JPS59219741A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To enable a photogaphic useful reagent, such as antifoggant or coupler, to be kept stable during storage and released at a good timing by substituting its active group at the specified position of the cyclic amide group of a specified compd. CONSTITUTION:The active group of a photographic reagent, such as antifoggant, is blocked, as shown in formula II, with a compd. represented by formula I in which Z is an atomic group necessary to form a 5-7-membered ring; at least one of R<1>, R<2>, and R<3> can be substd. by the active group of said reagent at the position of an electron attractive group, such as -CO- or -NH-, combining with a amide-N through bond and capable of being cleft by the intramolecular nucleophilic reaction of the amide-N or the intramolecular transfer from it during development; (n) is 0-4; and (m) is 1, 2, or 3. A desired reagent can be kept stable during storage and released at a good timing of a necessary time, such as development or fixing process, by incorporating said reagent in each proper layer of a silver halide photosensitive material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a true light-sensitive material, and more particularly, it relates to a photographic light-sensitive phase material containing a precursor compound in which an active group of a photographically useful reagent is blocked. Photographic reagents useful for photographic purposes can be added in advance to photonic materials to produce their effects, but they have a different q# characteristic than when they are used in a processing solution. . Its characteristics include the ability to effectively utilize photographic reagents that are easily decomposed under harsh, alkaline, oxidizing, or reducing conditions and cannot withstand long-term storage in processing baths; at the same time, the processing solution composition is simplified. , the ability to easily adjust the amount of reagents required at the required timing during processing (force), or to place the necessary reagents where needed, i.e., specific layers and Two examples include the ability to remove photographic reagents needed only from adjacent layers, and the ability to vary the amount of photographic reagents present as a function of silver halide development. However, if the photographic reagents are added in active form to the 4"-F, they may react with other components of the 4"-F during storage prior to processing. The expected performance cannot be achieved during processing due to decomposition due to heat or the effects of arching. Seven methods to solve this problem include: - Activation of photographic reagents groups and substantially inert T
: r form, i.e. photo Jj as photo reagent precursor
ti, there is a method of adding/JIJ to Kotou material. If it is not useful and the color is zero, by blocking the functional group that greatly affects the spectral absorption of the dye and shifting the spectral absorption to the shorter or longer wavelength side, Even if it coexists in the same layer as a silver halide emulsion layer having a corresponding photosensitive spectral region, it has the advantage that sensitivity does not decrease due to the so-called filter effect. If useful photographic reagents are antifoggants or development inhibitors, blocking active groups can suppress desensitizing effects due to adsorption to photosensitive silver halide and silver salt formation during storage. , required timing ↑ By releasing these photo test strips, there are advantages such as reducing fog without impairing sensitivity, suppressing over-development fog, or being able to stop development at the required time. be. If the useful ￥-true test mulberry is used as a developer, auxiliary developer, or on the upper side of a fog, it can prevent various photographic defects caused by the formation of semiquinones and oxidants due to air oxidation during storage by blocking active groups or adsorption groups. There are advantages such as preventing fog nucleation during storage by preventing the reaction or injection of electrons into silver halide, and as a result, stable processing can be realized. The photographic reagent is lO
In the case of whitening accelerators or bleaching/fixing 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. , it has the advantage of being able to exhibit the desired performance at the required time.

As mentioned above, the use of precursors for photographic reagents can be considered to be an extremely effective means for sufficiently enhancing the performance of photographic reagents.
These precursors Q must satisfy very strict requirements. In other words, are there contradictory requirements that the photographic reagent be stably present under storage conditions, and that during processing, the blocking group is released at the required timing and the photographic reagent is released promptly and efficiently? i: Must be compatible - Several blocking technologies for photographic reagents are already known. For example, those using blocking groups such as acylno, I, :, and sulbonyl groups described in the specification of Japanese Patent Publication No. 7-Hirogu, Roj No.
No. 27, same j! JP-B No. 341-
Jri No. 727, JP-A-Sho J'7-/3394L≠ No. 3
7-/3! Tag No. J, No. 37-1ltl, No. ≠θ, on the same evening, a photographic reagent is released as a quinone methide or quinone methion F KfU analogous gold compound is formed by intramolecular electron transfer as described in the specifications of No. 11/≠θ. Something that makes full use of block bases,
Those that utilize the intramolecular ring-closing reaction described in the specification of the former IJJ Star No. 33330, or JP-A-1-1f3
j 7-76 Tahiro/issue, same t7-/3? Known techniques include those that utilize the ring cleavage of t-members, etc. described in the ``Medori'', ``J7-/7'', ``G Hiroko'', and ``Ki''#J meter. For those that are stable under storage conditions, the release rate of photographic reagents during processing is too slow, requiring 4% alkali treatment at a pH of 1) H/-2 or above, or processing solutions with a pH of ~/. Even if the release rate is sufficient, it may gradually decompose under storage conditions, damaging the ship's own ship as a precursor, or the release rate of photographic reagents cannot be broadly controlled, which limits the usable pIT region. Therefore, it is an object of the present invention to provide a blocked photographic reagent which is photo-stable under storage conditions and which releases the photographic reagent at the required timing during processing. In particular, it is an object of the present invention to provide a blocked photographic reagent having a thickness that is greater than its release rate. In the photosensitive material, the blocked photographic reagent has at least one cyclic amide group, and the amide group's atomic atom interacts with an electron-withdrawing group that may be formed during development through a π bond. When bonded with ←, pr-, intramolecular nucleophilic reaction or intramolecular electron transfer of the nitrogen atom! This was achieved using a silver halide photographic light-sensitive phase material, which is characterized in that a photographically useful reagent is placed at a position where it cleaves by 1θIK.

Here, [electron-withdrawing property that may be generated during development] may originally have an electron-withdrawing group, or may have an electron-withdrawing group that may be generated during development. 1) means that a structure that generates an electron-withdrawing group is acceptable. An electron-withdrawing group refers to a substituted 2rK e H having a positive α value according to Hammett's rule, and specifically, 1, for example, a halogen atom, An acyl group, a benzoyl group, a carbamoyl group, a sulfamoyl group, an oxycarbonyl group, an imino group, a sulfonyl group, a sulfinyl group, a cyano group, a nitro group, a heterocyclic residue, etc. □ Particularly preferably an acyl group or an imino group , a sulfonyl group, a cyano group, or a nitro group.

The electron-withdrawing group that may be generated during development refers to R during development.
It refers to a group that generates an electron-withdrawing group through an e do Hydroxy group, sulfonamide group, carbonamyl group located at the position or para position,
A preferred example of a blocked photographic sample of the present invention representing a ureido group, a sulfamoylamino group or a carbamate group is represented by the general formula CI).

In the general formula (I) -a formula CI)K, represents an atomic group having a 2+-1 to 7-membered Dy, R' and R2* R3 each represent a substituent, and R, 1N, R- At least seven of these groups are electron-withdrawing groups that may be generated during development and are bonded to the amide nitrogen atom via π bonds, and at the same time, R1, R2,
At least one of R3 can be cleaved by an intramolecular nucleophilic reaction of the amide nitrogen atom or an intramolecular electron transfer of the amide nitrogen atoms 〇1, and is substituted with a photographically useful reagent. n represents 0 to ≠, and represents m&ma/ to 3;

The position where the amide nitrogen atom is cleaved by a nucleophilic reaction refers to a positional relationship where the nitrogen atom can react with an electrophilic group implanted in a photographically useful reagent. J'S refers to the position where a 3- to 7-membered member is formed.

In addition, the intramolecular transfer of nitrogen (preload)fff)
J [Thus f9'! : The cleavable position 1θ means the N-methyl position, benzyl position and allyl position.

Also, is the preferable electron-withdrawing group that may be generated by development 11'#vL a carbonyl group or an imino group? You can spend $.

Among the precursor compounds represented by the general formula (I), the most preferred compounds are the following general formulas ([) and (III).
).

General formula (I) General formula (CIII) General formula (I)
In I), Y represents the atomic group necessary for the current formation, and p
is O−λ, R and R represent substituents, and q&″iθ
-R representing 弘 preferably represents an alkyl group, an aryl group, an alkenyl group, an acyl group or a sulfonyl group, which may have a substituent. RGet Hensen's top substituent may have any known substituent, but preferably (halogen atom, alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, hydroxy group, acyloxy group, carbonate ester group, amino group, carphonamide group, sulfonamide group, ureido group, aminosulfonamide group, carbamate group, carboxy group, oxycarbonyl group, carbamoyl group, acyl group, sulfo group, alkylsulfonyl group,
Arylsulfonyl group, sulfamoyl group, cyano group,
represents a nitro group, q represents O-, R and -N
At least one of R5 bonded to the ortho- or para-position of R- is a methyl group substituted with ``4 true useful sample'' or a methyl group substituted with ``4 true useful sample substituted at benzyl position. or at least seven of R bonded to the ortho position of R4 or -NR'-,
In the general formula (III'), Z is a general Formula (I) and same 5
, R represents a methyl group substituted with a photographically useful reagent or a phenyl group substituted with one at the pen and zyl positions of the photographically useful reagent, and X and X are respectively JJII
Hydroxy group produced by water decomposition and good at °C, fi:
,'f: amino group which may be shown as FIG, carbonamide group, ureido group, carbamate group, sulfonamide group, sulfamoylamitaf 4i) ・Xl and X
are located at the ortho or rose position with respect to each other, and R preferably represents the substituent listed for R in general formula (II), and represents an integer of γ to θ and 2.

Particularly preferred among the trecasers represented by the general formula (n) are represented by the following general formula + IV) In the general formula (IV) - ff company (IV), A may contain a timing group. It represents a photographically useful reagent, 1 (represents a substituent on the Hensen ring, and S represents O~≠).

As photographically useful reagents, well-known Atsuma reagents bonded with heteroatoms, such as mercaptotetrazoles, mercaptotriazoles, mercaptopyrimidines, solkatbenzimidazoles, mercaptotetrazoles, benzotriazole%4, Anti-cuff agents and development inhibitors such as ink soles: p-phenylenediamine dichroic, high F loginone record! , p-amide/phenols, etc.; auxiliary development agents represented by pyrazolidones, hydrazines, caplace agents such as hydrazines; silver halide solvents such as Hypo; gamma oxides such as aminoalkyl-thiols, etc. White accelerators; or azo dyes, azomethane dyes, and the like. In addition, as a function of development, the photographic reagents mentioned above also have the redox ability to be released.
t D I R-Hydroquinones are also useful7? It can be mentioned as a photographic reagent. 77'J' mentioned above
((r'J useful reagent may be bonded via a timing group), and such timing % is +40
11rojt-1≠j/3! No. +r: Release of 7J true commercial circulation by intramolecular closed field reaction described in Book II, British Patent No. g'f, No. 207J, No. 363, JP-A-1973-/J ≠ In the molecule as described in Ko No. 31 Akira Jllll book, etc.'
``1L'F--transferring 4 truly useful tests: A photo with charcoal gas removal as described in JP-A-57-/7-Li No. II-2 Myokij, '5, etc. 1z) G'j patent application Shojt7-20311-
Examples include those which release a photographically useful reagent with the elimination of formalin, as described in Book No. 2, Mei A111. R7
Preferable as 1′ 〈 ・alkyl group, halogen atom, alkoxy group, hydro 4 ・cy group, sulfamoyl group, car 7
j; amide group, sulfonamide group, ureido It';
, , sulfamoylamine and nitro pattern are mentioned, more preferably (alkoxy group, hydroxy group, sulfamoyl group, sulfonamide group, carbonamide group, sulfo group and nitro group. S is preferably θ~2 and more preferably O
or/is.

Among the precursors represented by the general formula (III), those represented by the following general formula (V) are particularly preferred.

General formula (V) In general formula (V), A is a combination of general formula (1v), and R is preferably an alkyl group/norogen atom, hydroxy group, carphonamide group, sulfonamide group, or ureido group. or sulfamoylamino 4f, more preferably an alkyl group, hydroxy group, sulfonamide group or carbonamide group. t represents O~2,
More outrageous is O or /. The 10H groups in general formula (V) are in the ortho or /zero position with respect to each other.

The reason why the precursor compound of the present invention has excellent storage stability and at the same time rapidly releases photographically useful reagents during processing (although it is not clear, it can be considered as follows.
In other words, in the neutral to acidic pH range during storage I, β
Either β cleavage is difficult to occur, or even if cleavage occurs, it exists stably because it is in equilibrium with the closure reaction. Ten thousand,
Under the alkaline conditions during treatment, the attack of the alkaline component of the treatment solution or the nucleophile of a certain yuzu 'J'i? , VL to generate an anion. Since this anion is conjugated with an electron-withdrawing group via π electrons, its cleavage is particularly easy to occur under alkaline conditions, and the subsequent intramolecular nucleophilic reaction It is thought that a truly useful reagent is released without any movement.For example, the general formula (
In the case of the trecaser shown in III), current cleavage becomes possible only through the generation of an electron-withdrawing carbonyl group or imino group through cross-oxidation during development, and a photographically useful reagent is released from the anion generated by current cleavage. It is considered that Gl + 7) 1) evelopmen
Inhibitory to-releasing compounds, such as U.S. Pat.
The release mechanism of the number is different from that of the sulfonamide conductor described in 111, No. 3, 34 of Meiji.

In fact, the precursor compound having 11edox ability of the present invention has the ability to reduce f-
The stability is increased to +i++11 as above.

The preferred additive amount of ztu-yix for the compound of the present invention varies depending on the type of really useful reagent, but the amount of antifoggant and development inhibitor is 10 to 10 mol per mol of silver.Preferably, the amount of mercapto thread capri-antistatic agent is 10 to 10 mol per mol of silver. X10
moles, azole antifoggants such as benzotriazole from lo to 10 moles; developers from lo-2 to lo moles per mole of silver, preferably 0. /, 3 mol; pyrazolidone tilt co-developer: 10 to 1 mole of silver
10 mol, preferably io, s mol; 10 to 10 mol per mole of fogging agent Gf &-14,
Silver halide solvents such as hypo are preferably 10 to 3 to 10 moles per 7 moles of silver, preferably 10 to 10 moles per 7 moles of silver. 1 mol; bleaching accelerators such as aminoethane 1,000 mol;
4: t/0 to 10 mol.

The pigment or color diffusion transfer rate for the TF tool is 10 to 1 mol per 7 mol of silver, and the dyestuff is 3 x 10 to 0 per 7 mol of silver.
, S mol.

Here are some specific examples of precurries that are uninvented in Europe:1. It's 4c.

(1) (-2).

(3) (Hiro) (7) 802Nll□ (r) (ri) (/2) (/3) (/6) (17) (7za) (lri) (,20) DI General formula of the present invention Compounds indicated by CI) include, for example, N-hydroxymethylation of commercially available isatin derivatives, isatone [1r9 anhydride readers, benzoxacylinone derivatives, etc.] and subsequent N-halomethylation and photographically useful reagents or timing. It can be easily synthesized by a substitution reaction with a truly useful reagent to which the group is linked. Isatin derivatives having an alkoxy group such as V, I
-1, E3rsWll etc.・Journal of 1
-Jeterocyclic C11ernistr
y.

It can be synthesized according to the method described in Vol. Synthesis 1 of penzodiazebin-conion b was described by M. Ogata et al.
tr y.

and 1 industry, gig/ 1 volume, 10t7
F3,/? It was synthesized by the method described in 7A. In addition, among the precursors of this specification, 1 (compounds having edox function are, for example, G, N.

%Valker, , 7ournal of
Amezcan(:bemical 5ociet
y, Volume 77-, 314t u 1'4/913; Kametani et al., Che+nical January 1arlna-
The dimethoxy derivative whose synthesis method is described in detail in CelltiGal J3ulletin, +Negative Volume, Page 3.2t, 1971, is treated with, for example, Br3 or A11c13 to form the corresponding dihydroxy derivative, and then the above By the same method as above, it is possible to obtain a thoroughly useful reagent. j、It is possible to move a person 4C. Alternatively,
After introducing the dimethoxy compound = truly useful reagent,
M T& and BBr3? i: dihydroxy form VCf using
There is a method to guide Hfj. Compounds in which hydroquinone is in the rose position are also
n, etc.* G-N, W"" er+ and Kametani et al. can be similarly synthesized by applying the method described in the literature to hydroquinone dimethyl ethers.

A specific example of the synthesis of the solekase compound of Hon/+'3Saku is shown below.

Synthesis Example / <Synthesis of Exemplary Compound (1) 2 / - Synthesis of Methylolysatin Commercially available isatin 23EICO, /7 mol), 30 ml of 30% formalin solution, water x O ml, dioxane 10 ml
1 and heated under reflux on an oil bath for about 3 hours. After cooling, the precipitated crystals were collected to obtain crude crystals of the title compound. This was used in the next step without purification.

/-Synthesis of chloromethylisatin/-Methylolysatin 209 is converted into thionyl chloride
In addition to praying for 2 hours, I also had a 11-hour heat bath. After one reaction, unreacted thionyl chloride was distilled off under reduced pressure to obtain about 22% of the title compound.
I got 77.

m, p, /, 2/-/'23a C/-Chloromethylisatin Hiroshi, 7.9 (0.02 J mol) was dissolved in dry tetrahydrofuran≠OTnlVC, and to this solution was added /-phenyl-! ---Hiroshi Mercaptotetrazole,
≠317 (0.02j mol)'' and 2g% NaO
CH3s, os9 (o, o2s2g) of tetrahydrofuran 2om7! The solution was cooled 7' at room temperature. After completion of the dropwise addition, stirring was continued for approximately 7 hours (1'1) to remove the insoluble portion, and then the solvent was distilled off under reduced pressure to obtain crude crystals.The crude crystals were added to 10ml of methanol and heated. Thereafter, the mixture was cooled and 84 times removed to obtain yellow-orange crystals of Exemplified Compound (1), 21.

m, p, / A3-/6'lll C Synthesis Example λ Synthesis of Exemplified Compound (≠)

, 2 J-mol) in dry oak! Detrahydrofuran≠Oml
Dissolve in this solution the sodium salt of /-[IJ-(3-methylureido)phenyl]-s-mercazototetrazole6. 30 ml of a tetrahydroalan solution of I was added dropwise at room temperature. After stirring at room temperature for 1 hour, the resulting insoluble matter was lost, and the solvent was distilled off under reduced pressure to give a small product. Obtained. By recrystallizing from aceto/methanol, 7.3 g of exemplified adduct (Hiro) was obtained. m, p, /
7/-/7+2Il CofliJ Example 3 Exemplified Compounds (
Synthesis of /-Chloromethylisatin3. ;EiCo
, 0/Aphthal), /, J-Inophenylupyrazolidine-3-onv, 27f (0-, 0/Aphthal) and chloroborm tioml, and triethylamine 2.7me (/, /equivalent) at room temperature. All drops were added. Bring the reaction solution to room temperature3
After heating and stirring for 0 minutes, the precipitated crystals were collected, washed with water, and dried, followed by -chloroform-
Recrystallization from a mixed solvent of /acetone gave Exemplified Compound (71).

nl, p, /23-~/, 27°C Synthesis example
<-dimethoxyoxy-indole lA, l311C0
,02j mol), followed by methylolation and chlorophoration as shown in the synthesis of exemplified compound (1), followed by /-phenyl-! -Mercaptotetrazole was administered to 42 people.1.
41 of dimethyl ether (Product j, GI was obtained) This product Tj: In addition to 2 ml of dry methylene chloride, 30 ml of a solution of boron tribromide 133 and !me in methylene chloride was added dropwise under ice-cooling. After S was completed, stirring was continued for an additional hour, and then the 1'+5 solution was poured into ice water/+'70 Jn14, and 1-1 of the precipitated crystals were collected to obtain crude crystals.

1 from ethyl/methanol] Crystal T 4+ The exemplified compound (7 g) was prepared from 3. ．． I got 2g.

m, p, / 341 ~ / 37' C misfire 11.
The precursors used in 1 may be used in combinations of λ4'+Hi or more. The unblocked true trial cycle of the present invention is
Silver halide emulsion 1/+ of silver halide photographic light-sensitive materials
1, A14 layer, F f:)3. j J l candle, Ho Ii”
J l・, 77, intermediate layer, filter single layer, antihalation layer, 9+1M・cover sheet i71% other i
7JO may be added to any layer of the ζ11 sublayer.

Book))'r31! K to be added to the layer used in J) is the precursor used in the coating solution for forming m2), or the photosensitive resin. Sadly; 8. ! ' Solvents that do not give ¥, such as water, alcohol, etc.
14 71 (JS+: L T , +, 6) It is possible to dissolve 71 (JS +: L T , +, 6) in a high boiling point organic solvent and also in a low boiling point organic solvent and inject it into an aqueous solution. It can also be added as an emulsified fraction to JP-A-Sho!/-3.
91r33, 61,39941. ! , same ta ψ−3.
The precursor of the present invention may be added by impregnating it into the polymer latex by the method described in US Special Specifications ψ, L Tata, No. 363, etc. The precursor of the present invention may be added at any time during the manufacturing process. Although you may choose a song, it is generally preferable to do it immediately before applying. can be used as a photosensitive material ・Color photography In
The general method of producing a color image from a light material is to form a film of mulberry (1+) and anti-1 (color coupler), which has the ability to form a pigment. In this method, an azomethine or indoaniline dye is obtained by developing the silver halide photosensitive material 4>1 using an aromatic primary amine developing agent. This color development method is basically 3C, D, 4annes, L, Qo.
dowskyic, e IIJJ aoLノ, = thing, and since then many improvements have been made, t-L, /lB
The word σ used in the music world as a barrier is also σ.

In this method, continuous color writing has subtractive color force = (history, blue, green, and red [7 alternative 1/L jl'':'% light 1
-yellow, magenta, and cyan colors, each of which has an aftercolor relationship with the silver halide emulsion (11'il 1g)
When forming 011 and power 11 to form a yellow color image, use 61, for example, azila-7toanilide To form the cyanocolor image, primarily pyrazolone, bi'rasolobenzimidazole, cyanoacetophenone or ingsolone optical couplers are used, and to form the cyanocolor image (2r, primarily phenolic thread couplers such as phenol! and naphthols are used). be exposed.

(Jing Chang, Color Photography) Commercial photosensitive additives use the 1lilJ method, in which a coupler is placed in a developing solution, and the photosensitive coating material, which is a coupler, is contained in each photosensitive layer so as to maintain an independent function.
It is roughly divided into internal molding methods. In the latter, a coupler forming a color image is added to the silver halide emulsion. The 7'L coupler added to the emulsion is
The YB agent must be non-diffusible (withstand 70% release) in the binder matrix.

In the internal mold method, the processing steps for color photographic light-sensitive materials include the following three steps and four steps in terms of water extraction.

(1) Color development process (2) Whitening process (3) Fixing process condition The whitening process and the fixing process can be performed at the same time, that is, in the bleach-fixing process (e) This step desilvers the developed +=:A+ and undeveloped silver halide. Actual current processing consists of the two processes mentioned above: color development and desilvering. E; In addition to the +m process, there are preliminary processes to maintain the physical and physical quality of the image, or to improve the storage stability of the image. For example, a hardening bath is used to prevent excessive softening of 11 photosensitizers during processing, a stop bath is used to effectively stop the development reaction, and image 1g! It stabilizes ll! Examples include steps such as a III image stabilizing bath or a film removal bath for removing the banking layer of the support.

Conventionally known methods of adding couplers to emulsions or dispersing them, and adding them to gelatin/halogen 411 emulsions or hydrophilic colloids) are commonly used.

For example, a method of mixing and dispersing a coupler with a high boiling point organic solvent such as dibutyl phthalate, tricresyl phosphate, wax, grade fatty acids and their esters, etc. , No. ! , 3.2λ
, No. 027, and so on. Also, a method of mixing and dispersing a coupler with a low boiling point organic solvent/)) water-soluble organic solvent. Besides, 74 i! How to fractionate couplers using lli-point organic solvents/Dog dog US special edition>rs
,,2. rot, /7o issue, 2nd degree 0/, 17
The method described in No. 1, No. 2.2μ, No. 360, etc. The coupler itself has a sufficiently low melting point (e.g. 75"C
(below), it can be used alone or in combination with other couplers such as colored couplers 71' uncolored couplers. how to. For example, German special
``No. 1/Hiroshi 3゜707 etc. is used in J1. As a separating agent, anionic surfactants that are commonly used (for example, alkylbenzene sulfone former sodium, sodium di-octylsulfosuccinic acid, etc.) are used. amphoteric surfactants (e.g. N-tetradecyl/N-N dipolyethylene alpha betaine, etc.) and nonionic surfactants (e.g. sorbitan, monolamine, etc.). rate, etc.) are used.

The photographic emulsion layer of the 1R true light-sensitive material of the present invention contains a color-forming coupler, that is, an oxidative coupling agent with an aromatic 7th class amine developer (for example, a phenylenediamine derivative, an aminophenol νi9, etc.) in the color development process. It may also be a compound that develops color depending on the color. For example, as a magenta coupler! -Pyrazolone coupler, pyrazolobenzimidazole coupler, cyanoacetylucumaron coupler -1) Jl'! Examples of yellow couplers include acylacetamide couplers (eg, benzoylacetanilides and pivaloylacetanilides), and examples of cyan couplers include sodium couplers and phenol couplers. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule.

The coupler may be either equivalent or bi-equivalent to the silver ion.

Also, colored couplers have the effect of color correction, or couplers that release development inhibitors during development.
(DIR coupler) may be used.

In addition to D I R couplers, colorless D
It may also include an I It coupling compound.

When the photographic element of the present invention is applied to color diffuser plate II photography, it may be of the peel-off (beer-apart) type or of the Tokko Showa 1it-/1. JjtA, 4Ir-33t 7,
Tokukai Akira! 0-/30≠θ and British special A'r/,
33o, rip No.
41. of a peel-free type film unit as described in Hiroj issue. ? can be achieved.

Uninvented combination! II! ! I is a black and white photosensitive material K E
It depends on whether you are using it right or not. Examples of black-and-white photosensitive materials include X-ray film for direct placement, black-and-white film for general photography, lithography film, and scanner film y and t.

The present invention's "Silver Halide Zinc II" can be used to determine other components of the optical material, such as a method for preparing silver halide emulsions, halogen composition, crystal habit, grain size, chemical sensitizers, antifoggants, stabilizers, Surfactant, gelatin hardening agent, hydrophilic colloid binder, matting agent, dye, sensitizing dye, anti-fading agent,
Color mixing prevention agent, polymer latex, whitening agent, obi ■ L prevention sharpening, especially for temples, 1fill limited number, for example, I (esearch I) isclosure /7A
The description in volume p22-pj/(/77g, December 2007) can be referred to.

In addition, there is no particular method for the silver halide γj: fA photosensitive material exposure method, current method, etc. of the present invention.
For example, the above (l(, esearcb ]) isclo
1-
It's a monkey. Depending on the purpose of this photo processing,
It may be a photographic process that forms a silver image ink (black and white photographic process) or a photographic process that forms a dye image (color photographic process).The processing temperature is from /I"C to jO"C Although the temperature may be selected between 7♂°C or higher than 7♂°C, the temperature may be lower than 7♂°C.

The developer γυ used in black and white color processing can contain a known developing agent. As a developing agent,
Dihydroxybenzene 1 (e.g. hydroquinone), 3-pyrazolidones (e.g./-Fue book 3-
(pyrazolidone), amino heptanols (for example, N-methyl-p-aminophenol), etc. can be used alone or in combination. The developer generally contains other known preservatives, alkaline agents, I)H buffers, antifoggants, etc., and as necessary, a solubilizer, a color toning agent, a development accelerator, and a Kaiichita activator. , an antifoaming agent, a water softener, a hardening agent, a viscosity imparting agent, etc.

The so-called ``Lith type'' development process can be applied to the four-tone emulsion of the present invention. ``Lith type'' development process is a photographic reproduction of a line image or halftone dots of a halftone image. This refers to a development process in which the development process is carried out contagiously under low sulfite ion concentration using conventional dihydroxybenzenes as the main development agent in order to prevent serious damage.

Color developers generally consist of an alkaline aqueous solution -D) containing a color developing agent. The color developing agent is a known general aromatic amine developer, such as phenylene diamines (e.g., guamino-N, N-diethylaniline, 3-methyl-hiro-amino-N, N-diethylaniline, daamino-N).
-ethyl-N-β-hydroxyethylaniline, 3-methyl-l-amino-N-ethylaniline, Amidoethylaniline, guamino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.
rapbicprocessing Chemistry
y (published by Focal press, /ri6 in 2013), 2
26N 222 pages, US 471''K, l 3, 0/j issue, same λ, j ri λ, 3 wo hiro issue, JP-A-Sho≠,!'-74t2
You may use the one described in No. 33 etc.).

After color development, the photo-8 emulsion layer is usually bleached.

The bleaching treatment may be carried out simultaneously with the fixing treatment, or may be carried out separately. As bleaching agents, compounds of polyvalent metals such as iron (■), cobalt (■), lithium (Vl), copper (II), peracids, quinones, nitroso compounds, etc. are used. - The present invention will be briefly explained by giving examples.

Actual btu example/photographically useful sample of the precursor of the present invention Precursor compound 3.1x/θ-5 moles in ≠ml! of acetonitrile and the solution was dissolved in acetonitrile/Aml and 13 ritton-i (o
It was added to a mixed solution consisting of binson powder and liquid xomi.

(The flI!I constant pH was adjusted in advance by the pH of the buffer solution.) After a certain period of time, a certain amount of the reaction solution was collected, and the reaction was stopped with acetic acid. The released photographically useful reagent was quantified by high-performance liquid chromatography, and the pseudo-secondary reaction rate I constant was determined. From k', the half-life, t//2-θ, which is the time required for half of the precursor to react, was calculated from the equation 2/3/'. Similarly, for comparative compounds /-A and l-B, t/
/, 2 was determined and compared with the precursor compound of the present invention, and the results are shown in Table -/.

Table-7 Measurement of release rate of photographically useful reagent Compound I Title pHk' φ Exemplary compound (1) 10.0 ≠, 6.2X10-2/J'u
(4C) 10.0 3. rjy, 10-2/
lr〃 (ri) 10.0 2. , +7×10−
2 27〃 (//) 10.0
8/ri×io”tza comparative compound/-A/θ, 0 2
．． 3 x 10',! Ri o.

//, 0 2.0 Hiro x 10 3'IO///-I3
10. θ ta, A3×/θ-4720ii, or,
Q comparison compound /-A and / to tt×10”
-B's birch pickling is as follows □ / -A / -43 Table -/ shows that the release rate of the mercaptotetrazole antifoggant and phenidone of the precursor compound of the present invention is the same as that of the existing comparative precursor compound J- 0~io
□Example λ Regarding the effectiveness of the antifoggant precursor in the present invention - In order to evaluate the compounds of the present invention and their control (comparison) compounds, an undercoat layer was provided. On an acetic acid-resistant cellulose film support, the antifoggants listed in Table 7 and the partially blocked antifoggant of the present invention were dissolved in tricresyl phosphate together with a coupler (Cp-/). /I;1 Sample A-FE was prepared by coating an emulsion layer that had been emulsified and added. The amount of each substance applied is g
/m2 or rno ] /m2 in parentheses.

(1) Emulsion layer negative silver iodobromide emulsion, grain size/μ(silver A ×
/ 0 'mol/m2) Magenta coupler Cp'
-/ (/, JX/Omol 7m) Antifoggant or its precursor (Clear 2v) Gelatin (,2,j Og/In
) (λ) Retaining hΦ layer gelatin (/, 3097m
) λ, 4t-dichlorot-hydroxyS-triazine sodium salt <0.03I//111) After leaving these films for 4 hours at a relative humidity of 70%, Imagewise exposure for measurement was applied and the following color development process was performed □ Color development process Time Temperature l Color development 3'/j"3r'C2 藺 White
/, /30 "3 water situation" μ foot arrival ≠'! Wash with water p't
tt Stable /' Here, the composition of each processing solution in the color developer 4g4 processing step is as follows □ Color developer water tro
oml! ≠-(N-Ethylhydroxyethyl)amino-λ-methylaniline 1 volonate sII” 1i Sodium sulfate 9-Hydroxylamine sulfate 1jA-29 Potassium carbonate
30g potassium bicarbonate
/ , 21/potassium bromide
/ , 211 sodium chloride
0.2y nitrilotriacetic acid mQE sodium 7.2g
Add water /l (pi-)
/ 0, i) Bleach solution water 100
ml ethylenediaminetetra#ferric ammonium salt of acid / θOS ethylenediaminetetrahydrogen disodium 10 fl potassium bromide / jf01 / acetic acid
Add IO & water
l1lCpH/,,0) Fixer water za00
m(.

Thio1iiiIt, Autobell ammonium ljO
& thorium sulfite log sulfite h
Add water sac sodium 2.5g water
//(pI-14,0) Stable liquid water goo
mi formalin (37%) jd drywell add 3ml water
Table 2 shows the intrinsic properties obtained in No. 7.

From Table 2, it can be seen that in B and C using the compounds of the present invention, the capri was decreased with almost no decrease in sensitivity. In addition, in D using the DIR compound of the present invention, the image quality [density decreased (7, 0) was observed.Also, when the processed film was observed, it was found that the graininess started to improve. The anti-capri agent and coupler used here are as follows.

Comparative Compound CoA Comparative Compound--Bα Cp-/Example The following layers (1) to C3)? i: A cover sheet was prepared using the following procedure.

(1) Acrylic acid and acrylic (W butyl gO vs. λ
A layer containing Q (weight ratio) of copolymerized monolithic (//,!F/m ) and /,≠-bis(,2,J-epoxyturoboxy)-butane (0,2,2I/m ) .

(2) Acetyl cellulose (10077 acetyl cellulose is decomposed in water to produce 3t, All a7thyl group) (Hiroshi, J 117m2) and styrene and maleic anhydride 1゛-9 of 60 Methanol ring-opened product (0,,
2311/nl) b and a layer containing o, tJmeq, 7m of the compound listed in Table 3VC as a development inhibitor.

(3) Spreading of styrene-〇-p100 acrylate acrylic material-N-methylol acrylamide, 7 pairs ≠ 2.3
73 of copolymer latex and methyl methacrylate-acrylic soap-N-methylol acrylamide
≠ 3 (weight ratio) copolymer latex with f<U4 latex and F2 latex with H type ratio of t to 41
A layer with a thickness of λμ is mixed and coated so as to be C.

A photosensitive sheet was prepared by coating each layer on a polyethylene terephthalate transparent support as follows.

(1) Gelatin 3. og/ln, a mordant layer containing 3.0 g/m2 of the following polymeric latex mordant.

→CH2CH← (2) Titanium dioxide 7 pieces 117m, Ceratin 2°017
A white reflective layer containing m.

(3) A light-shielding layer containing 2.0117 m of carphone black and ceratin i, op/m.

(≠) The following cyan color patch-emitting redox compound θ.

e<zg/m, tricyclohexylphos 7ate o, o
ri9/m X, 2. J-Gt' Citadecylhydroquinone 0.0019% and Gelatin 0.0019% Ijj/m i containing layer□(j)
Red-sensitive red-sensitive inscribed positive silver bromide emulsion (silver content /.031
//m), gelatin/. 21! /m2, a red-sensitive emulsion layer containing the following nucleating agents o, o4 Lmg/m and λ-sulfo j-n-pentadecylhydroquinone sodium salt 0,7397 m2.

(t)2, j-) - t-pentadecylhydroquinone O1 Hiroshi/m, trihexyl phosphate 0
．． /I/rn and gelatin 0, 'I, 9/
Layer containing l112.

(7) Magenta dye-releasing redox compound of structural formula I ((:), 2/ #/m2), magenta dye-releasing redox compound of structural formula H (0.1117m2), ) lycyclohexyl phosphate <o.

-ory7m), J,j-di-t-pentadecylhydroquinone (0.00 g/m) and gelatin (
0.2g/sn ) containing layer.

Structural formula I Structural formula ■ (t) Green-sensitive intra + V type direct positive bromide bed emulsion (silk y6 with 0, I, 2 11 / m 2, dye-A O
, 97 n1g/m2, dye-B/. ,Zrim 1
17m), gelatin (θ.g/m), the same nucleating agent as layer U) (0.θ3rnll/m) and λ-sulfo J-n-pentadecylhydroquinone sodium salt (0, p/1n2 to 0). A green-sensitive emulsion layer containing.

Color chart-A Dye-B (ri) Same layer as (t).

(10) The following 4+i1 yellow dye-releasing redox compound (0, j31//m2', tricyclohegycyl phos7ate (0,/317m'') 1.2, j
-di-t-pentadecylhydroquinone (0,0/4
LIi/mouth 12) 5yohi gelatin (0, 7117m2)
A layer containing.

(//): # Sensitive m-type direct positive silver bromide "fJit with grudge against IJ agent/, θri g 7m 2), gelatin (),
9/m), the same nucleation i1 as Id(3) (0, Oll
mf 7m) 6yohi λ-sulfoj-〇-pentadecyl/tamidoquinone sodium salt (o, o7g
yIn ) A blue-sensitive emulsion layer having yiz.

(12) A layer containing gelatin/, 011/In'f.

After the photosensitive sheet was prepared with a color test chart (14) and sent to a wholesaler, a cover sheet was placed on top of the other, and between both sheets, the following processing solution was spread at 33'C to a thickness of K. (I used a 6mm U-pressure roller to unfold it). ) From Table 3, it can be seen that the compound of the present invention significantly increases the maximum concentration of H, and also lowers the minimum concentration of G and H. -10,000, used as a comparative example Al-phenyl-
J-Mercaptotetrazole has been found to have the disadvantage of significantly lowering the maximum concentration. Patent applicant: Fuji Photo Film Co., Ltd., 210 Nakanuma, Minamiashigara City, Fuji Photo Film Co., Ltd. Inventor: Keiji Morbayashi, Minamiashigara City 210 Nakanuma, Fuji Photo Film Co., Ltd. Inventor: Yukio Karino 210 Nakanuma, Minamiashigara City, Fuji Photo Film Co., Ltd. Amendments to the proceedings Mr. Commissioner of the Japan Patent Office 1, Indication of the case, 1986 Patent Application No. 91A1.
No. 32 No. 2, Name of the invention Silver halide photographic light-sensitive material 3, Relationship with the case of the person making the amendment Patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Fuji Photo Film Co., Ltd. Representative Tsutomu Ohnishi,
・-=へ'7) □□Soshizuku□□□ 4. Subject of amendment: "Detailed explanation of the invention" column 5 of the specification, Contents of amendment: Description in the "Detailed explanation of the invention" section of the specification. Correct as shown below.

l) Page 7, line 3 "α" all "δ" and correct it.

c) Number of pages ” and correct it.

3) No. 16 Toshita 1st line “Photography” "Photographic" and correct it.

tl,) 1st page bottom t~7th line “Hydrazine etc.” "Hydrazides, etc." and correct it.

! i’) No. 16 Toshita line 1 "-hypo" 紮 "Hypo" and correct it.

6) Structural formula (6) on the first page and correct it.

°7) Structural formula of 03 on page 22 " ” Correct it with〇 ) From page 36 to line 70 [Pivaloylacetanilides] "Pivaloylacetanilides" and correct it.

ri) The structural formula of the 57th member dye-B is

Claims (1)

[Claims] In a photographic light-sensitive material comprising a light-sensitive silver halide emulsion layer in which a blocked photographic reagent is combined, the blocked photographic reagent has at least seven cyclic amide groups; The atom is bonded via a π bond to an electron-withdrawing group that may be generated during development, and at the same time is cleaved by an intramolecular nucleophilic reaction of the nitrogen atom or electron transfer from the nitrogen atom. 1. A silver halide photographic light-sensitive material, characterized in that a photographically useful reagent is substituted at a position where it can be obtained.