureido group, an aminosulfonamide group,
carbamate group, carboxy group, mexicarponyl group,
It represents a carbamoyl group, an acyl group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a syl group, or a nitro group, and m represents an integer of O to G. ) A represents a useful photographic reagent, and when n=θ, it is a known photographic reagent bonded with a nitrogen atom or an oxygen atom, and specifically, a fog reagent represented by benzotriazoles or indazoles. Inhibitor; Developer represented by hydroquinones; Auxiliary ring f represented by pyrazolidones
Fogging agents such as hydrazines and hydrazides; Photographic reagents that represent dyes and have redox functions such as color diffusion transfer sensitive materials, such as hues or DIR-ha.f It shall also contain droquinones. If n == /, in addition to the above photographic reagents, mercaptotetrazoles antifoggants, void suppressors: p-phenylenediamines or aminophenols. Represents a developer such as a type.

Z represents a covalent linking group, is bonded to the 3-position of the phthalide group via an oxygen atom, and represents a group that rapidly releases A upon treatment (after cleavage as 2-Z-A). Examples of such a linking group include those that release A by an intramolecular ring-opening reaction described in JP-A-41-/4T, !T/33, British Patent WS, No. 2072JT-3, and JP-A-Sho-T7- /j
Those that release A by intramolecular electron transfer as described in Specification No. 23, etc., and those that release A with desorption of carbon dioxide gas as described in No. 1J [(j7-/7? things to do,
Alternatively, there may be mentioned linking groups such as those described in Japanese Patent Application No. 7-2θ3 Gudai, which release A with the elimination of formalin. The structural formulas of the two representative Zs mentioned above are shown below.

(A) Examples of the halogen atom in UX include fluorine, chlorine, and bromine atoms. The alkyl group of , , the aryloxy group has a carbon number of JA-Jj, the alkylsulfonyl group has a carbon number of /~-〇, and the arylsulfonyl group has a carbon number of 4-. It includes 24.

The amino group of , carbamoyl group, and sulfamoyl group may be similarly substituted with an alkyl group or an aryl group. A carbonamide group, a sulfonamide group, a carbamate group, an oxycarbonyl group, and a carbonyl group are each an alkyl group having 0 carbon atoms or 6 to 0 carbon atoms.
．． It includes those substituted with 2d aryl group.

The alkyl group, alkenyl group, and aryl group mentioned above are
It also includes those in which the various substituents mentioned above are further (disubstituted). m preferably represents O to C.

The selection of X is determined by the pH of the processing solution in which the photographic element containing the photographic reagent precursor of the present invention is processed and the required timing period. For example, in the case of processing using a high pH processing solution or when slow timing is required, an electron-donating group such as an amino group, an alkyl group, or an alkoxy group is selected as X. Reverse (=pH
When processing with a low pH processing solution of q-tt or when fast timing is required, X should be an electron-withdrawing group such as a halogen atom, an acyl group, a sulfonyl group, a cyano group, or a 21. By selecting the group, the desired purpose can be achieved.

JP-A-7-77JF/1999 discloses a precursor compound in which a mercapto-substituted heterocyclic antifoggant, represented by mercaptotetrazole 42, is directly bonded via a sulfur atom. Although the release performance of these precursors for photographic reagents is certainly excellent, their thermal stability during storage is not necessarily satisfactory, and they have drawbacks such as a significant decrease in sensitivity. In contrast, the compounds of the present invention, such as precursor compounds to which benzotriazoles are directly bonded, have excellent thermal stability and
It does not have the above-mentioned drawbacks, and moreover, during processing, the release of benzotriazoles occurs well in the evening and in the morning, reducing fog without impairing sensitivity. These characteristics are the same for the 11-drug precursors to which pyrazolidones are directly bound, and even under thermoconditions, there is almost no decrease in sensitivity or increase in fog due to the formation of semiquinones or decomposition. Moreover, during salt treatment, pyrazolidones are released quickly and exhibit a remarkable development accelerating effect.

Therefore, the blocked photographic reagent 4 represented by the general formula (1) of the present invention is supplemented with an azole antifoggant such as benzotriazoles or a pyrazolidone 41#! Compounds to which the drug is directly attached have particularly favorable characteristics.

The amount of the compound of the present invention to be added varies depending on the photographic reagent, but the amount of antifoggant or developer inhibitor such as benzotriazole is 10-8 to 10-1 mol, preferably 10 to 10-2 mol, per 7 mol of plane. mol, and the auxiliary developer such as pyrazolidones is 10-' to 10 mol per mol of silver, preferably /θ-2~! It is a mole.

The following are two specific examples of useful blocked photographic reagents of the present invention, but are not limited thereto.

(1) That is, 0-phthalaldehydic acid and its derivatives (
(1) (n=θ) can be easily obtained by reacting II) with A having an -NH group or 10H group through thermal dehydration condensation. On the other hand, (1) (n=/') is the above-mentioned JP-A-Sho! Ku/4tJ'/31, British Patent No. 20723 No. 3, JP-A-Shoj? -/j4t co34 No., t7-/7ri/4t No. 2, and the reaction of (...) with thionyl chloride according to the synthesis example described in the patent application Sho J Cuco θ5aat. (1) or straight t! (IV) is obtained by the reaction of (II) with Z, and a base (e.g. t-7
Z-A can be obtained by reacting A in the presence of triethylamine or triethylamine, etc., but after reacting A and the two parts in advance to form Z-A, dehydration of Z-A and (1). It can also be obtained by condensation reaction (2).

Specific synthesis examples of the compound represented by the general formula (1) of the present invention are shown below.

Synthesis example/〈Synthesis of compound (co)〉 □Commercially available 0-phthalaldehyde acid in 200 ml of dry toluene,
θt(o, o4t4f)! -Methylbenzotriazole, t, 3f (θ, θ damol) were added, and the mixture was heated under reflux for 1 hour using a dehydrating reflux device at an oil bath temperature/t o 'C1:.

When hot, insoluble materials were filtered, and after cooling, the mixture was crystallized with ether to obtain 7 f of crude crystals. When this crude crystal is recrystallized with loloform-ether, the desired 3-(j-
Methyl-/-benzotriazolyl)phthalide (,2) is j.

II was obtained. m, p, /31 to /4tO0C0 Synthesis Example - Synthesis of Compound (/, 2)> Commercially available O-phthalaldehydic acid t,ot (0.09 mol), /,! in 2jtOml of dry toluene. -D phenylpyrazolidin-3-one9. ! f (0.04t mol)
and a catalytic amount of p-)luenesulfonic acid were added, and the mixture was heated under reflux at an oil bath temperature of /OoC for 1 hour using a dehydrating reflux device. After cooling the reaction mixture, the crude crystals were distilled off under reduced pressure.
4t and 2f were obtained. The desired 3-(/
,,1-diphenyl-3-keto-virazolidinyl)
Phthalide (80,9.!f was obtained. m, p, /liter/j, 2°C0 Synthesis Example 3 <Synthesis of compound (,2/)> Commercially available -Phthalaldehydic acid A, Of (0,041 mol) was added thereto, and 1 ml of a 1 on) toluene solution of phosgene was gradually added dropwise thereto, and the mixture was stirred at room temperature for 70 hours.

After the reaction, the excess phosgene was removed by distilling off the solvent under reduced pressure at a temperature below 3o"c to obtain a pale yellow oil of crude chloroformic acid phthalidyl ester. Due to instability, it was used in the next reaction without purification. provided.

continue,! -Methylbenzotriazole 4tf (o, o
3 mol) and pyridy3. ．． The tetrahydrofuran solution (700 ml) of chloroformic acid phthalidyl ester obtained above was added dropwise to 2 ml (0° θ damol) of the tetrahydrofuran solution (, 2θθm7) in a water bath while maintaining the temperature at about 0C. After continuing to stir for 7 hours, the mixture was further stirred at room temperature for 7 hours.

The reaction solution was poured into ice water, the precipitated crystals were collected in a furnace, and recrystallized from a methanol-ethyl acetate mixed solvent to obtain the desired 3-(!-methyl-/-benzotriazolylcarboxy)phthalide (,2/). .3V was obtained. m, p, /
Kot～/J/'C0 Synthesis example <Synthesis of compound (,2,?)>! -Methyl-/-Synthesis of hydroxymethylbenzotriazole! -)f Rubensotriazole 1lOf (0.3 mol)
, 3 Oml (0.3 J mol) of 3j thiformin solution was added to water and 2 J Oml, and heated and stirred for an hour on steam. After cooling the reaction solution, the precipitated crystals were collected in a furnace and mixed with methanol and water. The title compound 3!1 was obtained by recrystallization from a solvent. m, p, ゛/-2
~/Coj 'C0 Synthesis of Compound (,23) Commercially available 0-phthalaldehyde acid d, Of (0,0 damol), in dry toluene, 2zoml,! -Methyl-/-Hydroxymethylbenzotriazolet,! f(0,0 tamol) and p-)luenesulfonic acid/F were added, and the mixture was heated under reflux on an oil bath at 1o0c for 1 hour using a dehydrating reflux device.

After cooling the reaction solution, toluene was distilled off under reduced pressure to form an amorphous
Ko f was obtained. This crude product was purified by column chromatography to obtain the desired 5-(t-methyl-/-benzotriazolylmethyloxy)phthalide (J
J) was obtained / , 2F. m, p, /3! -/ij
"c.

The precursors used in the present invention may be used in combination.

The blocked photographic reagent (precursor) of the present invention is
Any of the silver halide emulsion layer, coloring material layer, undercoat layer, protective layer, intermediate layer, filter layer, anti-tulsion layer, image receiving layer, cover sheet layer, and other auxiliary layers of a silver halide photographic light-sensitive material. (Two may be added.

In order to add the precursor used in the present invention to these layers, the precursor can be added to the coating solution for layer formation either as is or in a solvent that does not have an adverse effect on the photographic material, such as water or alcohol. It can be added after being dissolved at an appropriate concentration. Alternatively, by dissolving the precursor in a high boiling point organic solvent and/or a low boiling point organic solvent,
It can also be added after being emulsified and dispersed in an aqueous solution. Also,
Tokukai Akira! l-39tts issue, same j/-! 94t2, same j4t-3, 2jjr, US patent 4tl/? ? , 36
It may be added by impregnating it into a polymer latex by the method described in No. 3 or the like.

The precursor of the present invention may be added at any time during the manufacturing process, but in general C2, it is preferably immediately before coating.

The compounds of the present invention can be used, for example, in coupler-type color photographic materials.

A common method for forming color images from color photographic materials is to convert silver halide materials into aromatic primary amines in the presence of color couplers that have the ability to form dyes by reacting with oxidized developing agents. This is a method for obtaining azomethine or indoaniline dyes by developing with a developing agent. This color development method is basically developed by DMannes & 1. Qodowsky (2013) was invented by John F., and has undergone various improvements since then, and is used worldwide today in the industry.

In this system, subtractive color reproduction is usually used for color reproduction, with a silver halide emulsion that is selectively sensitive to light, green, and red, and a color image-forming agent that has two color relationships (yellow, magenta, and cyan), respectively. To form a yellow image, for example, acylacetanilide or dibenzolmethane couplers are used, and to form a magenta image, pyrazolone, pyrazolobenzimidazole, and cyanoacetophenone are mainly used. Alternatively, indacylon couplers are used, and phenolic couplers, such as phenols and naphthols, are used primarily to form cyan images.

Normally, color photographic materials are roughly divided into two types: an external method in which couplers are placed in a developing solution, and an internal method in which couplers are incorporated in each photosensitive layer of the material so as to maintain their independent functions. Ru. In the latter ζ2, the coupler forming the dye image is added to the silver halide emulsion.

The coupler added to the emulsion must be non-diffusible (diffusible) in the emulsion binder matrix.

In the internal mold method, the color photographic phase material processing process basically consists of the following three steps.

(1) Color development step (2) Bleaching step (3) Fixing step The bleaching step and the fixing step can be performed simultaneously. That is, it is a bleach-fixing process (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 mentioned above, the actual development process also includes auxiliary steps to maintain the photographic and physical quality of the image, or to improve the shelf life of the image. Accompanying. For example, a hardening bath is used to prevent excessive softening of the photosensitive film during processing, a stop bath is used to effectively stop the development reaction, an image stabilization bath is used to stabilize the image, and a desorption bath is used to remove the backing layer of the support. Examples include processes such as a membrane bath.

Conventionally known methods of adding or dispersing couplers to emulsions and methods of adding them to gelatin/silver halide emulsions or hydrophilic colloids are applicable.

For example, a method of mixing and dispersing a coupler with a high boiling point organic solvent such as dibutyl phthalate, tricresyl phosphate, wax, higher fatty acid and its ester, etc., for example, U.S. Patent No. 3041.9J9, Co., j, 2. .2.
The method described in No. 0.27, etc. Another method is to mix and disperse the coupler with a low boiling point organic solvent or a water-soluble organic solvent. A method of dispersing couplers in combination with a high boiling point organic solvent.

For example, U.S. Pat.
/, No. 171, No. 2,94t, No. 360, etc. When the coupler itself has a sufficiently low melting point (for example, 2t0c or less), a method of dispersing the coupler alone or in combination with another coupler to be used in combination, such as a colored coupler or an uncolored coupler. For example, German patent no. /413゜707 etc. are applicable.

Dispersion aids include commonly used anionic surfactants (e.g. sodium alkylbenzene sulfonate,
Sodium di-octersulfosuccinate, sodium dodecyl sulfate, sodium alkylnaphthalene sulfonate, Fischer type couplers, etc.) Zwitterionic surfactants (such as N-tetradecyl/N-N dipolyethylene alpha betaine, etc.) Nonionic surfactants (eg sorbitan, monolaurate, etc.) are used.

Couplers used in combination with the compound of the present invention include, for example, the following known couplers.

A specific example of a magenta colored coupler is disclosed in US Patent λ.

No. 400.711, same, 9.8'! , /; No. 01,
Same j, O6,2, lj3, Same 3. /Core, 2t No., J, J//, No. 4174, No. 3. Da/9, 3ri No. 7, same! ,! /9.4t Kota, same J,! ! r, j
No. 1, J, J, 2, J, No. 2.2, No. 3. ni lj.

jO4, same 3. tJ4t, もO/No., same 3. /9/
, 4t4t! No., West German Patent/, 110, lj4 No., West German Patent Application (OLS),! , RiθF, No. 441,
Same, 4t/7. ? No. 4tj, same, 4111. the law of nature! 9
No., same 14t, 4t, 4t4, special public Shogu θ-g0
No. 37, Tokukai Sho! /-, ZOrλ No. 6.2-J,
! f'9 coco issue, same 4t9-/29137, same tar 741027, same! No. 0-/39336, same, tKorg, 2/ko/ No., ' same, No. 9-741021, same! O-
6θko 33, same j/-, 24j4t/, same! 3-I
t/, No. 22, etc.

A specific example of a yellow coupler is given in US Patent 2. t7! ,01
No. 7, No. 3, 2 Goz, Zot No., No. 3゜G O♂, /9y
No., same j, 33/, /, tJ No., same 3, j? Ko, 3
．． No. 22, No. 3.7.21.07, No. j, F9/,
4t4tj, West German patent/, t4t7.211,
West German Application Publication Co., 2/? ,? /No.7, same, 1.24
/, j/s/ issue, same, 2, 4t/4.004, British patent/, ri, 2! , 0ko θ, special public Shoj/-70713
No., JP-A-4T7-16733, JP-A No. 4T/-237G No. 7, Same! /-/θ, ZtjA, same! 3g/issue to θ-, same! 0-/2 JJ Guco issue, same! θ−/3θ4
14t, No. 2, same j/-, 2//, No. 27, same! θ−
No. 77410, same! Ko/ko 41.24, same 3.2
-111219, etc.

A specific example of a cyan coupler is shown in US Pat. No. 3, No. 3.

Octopus No. 9, same 2 + 4' j 4' T J 7-
No. 9,293, same! 2/, 901
Same number.

79! , /, 2! No., same j, 0J41. No. t92, No. 3, j//, No. 4174, No. 3.4761.3! ! issue,
Same 3. ¥7/l! No. 63, same J, 3t3, ri7
! No., J,, t9/, No. 373, 3.74? ,
G// No. 4t, θ041.9.22, West German Patent Application (Or, 8) a, <tia, trJo No. 2, 4
1341.

3.2nd issue, JP-A-41J--J9♂3? No., same j/-
2to34 issue, same 4tJ? -! 0Jj- issue, same j/
-/<ttt, zt issue, same j, 2-494.24 issue, same! This is the one described in λ-W θ 3.2.

As a colored coupler, for example, US Patent 3゜4!2
g, No. 160, same, j, 2/, 90! No. 3.03
ri, J'9.2, special public Sho Doug-20fu 6, same! /-
,2,2jJj, same 4t co//3θda, same da 4t
-32 Gugo No. 7, Tokukai Sho! /-, 2dθ34 in the specification, jko 4t, 2/, 2/ specification, West German patent application (
OLS), 4t/l, and those described in No. 9j can be used.

As a DIR coupler, for example, U.S. Pat.
．． 27, Rijg issue, same 3. /7. ．． No. 29/, J, 7θ/, No. 71'j, No. 3,790, 3t4, No. 3. <j, Z, 3gj, West German patent application (OLS)
Ko, 4t/4t, θθg No. 341.301, same Ko, 1t4t, No. 329, British Patent No. 3, 4!
! Da issue, Tokukai Akira! 9d Koku to Ko, same 4t? -/, 2
Ko33! Those described in Japanese Patent Publication No. Sho II-/Ni/R No. 7 can be used.

In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor upon development, for example, U.S. Pat. , j
No. 7, No. 522, West German patent application (OT, 8),
4t/7. Those described in Japanese Patent Application Laid-open No. 7.2-11271 and Japanese Patent Application Laid-open No. 41-971d can be used.

High boiling point organic solvents are used, for example, in US Patent No. 2. J, 22°027
No., same, 2, , t j j, , t / * No.,
Same, 2. r3! , No. 179, Special Publication Showa 4t4-JJλ33
No., US Patent J, No. 217.7JV, British Patent No. 9! F,
Da4t1, Unexamined Japanese Patent Application Shogu2-/θ3/, British Patent/1.2
22.7! ! No., U.S. Pat.
No. 071, US Patent λ, 3! ! , Kobuko, same.

rj, 2.3! No. 3, same j, +t to 3, No. 713, same j, 47g, No. 737, same! , 47/;, /Guco issue, 3,700. <rj4 No. 3. ri4tt, iri7, same J, rJ7. rdJ issue, 0L82,! jl.

//ri issue, Tokukaisho! /-Core 92/No., same, t/-27
9,,2,2, same j/-λdOj,! r number, same j/-
, No. 24034, No. 243.2, Tokuko Akira?
-Kota 4t67, U.S. Patent 3. Ri3bu, No. 303, same? , 74t/, /gu/ issue, Tokukai Sho! ! -/j co/number etc. C- is written.

When the photographic elements of the present invention are applied to color diffusion transfer photography, peel-off (beer-apart) type or
4-/4j! No. 4t/-jj4?7, Tokukai Sho!
0-/3θaO and British Patent/, 33θ,! Cog No. (Integrated as described in 2)
Type, Tokukai Akira! ? It is possible to adopt a structure of a film unit that does not require peeling as described in No.-//934#.

In either type of format described above, the use of a polymeric acid layer protected by a neutralizing timing layer can be used.
This is advantageous in widening the allowable range of processing temperatures.

The precursor represented by formula CI) may be added to any compound containing a silver halide emulsion, as long as it is combined so that it can effectively act on the development of a copper halide emulsion. A photosensitive layer such as a dye image-providing compound-containing layer or other auxiliary layer; an auxiliary layer such as an image-receiving layer or a white reflective layer; or a neutralization mechanism such as a neutralization layer or a neutralization timing layer. Particular preference is given to adding it to the neutralization layer or the neutralization timing layer.

Internal latent image type silver halide emulsions can be advantageously used in the present invention, and emulsions of this type include, for example, U.S. Pat. j9.2
．． ．． 2. TO No., same j9.2θd, 3Ij No., same J
, 4t4t7.222, same 3. ri 4/, ko 2 issue, and ri 3. Examples include conversion type emulsions, core/shell type emulsions, and emulsions incorporating different metals, as described in 3j, θ/R, etc.

Negative-working dye image-providing compounds useful in the present invention include couplers that react with oxidized color developing agents to form or release dyes, specific examples of which are described in U.S. Pat. ．． 2.2
? , No. 330 and Canadian patents dO,2, dθ7, etc. C: is written.

Preferred negative-working dye image-providing compounds for use in the present invention include dye-releasing redox compounds that release dyes by reacting with developing agents or electron transfer agents in an oxidized state. is Japanese Patent Publication No. 4TT-, :93
No. 126, same ta-z4to, no. z1, same! /-//3
It is described in No. 42da and J Go-7107, No. 2. In addition, immobile positive-working dye image-providing compounds that can be used in the present invention include those that do not accept any electrons (i.e., are not reduced) or at least seven electrons during photographic processing under alkaline conditions. There are compounds that release diffusible dyes after receiving one electron (that is, being reduced); a specific example of this is
No., same! No. t/-4361, same! Korg L/RI issue,
53-6ri No. 033, same! 3-//θl Ko No. 2, same!
! -//θ727 and j4t-/30927.

Specific examples of yellow dye image-providing compounds that can be used in the present invention include Japanese Patent Publication No. 261T, U.S. Pat.
ri No. 9, Tokko Sho, T7-/2/410, JP-A-61-//Data No. 30, same! Goo/1ist4 issue, same! Niichi/I/3θ, same! t-2/θ72 issue; JP-A-74 t-7ri 03/ issue; JP-A-Sho! J-441036 and the same J Guco J! , No. 27; U.S. Patent a, 14tt.
, tri/, 14tr, ≦4t,? ;Re5e
arch Disclosure /7d 30 (/ri7/) issue, same/14t2! (/ri 27).

Also, specific examples of macenta dye image-providing compounds are listed in the US patent! , 41j3, 107, Special Publication No. 46i-1J 9
No. 60 and Japanese Patent Application Publication No. 7.27; US Pat. the law of nature,? / , /4
No. t4, 3. Ta J, 2. Jθ1, Unexamined Japanese Patent Application Shojθ-/
/! ! , Zr No., same j, 2-/θg727, same j3-
2. ? Go, No. 21, Same j4t-4jrO3 No., Same, t
s-: ttto41 issue, ttto 74133- issue, same! J-gu θ, 2f No., same J6-730, t No. 7, same! 27/θbu No. 0, 33-7j: Unexamined Japanese Patent Publication No. Shoj3-j
No. 4t1.2θ7°/θg, U.S. Patent No. 4t1.2θ7°/θg, 2J'7, . It is written in No. 292.

Furthermore, specific examples of the cyan dye image-providing compounds are disclosed in Japanese Patent Publication No. 41F-3,2730, Japanese Patent Application Publication No. 1999-1990! Ko! /, No. 22 Tokukai Showa 9-/Kogo 33/ No., same j/-10 Tata, 2
/ issue, same! Gatortag No. 37, same! 3-/g93.2/
Same issue! Ko! ! No. 27, same! 3-4t7t, ZJ,
Same j 3-/4t332.9, same! Goo99413
/ issue and jj-710za/issue; Tokukaisho! 3-ni da 0
3! Same as J Ku/2//, 2j i U.S. Patent 1,
/4t, 2, J'ri No. 7, same evening, /ri! .

Tuck, 4t, /47,! 4tgt, same, /gr, t4t, 2, European patent! 3.037
issue, is, oyo issue HRe5earch Discl
osure/2. tso (iq2tr) issue, same/4.4
t7j (/ri7j) and the same/go, 417t (/977
).

Compounds of the invention can be used, for example, in The Theory
of the Photographic Pr
ocess.

Chapter /2. Pr1nciples an
rlChemistry of Co1or P
photography■, 5 silver dye
Bleaeh Process.

Guth ed,,'l',H,James ed,
, Macmillan.

New York, /977, PI),? l? −，? 4
It can also be used in a silver dye bleaching method as described in 4+1.

The compound of the present invention can also be used in white spot photosensitive U-printing. Examples of black-and-white photosensitive materials include X-ray film for direct medical use, black-and-white photosensitive film for general photography, lithium film, and scanner photosensitive material. etc. can be mentioned.

Other constitutions of the silver halide photographic light-sensitive material of the present invention, such as a method for producing a silver halide emulsion, a composition,
Crystal habit, particle size, chemical sensitizer, antifoggant, stabilizer, surfactant, gelatin hardener, hydrophilic colloid binder, matting agent, dye, sensitizing dye, antifading agent, color mixing inhibitor, polymer There are no particular restrictions on latex, brighteners, antistatic agents, etc. For example, Re5earc
hDisclosure /Volume 7d p, 2.2-pj
You can refer to the description in /(/ri 1971/, February).

Furthermore, there are no particular limitations on the exposure method, development method, etc. of the silver halide photographic material of the present invention; for example, the above (Re
search Disclosure)th, 2/~3θ
Any of the known methods and known treatment liquids as described on page 1 can be applied. This photographic processing may be either photographic processing that forms a silver image (black and white photographic processing) or photographic processing that forms a dye image (color photographic processing), depending on the purpose. Processing temperature is normal/
From tr'C! Between θ0C (=selected, //+1
The temperature may be lower than C or higher than jOoC.

The developer used in black-and-white photographic processing can contain known developing agents. As a developing agent, dihydroxybenzenes (for example, 1-ide I-coquinone),
3-pyrazolidones (for example, /-phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-p-aminophenol), and the like can be used alone or in combination. The developing solution generally contains other known preservatives, alkaline agents, pH slowing agents, antifoggants, etc., and, if necessary, solubilizing agents, color toning agents, development accelerators, etc.
It may also contain a surfactant, an antifoaming agent, a water softener, a hardening agent, a viscosity imparting agent, and the like.

The photographic emulsion of the present invention can be subjected to a so-called "lith type" development process. "Lith type" processing refers to the photographic reproduction of line images, or halftone dots (
: A developing process in which dihydroxybenzenes are usually used as a developing agent and the developing process is carried out in an infectious manner with a low sulfite ion concentration for photographic development.・Ftsuku Processing ° Chemistry J (Described in /?44/, pages 3-15j).

When forming a dye image, conventional methods can be applied.

For example, negative-positive method (for example, "Journal o
fthe 5ociety of Motion
Picture and Television
13ngineers”, t/vol. (7953),
447-707); developed with a developer containing a black and white developing agent to form a negative silver image, followed by at least one uniform exposure or other suitable fogging treatment, followed by color development. A color reversal method in which a dye-positive image is obtained by performing development; a silver dye bleaching method in which a photographic emulsion layer containing a dye is exposed and developed to form a silver image, and this is used as a bleaching catalyst to bleach the dye.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (e.g., guamino-N, N-diethylaniline, 3-methyl-guamino-N, N-diethylaniline, teramino-N-ethyl-N-β). -hydroxyethylaniline, 3-methyl-g -amino-N-ethyl-N-β-hydroxyethylaniline, 3-methylder-amino-N-ethyl-N
-β-methanesulfamide ether aniline, guamino-3-methyl-N-ethyl-N-β-methoxy ether aniline, etc.) can be used.

Written by Kono et al., F.A., Mason Photography
hicProcessingChemistry(Fo
cal press-1-11%/ri 36 years)-
pp. 24-229, U.S. Pat.

/riJ, 0/! Same number! Octopus, Gogu No. 3, Tokukai Showa 4
Those described in No. t/-44tWjj may be used.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Bleaching agents include iron (seal) and cobalt (
Compounds of polyvalent metals such as mV), chromium (Vl), and copper (1), peracids, quinones, and nitroso compounds are used. The present invention will be further explained below with reference to Examples.

EXAMPLE / To evaluate the effectiveness of the antifoggant precursors in the present invention, compounds of the present invention and their control compounds, a first coat of cellulose triacetate film was prepared on a cellulose triacetate film support provided with a subbing layer. Sample A -1 was prepared. The coating amount of each substance is shown in parentheses as y 7m 2 or mol/m .

(1) Emulsion layer negative silver iodobromide emulsion, grain size /, 4tμ (silver /, dX10-2 mol/m2
) Magenta coupler Cp-7 (/, 33X/θ-3mol/m2) Antifoggant or its precursor (specified in Table 1) Gelatin
(K, tot/m2) (2) Protective layer gelatin (7,30f 7m2)
4t-dichloro-6-hydroxy-8-triazine sodium salt (0.03 f/m2) These films were left at 0°C, 20% relative humidity for 74 hours, and then sensitometric images were obtained. Then, the following color development processing was performed.

Color development process Time Mixture l Color development J / / t I 3r 15 C2 drift
White t '30' 3 Washing 2' 4 Fixing 4t1 5 Washing y' 6 Stable 7' Here, the composition of each processing solution in the color development process is as follows.

color developer water roomy
Gu(N-ethyl・-N-hydroxyethyl)amino-methylaniline sulfate jf Sodium sulfite If Hydroxylamine sulfate Cof Potassium carbonate
301 Potassium bicarbonate /, cof
Add potassium bromide /, 2F sodium chloride θ1.2f trisodium nitrilotriacetate /, 2 to water
/1 (pH10, /) Bleach solution water! 00ml
Ferric ammonium salt of ethylenediaminetetraacetic acid /θθ2t didiaminetetraacetic acid disodium-'' 109 Potassium bromide /jOf acetic acid
109 Add water
/1 (pHt, θ) Fixer water 200ml
Ammonium thiosulfate /30? Sodium sulfite 10f Sodium hydrogen sulfite 2. jf add water
/l (pH Otsu, θ) Stable liquid water 700ml
Formalin (Section 32) Tml dry well Add 3ml water
Table 1 shows the photographic properties obtained in /l.

No./Table 1 - A (control) B (invention) (4t) /, yy<i
(y 'C (present invention) (,2J) /
,/x10'D (present invention) (,+)
a, 5xlo-5E (this invention) (ri)
z,,rx/.

F (comparative example) A-/ /, /X10
'G (comparative example) A-, 2, koX/θ-5H (comparative example) A-31', rXlo '■ (comparative example)
A-a, 2. ．． 2x/θ*Relative sensitivity 2 fog+θ
The reciprocal of 1.2 color development; when controlled, the value is 0, / 0.6d 100
/, tjo, 0? 0.17
93 /, j! 0.10 0.6/
ta♂ /, 620, // 0
．． dj 10 pieces / , 6!0.
10 0. jta 9! Ha! 30.0
9 0.4tj 4J'/,
,2rO,/θ 0.4t9 daj
/,,24tθ,θ1 0. Gu, 2
33 /, /7θ, 07
0. Jj 37 /
From Table 1, it is clear that the capri is suppressed with almost no decrease in sensitivity in samples B to E using the compounds of the present invention. It is.

The comparative antifoggants and couplers used here are as follows. ) Compounds shown in Table 2 (co-developers) and their precursors were coated with couplers (Cp-
Sample 1-
The coating amount of each substance after preparing N is y 7m'' or m
o I , shown in parentheses as A2.

(1) Emulsion layer Negative history silver iodobromide emulsion, grain size 7.4tμ (Silver 4X10"mol/fn2) Magenta coupler〇p-i (/, 'J JX/0-3mul/h12)
(auxiliary developer) or its precursor (/, JJX/
θ-3mo Otori/m2) Gelatin
(,2,6Of/m2) (2) Preservation II layer gelatin (/,3θt/m2), 4
t-dichloro 4-hydroxy-3-triazine sodium salt <0.0! After exposing these films to ao'C and 201% relative humidity (for 2/4 hours), they were subjected to imagewise exposure for sensitometry and color development was performed in the same manner as in Example. The photographic properties obtained are shown in Table 2.

ko ￥ h ￥ toad ball mo-shizuku
--In the sample where Σ Z was added as is, an increase in fog and desensitization occurred, but in Sample JL using the compound of the present invention, sensitization was achieved with almost no increase in fog.

The auxiliary developing agents D-/ and D-co used here are as follows.

1) -/D-Co Patent Applicant Fuji Photo Film Co., Ltd. Continuation of Page 1 Watchdog 257100 7132-307
100 ) (C07D 405/12 31100 307100 ) (C07D 405/12 249100 7132-4 C
307100) (C07D 405/12 257100 7132-4 C
307100) 0 Inventor: Yunan Ito, Fuji Photo Film Co., Ltd., 210 Nakanuma, Ashigara City 0 Inventor: Keiji Morbayashi, 210 Nakanuma, Minamiashigara City, Fuji Photo Film Co., Ltd. Procedural Amendments Commissioner of the Patent Office 1, Indication of Case Showa SR, patent application No. 1/130
! No. 2, Title of the invention Silver halide photographic material: 3
．． person who makes corrections

Claims (1)

[Scope of Claims] A photographic light-sensitive material comprising a light-sensitive silver halide emulsion layer in which a blocked photographic reagent is combined, characterized in that the blocked photographic reagent is represented by the following general formula (1). A silver halide photographic light-sensitive material. General formula (1) () (wherein, when Ajin==o, it represents a photographic reagent bonded to the phthalide nucleus via a nitrogen atom or an oxygen atom,
When n=/, it represents a photographic reagent that is bonded to Z (=) via a nitrogen atom, an oxygen atom, or a sulfur atom. 2 represents a covalent linking group bonded to the butarido nucleus via an oxygen atom where n represents θ or /. group, aminosulfonamide group, carbamate group, carboxy group, carbonyl group, carpamo-f group, acyl group, sulfo group, arylsulfonyl group, arylsulfonyl group, sulfamoyl group, cyano group, nitro group. nl represents an integer from O to G.)