JPH02843A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To solve the problem of after-colors by sensitizing dyes by incorporating specific compds. into a silver halide emulsion layer or other hydrophilic colloidal layers. CONSTITUTION:The silver halide emulsion layer is provided on a base and at least one kind of the compds. expressed by formula I are incorporated into this emulsion layer or the other hydrophilic colloidal layers. In formula I, A denotes a block group which can release a dye elution accelerator at the time of processing; B denotes the dye elution accelerator coupled to A via a heteroatom. The problem that the sensitizing dyes incorporated in the silver halide photosensitive material are not completely eluted during processing and the coloration remains (so-called 'after-colors') is solved in this way.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photosensitive material, and in particular contains a compound in which the active group or adsorption group of a dye elution promoter is blocked, and has no residual color. This invention relates to an improved silver halide photosensitive material.

(Background Art) In recent years, sensitizing technology using sensitizing dyes has been developed, and attempts have been made to produce silver halide photosensitive materials using large amounts of sensitizing dyes. In particular, the method using tabular silver halide grains is suitable for obtaining a silver halide photosensitive material with high sensitivity using a large amount of sensitizing dye.

U.S. Patent No. 4,434.226, U.S. Patent No. 4,439.5
No. 20, No. 4,414,310, Pt54゜43
3.048, 4.414,306, 4.4
No. 59,353, JP-A-59-99433, JP-A No. 62-
No. 209445 and other publications disclose methods for manufacturing and using tabular grains, and include improvements in sensitivity including improvement in color sensitization efficiency using sensitizing dyes, improvement in the relationship between sensitivity and granularity, and specific optical properties of tabular grains. α is known for its benefits such as improved sharpness and covering power.

(Problem to be Solved by the Invention) However, there is a growing problem that the sensitizing dye contained in the silver halide photosensitive material does not completely dissolve out during processing and leaves behind color in the photosensitive material (so-called residual color). .

Therefore, an object of the present invention is to provide a silver halide photosensitive material that solves the problem of residual color caused by sensitizing dyes.

(Means for Solving the Problems) An object of the present invention is to have at least one silver halide emulsion layer on a support, and in which the emulsion M or other hydrophilic colloid layer has the following general formula (I). This was achieved by a silver halide photosensitive material characterized by containing at least one compound represented by the following.

General formula (1) A represents a blocking group capable of releasing a dye elution promoter during processing, and B represents a dye elution promoter bonded to A via a heteroatom.

General formula (1) will be explained in detail below.

Some known blocking groups can be mentioned. For PI, Tokko Sho≠r-2, ri4
Layer number, Tokukaisho! Corr, rJr No. 77-42. rJ
No. U, American 7ff3. J//.

4-layer No. 74, special public Akihiro 7-Mari, rot No. (US watch 3
．． 6/j, t/7) that utilize blocking groups such as acyl groups and sulfo-el groups; −
/7. J4ri No. (US Patent 3゜rtt, No. 477), same! Yoichita, No. 626 (IFl'J made in the United States, 7rii,
rio), same jj-31.

No. 227 (U.S. Patent≠, ooy, okota), JP-A No. 6
4-77, f4 (No. 2 (US%ffu, 307°171
issue), same! Tar 10j, No. 4412, Tar 10j,
A blocking group that utilizes the so-called reverse Michael reaction described in t≠O issue; Tokuko Sho! Hiro-32゜727, U.S. Clock No. 3
．． 67 Hiroshi, ≠7r, same No. 3. 3, ≠ No. 10, same No. J, P 3,461, JP-A-77-/31. Rihiro section number, same! 7-13! , No. 1, No. 77-/Jj, No. 4μθ Blocking group utilizing the production of quinone methide or quinone methide compounds by intramolecular electron transfer; JP-A No. 5
r-xi, io, same! Turco/I.

≠ Those that utilize the intramolecular ring-closing reaction described in No. 3P; JP-A-Sho! t7-74. J Hong No. 1 (US Patent Hong, 33r, 20
0), same j7-/l! , 2≠No. 2, 77-/7ri,
Hiroko, Tata 737. Tada J issue, same! Tarl san〇, u4ri issue, same! Turquoise, 7 layer No. 1, 40-44
1.03≠ stated in issue! or t-membered ring cleavage; or JP-A No. 20/2017, No. 017, No. 4
/-417°73ri, same t/-W! , j417, which utilizes a certain number of nucleophilic agents for unsaturated bonds.

General formula (I) can preferably be represented by general formula (U).

General formula (II) In the formula, A represents a blocking group capable of releasing +X 1 addition D during treatment, D represents a dye elution promoter bonded to Xl via the heteroatom of D, and the heteroatom of X1tlX1 Represents a covalent linking group bonded to A through an atom, and ml represents O or l.

To the dye elution accelerator j represented by D''C of general formula (n),
It has a heteroatom and has the effect of promoting dye elution by itself, but if it is contained in a silver halide photosensitive material, it may cause harmful fogging, decrease in sensitivity, or damage the photosensitive material during storage. Change photographic characteristics (sensitivity, gradation, fog, etc.).

However, in the present invention, fiD is directly bonded to C and A via the heteroatom (m 1 =') or bonded via Xl (ml-1), and photographic processing (developing, fixing, etc.)
By doing this, it is possible to detach from the person, so the above-mentioned inconvenience does not occur. D is the general formula (lit) or f
A compound represented by l(1111') is preferred.

A+X, 10)D General formula (III) General formula (III’) In the formula, R1 is an aliphatic group having a Korg number of carbon atoms/~l, Ll-.

In the formula 0, Z and W represent -~= or -C-R4, and %14 is a hydrogen atom, a halogen atom, an amide group, a hydroxyl group,
Represents an alkenyl group, aryl group, aralkyl group, L
l is a hydrogen atom or an aliphatic M having a valence of λ to μ and having a carbon number of l to r
, R2 represents an aliphatic group having a carbon number of up to 117) λ, Xl is R5R5R5 R5Ra Rs and R6 is a hydrogen atom or a lower alkyl group. 72 represents 0 or l. ”, R
2, R3 represents a hydrogen atom, an alkyl group, an acyl group,
R2 and R3 may be connected to form a heterocyclic a-ring. 11 to 01 /, ko, or 3.

In the dye elution accelerator represented by D'''C, R1 and L1%
λ of carbon number/-1 represented by L2 ~ Hirovalent aliphatic! &
may be saturated or unsaturated, linear, branched or cyclic.

The following examples are typical examples.

-ch2-1-ct-t2 ct-i2-1+CH2.

-C)l=C)1- -C-C)i+, -cI-12-CI-1=ct-1-
The 11-substituted or unsubstituted alkyl group represented by H3 FL2s and R3 is preferably one in which the number of carbon atoms in the alkyl group is tr (for example, methyl, ethyl, propyl 2,
Substituents include halogen atoms (chlorine atoms, bromine atoms, etc.), hydroxyl groups, alkoxy groups (such as methoxy, ethoxy, etc.).
), sulfonyl & (Fl, t(dmethanesulfonyl, ethanesulfonyl), carbomoyl group, sulfamoyl crystal, carboxyl group, sulfo group, amine group (e.g. acetylamino) or sulfonabad group (e.g. methanesulfonylamine), etc. The ring formed by connecting R2 and R3 includes a virol ring, an imidazole ring, a pyrazole ring, a piperidine ring, a pyrrolidine ring, and a biR
Examples include radine ring and morpholine ring.

The acyl group represented by R2 and R3 has 3 carbon atoms.
The following are preferred, and conjugative examples include methoxycarbonyl group, acetyl group, and benzoyl group.

Here, when Ll is a hydrogen atom, it is It ICo, and L
When l is a divalent aliphatic group having carbon number/-1, A! 1 is 7.
3 is displayed on Komata.

Xl in general formula (n) represents a covalent linking group, is bonded to A via a heteroatom, and is cleaved into X and -D during photographic processing (e.g., development, fixing, etc.) and then immediately niD
represents a group that releases

As such a linking group, JP-A-3≠-/≠! Specification No. 131 (British Patent Association Open Co., No. 010.r/IA), U.S. Patent Nos. a, a4Lt, yt-, HirooP, ico3
No., UK! Total number -00t.

711, which releases EriD in the intramolecular ring-closing reaction, British Patent No. 2.07, No. 363, JP-A-77-/
J≠, those which release D by partial electron transfer as described in the specification of No. 3, etc., accompanied by desorption of carbon dioxide gas as described in JP-A No. 7-/7, R, No. λ, etc. Something that emits D, or Tokukaisho! Examples include linking groups such as those described in No. 2-23 Hirokoko which release D upon elimination of formalin. The structural formulas of the representative X1s described above are shown below together with D.

10CH2-D -0-C-OCH2-D 0-CH2 C)12-]) The attack of 0H ions and SO3 ionone and the subsequent reaction are compounds that release dye elution accelerators. Among them, particularly preferred compounds are those represented by the following general formula (IV
) can be mentioned.

The type of general formula (IV) xi to be used is selected depending on the timing of release of D, release control, the type of D used, etc.

Glocked dye elution promoter used in the present invention%
R7s R8 and R9 may be the same or different, and each represents a hydrogen atom or a group that can be substituted, and R7 and R8 and R7 and R9 may be bonded to form a carbocyclic or heterocyclic ring.

Yl is a nucleophile on the carbon of nl = / person, person, person (typical examples are crystals, and tz nido a group (here, RIG s
R13 and R14 may be the same or different and each represents a hydrogen atom or a 11-substituted group, and Xl and ml have the same meanings as in the general formula (IIJ).

The compound represented by general formula (IV) is used as a nucleophile (for example, ot-t-
ion, so3''-ion, hydroxylamine, etc.) to the unsaturated bond, the dye elution promoter represented by D can be removed.

As a blocking method for active groups that utilizes the addition of nucleophiles to such unsaturated bonds, JP-A-Sho! Turco 010! No. 7,
JP-A-4/-41!7!2, JP-A-A/-ta! 3μ7
number can be used.

Next, general formula (IV) will be explained in detail.

R7 represents a hydrogen atom or a substitutable group, and examples of substitutable groups include an alkyl group (preferably one with a carbon number of -20), an alkenyl group (preferably one with a carbon number of 2 to 0), an aryl group (preferably one with a carbon number of 1-0)
, an alkoxy group (preferably one having a carbon number of 1-λO),
Aryloxy group (preferably one having 1-10 carbon atoms)
, alkylthio group (preferably one with 1-20 carbon atoms)
, an arylthio group (preferably one having 6 to 20 carbon atoms)
, amino group A represents an unsubstituted amino (preferably a primary or tertiary amino substituted with an alkyl having 1 to 10 carbon atoms or an aryl having t to 20 carbon atoms), a hydroxy group, etc.
These substituents may have one or more of the following substituents.
, When there are two or more ItS groups, they may be the same or different.

Here, specific substituents include halogen atoms (fluorine, chlorine, bromine, alkyl groups (preferably carbon atoms 1-2
0), an aryl group (preferably one with l-coQ carbon atoms), an alkoxy group (preferably one with a carbon number of / to -0), an aryloxy group (preferably one with a carbon number of 4-20), Alkylthio group (preferably 11.< means number of carbon atoms/-2O
o%], arylthio crystal (preferably L< means carbon number l-co0
), an acyl group (preferably one with a carbon number of 0 to 0), an azilabano group (preferably an alkanoylamino with a carbon number of l-coO, a benzoylamino with a carbon number of l-coO;
, a nitro group, a cyano group, an oxycarbonyl group (preferably an alkoxycarbonyl group with carbon number/~0, a carbon number t-
20 aryloxycarbonyl], hydroxy group, carboxyl group, sulfo group, ureido group (preferably alkylureido with carbon number/~-〇, arylureido with carbon number t-λO), sulfone abado group (preferably carbon number l
-O alkylsulfonamide, alkylsulfonamide having t-20 carbon atoms, sulfasoyl group (preferably alkylsulfamoyl having 1-20 carbon atoms, 6 carbon atoms)
～−〇arylsulfamoyl), carbamoyl group (
Preferably alkylcarbamoyl having 1-10 carbon atoms, 6 to 6 carbon atoms. 20 arylcarbamoyl), acyloxy group (preferably 1-coQ carbon number 2), amine group (
Unsubstituted amino, preferably alkyl- having 1-20 carbon atoms
% or quaternary or tertiary amino substituted with aryl having 6 to 0 carbon atoms), carbonate ester group (preferably alkyl back acid ester having carbon number/-20, aryl carbonate ester having 4 to 2Q carbon atoms) J.

Sulfone group (preferably alkyl sulfone having 7 to -0 carbon atoms, aryl sulfone having t to λO carbon atoms), sulfinyl group (preferably alkyl sulfinyl having carbon number/-J (>), aryl urei having t to 0 carbon atoms) I can mention Nirn.

Furthermore, R7 may be combined with R8 or R9 to form a carbocycle or a heterocycle (eg, ! to 7-membered m). R,,R
9 may be the same or different, and each represents a hydrogen atom or lt
It represents a substitutable crystal, and substitutable groups include halogen atoms (fluorine, chlorine, bromine), alkyl groups (preferably those with 1 to 10 carbon atoms), and aryl groups (preferably those with 1 to 10 carbon atoms). ), alkoxy group (preferably carbon number l
2, aryloxy group (preferably with 4 to 10 carbon atoms), alkylthio group (preferably with 4 to 10 carbon atoms), 2, arylthio group (preferably with 6 to 10 carbon atoms), ), an acyloxy group (preferably one having 2 to 20 carbon atoms), an amine group (unsubstituted amino, preferably 1 substituted with alkyl having 1 to 0 carbon atoms, or aryl having 6 to 7 carbon atoms) or tertiary amino), a carbonamide group (preferably an alkylcarbonamide with a carbon number of 1 to 7, an arylcarbonamide with a carbon number of t-20), a ureido group (preferably an alkylureido with a carbon number of 1 to JQ, Aryl ureido having 6 to 7 carbon atoms), carboxy group, carbonate ester group (preferably 1-7 carbon atoms)
alkyl carbonate ester, aryl carbonate ester having 6 to 0 carbon atoms), oxycarbonyl group (preferably alkyloxycarbonyl having 1-10 carbon atoms, 4-J carbon atoms)
Aryloxycarbonyl group of O, carbamoyl group (preferably alkylcarbamoyl having 1 carbon atoms, arylcarbamoyl having t-20 carbon atoms), acyl group (preferably alkylcarbonyl group having carbon atoms/-20 carbon atoms, 4 carbon atoms) - arylcarbonyl of carbon number), sulfonyl, sulfonyl & (preferably tL<tz alkylsulfonyl having 1 to 20 carbon atoms, aryl sulfonyl of carbon xe+ to carbon number 0), sulfinyl group (preferably alkyl of carbon number l-coQ) sulfinyl, arylsulfinyl having 6 to 20 carbon atoms), sulfamoyl group (preferably alkylsulfamoyl having 7 to 0 carbon atoms, 717-rusul7 amoyl having t-20 carbon atoms), cyano group, and nitro group.

The substituents represented by R8 and R9 may have one or more substituents tl-, and when there are two or more substituents, they may be the same or different; The same substituents as those for R7 can be mentioned.

R10%R11s R12, R13 and R14 may be the same or different, and each represents a hydrogen atom or an exchangeable hydrogen atom, and the member-based substituent is an alkyl group (preferably carbon number/-J (7) ), alkenyl group (preferably one with 2 to 7 carbon atoms), aryl group (preferably one with 1-7 carbon atoms λ, alkoxy group (preferably % carbon number/-20f)), acyloxy &+ an acyloxy group (preferably one having λ to -0 carbon atoms), an amino group (unsubstituted amino, preferably an alkyl group having 1 to 10 carbon atoms, or an alkyl group having t to 20 carbon atoms); Aryl-substituted secondary or tertiary avanones, carbonamide crystals (preferably alkylcarbonamides with carbon numbers 1 to λO, arylcarbonamides with carbon numbers t#0); ureido groups (preferably carbon atoms 1 to λO); -KoO
an alkylureido group having a carbon number of t-JO], an oxycarbonyl group (preferably an alkyloxycarbonyl having a carbon number of l-coO, an aryloxycarbonyl having a carbon number of l-coO), a carbamoyl group (preferably a carbon Alkyl carbamoyl number/-20, carbon number 6 to J
(arylcarbamoyl of 7), acyl group (preferably alkylcarbonyl having 1-20 carbon atoms, t-20 carbon atoms)
arylcarbonyl], sulfonyl group (preferably alkylsulfonyl having 1 to 20 carbon atoms, carbon number j #J (7
arylsulfonyl), sulfinyl group (preferably alkylsulfinyl having carbon number/~-〇, carbon number 4-J
(arylsulfinyl of 7), sulfamoyl & (preferably alkylsulfamoyl of 1-coQ carbon atoms, arylsulfamoyl of 4 to 20 carbon atoms). Among these, preferred substitutions of R13 and R14 Examples of the group include oxycarbonyl group, carbamoyl group, acyl group, sulfonyl group, sulfamoyl group, sulfinyl group, cyano group,
Mention may be made of the nitro group. These rt substituents 1
The substituents may have two or more substituents, and when there are two or more substituents, they may be the same or different. Examples of the substituents include the same as the substituents for R7 above.

Next, among those represented by general formula (IV), those represented by general formulas (V) and (Vl) can be mentioned as preferable ones.

General Formula (V) General Formula (1) In the general formula (V), Zl represents an atomic group necessary to form a carbocyclic or heterocyclic ring.

In terms of discipline, for example! Contains a membered ring, a 7-membered carbon ring, or 7 or more nitrogen, oxygen, or sulfur atoms! The term "membered ring" refers to a membered ring or a 7-membered ring heterocycle, and also includes those in which these carbocycles or heterocycles form a fused ring at an appropriate position.

Specifically, cyclobentenone, cyclohexenone, cycloheptenone, benzocyclohebutenone, benzocyclointenone, benzocyclohexenone, ≠-pyridone, Hiro-quinolone, corpilone, Hiro-pyrone, l-thiokoviron, /-thiohiro- Viron, coumarin, chromone, uracil, etc. (Rls and R14 are synonymous with those of the above general formula (IV)) R15% R16 and R17 are hydrogen atoms, alkyl groups, alkenyl groups, aryl groups, aralkyl groups,
Represents an acyl group, etc.

Here, these carbocycles or heterocycles may have one or more substituents, and when one or more substituents are present, they may be the same or different. Examples of the member-like substituents include the same substituents as R7.

Also, Z2 in general formula (Vl) is Z2 in general formula (V)
It means the same thing as l, specifically 7 clobentanone,
Examples include cyclohexanone, cycloheptanone, benzocycloheptanone, benzocyclointenone, benzocyclohexanone, di-tetrahydrobiriton, dihydroquinolone, and tetrahydropyrone. These carbocycles or heterocycles are It! It may have one or more L1 groups, and when there are two or more substituents, they may be the same or different. Specific substituents include the same substituents as the above-mentioned R7.

R8, R9, XI%Y, and ml are general formula (IV)
It is the same as mentioned above.

In general formula (IV), R7, R8, R9% Rlos
Rll% R12, R13 and R14 are selected according to the general formula (
fV) is selected depending on the pH1 composition of the processing solution being processed and the required timing time.

In addition, the compound of the present invention can be used in addition to pt- during photographic processing (e.g., development, fixing, etc.), especially sub@t#1 ion human a.
xylamine, thiosulfate ion, metabisulfite ion,
Tokukai Akira! ? -/Hydroxamic acid and its related compounds described in R-rat No. 3, oxime compounds described in JP-A-60-7772 and dihydroxybenzene-based developing agents described below, /-phenyl-3-pyrazolidone-based developing agents, p- By using a nucleophilic substance such as an aminophenol developing agent, the release rate of the dye elution promoter can be controlled over a wide range.

The amount added is usually 1 to io' to the compound of the present invention.
The amount used is twice the molar amount, preferably about 102 to 106 times the molar amount.

Next, examples of the composition of the compound of the present invention will be shown, but the present invention is not limited thereto.

2tis H3 In addition to the above-mentioned compounds, those described in the following publications can also be used as the compound represented by the general formula (II).

Tokukai Akira! Turco 010! No. 7, JP-A-7/-≠3732
No. 4/-2, 3rd edition, No. 7.

The compound represented by the general formula (fl/) can be synthesized according to the method described in the above-mentioned patent, and can also be easily synthesized according to the synthesis method described below or according to it.

Synthesis of Exemplary Compound (1)
s Ann, Chem, Bd, t/co, 1ti(iy
Eri synthesis was performed according to the following method described in zr).

/+J-') fif le urine $J74Jil (J, /4t-
Maron #1769 (1.4 comol) is dissolved in AOOml of glacial acetic acid at 60-700C.

Next, add anhydrous vinegar tIRIJ01 and slowly dissolve it.
Raise the temperature to C. After stirring for an hour, leave it at room temperature overnight, and put it on ice! I-acid and acetic anhydride are distilled off under reduced pressure. Pour the residue into ethanol 1001d while hot, separate the precipitated crystals from house to house, and add concentrated hydrochloric acid 310111 and water aoo
After the infant was refluxed for 2 hours at yst, it was left to stand for t hours under water cooling. Separate the precipitated crystals in a furnace, wash with a small amount of ethanol, and! -360 g of dimethylbarbic acid was synthesized.

Three tablespoons of water are added to this /j-dimethylbarbyl eR/1011, and phosphorus oxychloride r00d is gradually added dropwise. After heating under reflux for 1.5 hours, the phosphorous heptachloride is distilled off under normal pressure, and the residue is poured hot onto ice. Separate the precipitated crystals and extract the p liquid with chloroform (X J )
L, anhydrous sulfur #Rt Dry with thorium. Next, chloroform was distilled off, and the resulting residue was combined with the previous crystals and recrystallized from water to synthesize DEBU-Qaa-/3-dimethyluracil rog.

COt-Kuclo/, J-dimethylurazilco19 acetonitrile solution 7014 under water cooling (internal temperature z OC)
, and He Chlorosaxibado lt9 were added. After the internal temperature gradually rose and reached 3!0C, it was stirred for an additional 7 hours. 70 ml of water was added to the reaction solution, and the precipitated crystals were collected by filtration, washed with cold acetonitrile irm and a mixed solvent of water/IR1, and dried to obtain j,A-dichloro-/,J-dimethyluracil/rg. .

Then Kodimethylaminoethanethiol hydrochloride rI
, μg of sodium methoxide (% methanol solution) was added dropwise to the methanol/jut@ solution under nitrogen, stirred at room temperature for 70 minutes, and then filtered. The filtrate was concentrated to dryness under reduced pressure and dissolved in acetonitrile/j'll.
Dripping rotoeli,! .

t-dikuoa-/, J-dimethylcracilit.

The mixture was added dropwise at room temperature into a system in which tg was dissolved in acetonitrile Q1.

The reaction mixture was stirred for 2 hours and then filtered. The filtrate was concentrated under reduced pressure. After adding 20 d of ethanol and 71 ml of 0% hydrochloric acid ethanol to the residue, the ethanol was removed under reduced pressure, ethyl acetate was added to the residue, and the precipitated crystals were collected by filtration to obtain the hydrochloride of exemplified compound (1). /J, 2g was synthesized. Melting point: 41-/44°C Exemplary compound (Synthesis of power) Into a 100-cm reaction vessel equipped with a distiller style, put -1 ethylhexylamine zog, methyl carbamate 2, 11 and 100 m of toluene, and add the catalyst.

19 dibutyltin oxide was added and stirred while heating.

Except for methanol produced during the reaction, the reflux temperature is //17
When the temperature reaches 0C () the boiling point of luene), remove the distiller wind,
Instead, a 6-member reflux system was applied, and the mixture was stirred for an additional 30 minutes, and then allowed to cool. Toluene was removed under reduced pressure, the residue was washed with n-hexane, collected by filtration, and N-(coethylhexyl)Mllt/
, SF gain.

Obtained N-(λ-ethylhexyl) urine 810g, -+
r oy acid 369, vinegar FIR/00111 solution
ooc and stirred for an hour. After cooling, remove acetic acid under reduced pressure, add 100ml of water and chloroform odd.

I extracted it.

Is the organic layer saturated with bicarbonate? After washing with IJum solution and then saturated saline and drying over anhydrous magnesium sulfate, chloroform was removed under reduced pressure, and the residue was washed with n-hexane and filtered. I got reference 9.

Obtained utabe (coethylhexyl)barbylic acid a
Add oxychlorinated water to the mixture, and gradually add water dropwise. After heating under reflux for an hour, the phosphorus oxychloride is distilled off under normal pressure and the residue is poured hot onto ice. Furthermore, extract the organic layer 3 times with 0 Roformco 00d and collect the organic layer.
Dry with anhydrous magnesium sulfate. Next, chloroform was removed under reduced pressure, and n-hexane was added to the resulting residue.
The precipitated crystals were collected by filtration. Recrystallize from ethyl acetate to obtain 4-
p a a-J -(coethylhexflu)uracil 3
-g was obtained as yellow crystals.

Dimethylformide of the obtained t-chloro-5-(coethylhexyl)crazilcoOg! In Od solution, il
To the mixture was added 1 g of potassium carbonate, 1 g of iodomethyl chloride, and the mixture was stirred at room temperature for 1 hour. The reaction solution was filtered, the filtrate was poured into water, and the mixture was extracted twice with aaform 10ON.

After washing the organic layer with saturated brine and drying over anhydrous magnesium sulfate, chloroform was removed under reduced pressure to obtain 6-chloroa-J-(coethylhexyl)-7-methyl-urazilco 19 as an oil.

'tl et al. 4-/mouth a-3-(coethylhexyl)-/-methyl-uracil λ09 solution in acetonitrile! OxJIlc N-chlorosuccinimide was added to the mixture, heated to 100°C, and stirred for an hour.

After cooling, acetonitrile was removed under reduced pressure, water was added to the residue, and the mixture was extracted with chloroform 100111. After washing the organic layer with saturated brine and drying over anhydrous magnesium sulfate, chloroform was removed under reduced pressure, and the residue was purified by silica gel chromatography to obtain an oily substance. , A-Sil Rolow 3-(Coethylhexyl)-/-Methyluracil 22
I got g.

Then /-(kodimethylaminoethyl)-! - Sodium methoxide (21% methanol solution) 209 was added dropwise to 10 fl of mercaptotetrazole hydrochloride and metal λ01 solution under nitrogen, and after stirring at room temperature for 10 minutes,
Filtered. The filtrate was concentrated to dryness under reduced pressure, dissolved in acetonitrile, and added through a dropping funnel to j,4-
Dichloro-5-(J-4+ruhexyl)-/-methyluracil was added dropwise at room temperature to a system in which B was dissolved in acetonitrile. The reaction mixture was stirred for 7 hours and 30 minutes and then filtered. The filtrate was concentrated under reduced pressure.

After adding ethanol solution and cos hydrochloric acid ethanol solution to the residue, the ethanol was removed under reduced pressure, ethyl acetate was added to the residue, the precipitated crystals were collected by filtration, and the exemplified compound (hydrochloride/7. t9 was synthesized.Melting point/cog~lco4'C
hem, Pharm, Bu eyes Kota (5),! !
It was synthesized by the following method described in /Co13Co0 (/Wrt).

Cyclohexane-/! -Dione/4t, TFL, pyridine 109 was added to the chloroform 300111 solution, and benzoyl chloride/19 was added dropwise. φ at room temperature
After stirring for an hour, the reaction mixture was poured into ice water. The organic layer was washed with dilute hydrochloric acid, then with saturated sodium bicarbonate solution, and then with brine, dried over anhydrous magnesium sulfate, and concentrated to dryness under reduced pressure to yield 3-penzoyloxycyclohexenone as a crude product. °C obtained. The obtained 3-benzoyloxycyclohexenone-,2 was added to a solution of anhydrous aluminum chloride soy and 3 Om of dichloroethane without purification. After stirring at room temperature for 17 hours, the reaction mixture was poured into cold hydrochloric acid (10 g), and the organic layer was extracted twice with dichloroethane and the aqueous layer.

The organic layer was collected, washed with brine, dried over anhydrous magnesium sulfate, and then dichloroethane was removed under reduced pressure. The minimum amount of diethyl ether/N thorium hydroxide solution that could be dissolved in the residue was obtained. The aqueous layer was made acidic with concentrated hydrochloric acid, extracted with diethyl ether, the organic layer was dried over anhydrous magnesium sulfate, and the diethyl ether was removed under reduced pressure. When the residue was recrystallized by adding n-hexane, cobenzoylcyclohexane/J dione/39 was obtained.

The obtained cobenzoylcyclohexane/.

! -Zeon! Oxalyl chloride sample 1 was added to I under water cooling, and after stirring for 3 hours, excess oxalyl chloride was removed under reduced pressure. The reaction mixture was evaporated under reduced pressure 114', λg
Cobenzoyl-3-chlorocyclohexenon-co was obtained. bp, /r! 〜lriA'C,/0,/mm
Hg Next, under nitrogen flow! -Mercapto t-(λ-(/-
imidazoyl)ethyl)tetrazole! 11 Acetonitrile/! 1 solution, /, r-diazabicyclo[! ,μ
After adding dropwise an acetonitrile solution of lO' undecene-7 (DBU) 4A49/all and stirring at room temperature for 5 minutes, 10 rd of an acetonitrile solution of cobenzoyl-3-chlorocypahexenone 2, t9 was added and stirred at room temperature for an hour.

Then, the acetonitrile was removed under reduced pressure, 1 ml of salt rR 011 was added, and the mixture was extracted with chloroform 100-. After washing the organic layer with saturated brine and drying over anhydrous magnesium sulfate, chloroform was removed under reduced pressure, ethyl acetate was added to the residue, and the precipitated crystals were collected by filtration. Exemplary compound a [7.
3jp were obtained.

Melting point /lr-/7/'C Synthesis of exemplified compound Q (A) (BJ (C) Cyclohexane co09 (0, λ mol) and formic acid ethyl ester /49 (0,2 mol) '5 were dissolved in dry ether. 〇〇R
Na) 1 (40%) while cooling in a water bath.
Content) / 69 (0, II Mok) f / time.

After addition, stir at room temperature for 4 hours. Reaction mixture (
While cooling the mixture in a water bath again, an ether solution of Pα3 core 9 (0, -mol)/jOwl was added dropwise. After the addition was completed, the mixture was stirred at room temperature for 3 hours, and the precipitate formed was removed in a vacuum oven. Concentration of the mother liquor yields an oil (3/9 C1).

Then, coethylaminoethanethiol hydrochloride λPg
, sodium methoxide (21% methanol solution) r! under nitrogen in a methanol tortttH solution. After adding I dropwise, the mixture was stirred at room temperature for 10 minutes, and then filtered. The filtrate was concentrated to dryness under reduced pressure and dissolved in 100 ml of acetonitrile.
319 in (C) is acetonitrile to
It was added dropwise to the system dissolved in wt under water cooling. The reaction mixture was stirred for 3 hours and then filtered. The filtrate was concentrated under reduced pressure.

Add ethanol to the residue, 40% hydrochloric acid in ethanol
After adding Owd, ethanol was removed under reduced pressure, Tl-1F was added to the residue, and the precipitated crystals were filtered to synthesize an exemplary compound (DJ hydrochloride, ≠21).

Synthesis of Exemplified Compound I J, Am.

Chem, Soc, r/ , JxAt (/Pt5'
It was synthesized by the following method described in ).

Add 120m of carbon disulfide to 32g of aluminum chloride℃
, the slurry was mixed with chlorophenol
The mixture was gradually added to a solution of carbon disulfide zO*l, and stirred at room temperature until no hydrogen chloride gas was generated. next,
Hexachloropropane j4. Add 1 drop of λg over 20 minutes, stir at room temperature until no hydrogen chloride is generated, then distill off carbon disulfide under normal pressure, and add cold acid water (concentrated sulfuric acid Q1, water 100w) to the residue. After stirring for io minutes, the precipitated crystals were collected by filtration and recrystallized with diethyl ether.
3. Hiro, 6-dolichlorocoumarin lr,ag was obtained. Melting point /3j ~/jroc Next,! -Mercapto/-(λ-dimethylaminoethyl]tetrazole 3g in methanol lQν solution under nitrogen stream, ?)lium methoxide (Jr% methanol solution) i, tg were added, stirred for 3 minutes at room temperature, and concentrated under reduced pressure. did. Add 10 td of acetonitrile to the lA residue, and! Then, a solution of 3 g of trichloroa-coumarin in 10 ml of acetonitrile was added dropwise.

After stirring at room temperature for 2 hours, it was filtered, and the filtrate was concentrated to dryness under reduced pressure. Ethanol in the residue! After adding 4 Atd of hydrochloric acid ethanol solution (CoO%), the ethanol was removed under reduced pressure. Ethyl acetate was added to the residue and the precipitated crystals were collected by filtration to reveal the hydrochloride of Exemplified Compound I! ,
/ll was obtained.

Melting point: 7/-/7j °C The compound of general formula (1) of the present invention may be added to any layer such as a photosensitive emulsion layer or a non-photosensitive layer. Preferably, it is contained in a non-photosensitive layer.

The loading amount of the compound of the present invention is 0.00101 in total powder @
Moltyl 10 ruti, preferably 0.001 mol to j(7
In terms of molar ratio, txo and o are particularly preferably 1 mol to -0 mol.

The compounds of the present invention include alcohols such as methanol, TI
-Dissolved with IF, acetone, gelatin, surfactant, etc.
It can be dispersed and added to the coating solution. Also, like the coupler, it can be dissolved in a high boiling point organic solvent and emulsified and dispersed using a homogenizer.

The method of the present invention exhibits an SS effect when a sensitizing dye is applied to a C. spectrally sensitized black and white silver halide photographic material, which is rapidly processed, preferably within Po seconds, particularly within 70 seconds.

The development processing method of the present invention basically comprises the steps of black and white development, fixing, water washing, drying or μ development, fixing, stabilization and drying of the exposed silver halide photosensitive material.

The most preferred developing agent used in the developer used in the trench treatment of the present invention is a combination of dihydroxybenzenes and /-phenyl-3-birasolitons from the viewpoint of obtaining good performance. Of course, a p-aminophenol type developing agent may also be included.

The dihydroxybenzene phenomenon crude drugs used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 3-dichlorohydroquinone, and! −
Dichlorohydroquinone, ko, J-Sif0mhydroquinone, ko,! - Dimethyl hydride, aquinone, and the like, but hydroquinone is particularly preferred.

As the p-aminophenol developing agent used in the present invention, 1) N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, IN-(≠-hydroxyphenyl; There are glycine, co-methyl-p-aminophenol, p-benzylaminophenol, etc., among which % he-methyl-p
-Aminophenol is preferred.

The 3-pyrazolidone developing agent used in the present invention is/
-722-3-pyrazolidone, /-)22-p,4
t-dimethyl-3-pyrazolidone, /-722ruhiro-
Methyl-≠-hydroxymethyl-3-pyrazolidone, /
-Phenyluda, l-dihydro-axymethyl-3-pyrazolidone, /-phenyl-! -Methyl-J-ni'Fso IJ
t”: /, /-p-aminophenyl-e, p-dimethyl-3-pyrazolidone, /-p-)lylu≠, Hiro-dimethyl-3-pyrazolidone, /-p-tolyl-≠-methyl-Hiro-hydroxymethyl -3-pyrazolidone, etc.

The visual agent is usually 0.01 mol/! ~1. Preferably, it is used in an amount of λ mol/j.

Examples of sulfite preservatives used in the development process of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, sodium sulfite, sodium bisulfite, and potassium metabisulfite. Sulfite has a Ql of 2 mol/1 or more, especially 0. mol/j or more is preferable. Also, the upper limit is
! Preferably it is up to mol/j.

It is preferable that the pH of the developer used in the development process of the present invention is within the range of /3. Even better! pH10
The range is from to /.

p) The alkaline agents used for setting 1 include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and tertiary phosphorus! 1! :? -) Contains pH regulators such as potassium triphosphate.

Patent Application No. 4/-11701 (Borate J, Japanese Patent Application No. 1973-11701)
Buffers such as 23 Reference No. 33 (for example, sucrose, acetoxime, !-sulfosalicylic acid), phosphates, carbonates, etc. may be used.

Further, a hardening agent may be used in the developer. As the hardening agent, dialdehyde hardeners or their bisulfite adducts are preferably used, and examples of such hardeners include glutaraldehyde and its bisulfite adducts.

In addition to the above components, additive DO agents include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol; Organic solvents such as ethanol and methanol %J:/-Phenyl! -mercaptotetrazole, λ-mercaptobenzimidazole-! −
Mercapto compounds such as sulfonic acid sodium salt, j-
It may also contain an antifoggant such as an indazole compound such as di-a-indazole, or a pent-triazole compound such as j-methylbenz-triazole.
h Disclosure Volume 174, 4/744A7
, Section XXI (72nd issue, / 7th year) development accelerators and, if necessary, toning agents, surfactants, antifoaming agents, water softeners, JP-A-Sho! It may also contain the amino compounds described in Reference J-104.

In the development process of the present invention, a silver stain preventive agent is added to the developer, such as JP-A-Sho! Compounds described in No. t-24!3 No. 7 can be used.

The developer of the present invention includes European special IFF oistr
Amino compounds such as alkanolamines described in Japanese Patent Application Laid-open No. JP-A-104-104 can be used.

In addition, "Photographic Processing Chemistry" by F. and A. Mainen, published by Focal Press (
/ F t in 2010], pages 4 to 22, U.S. Patent No. 3,01j, same! octopus.

The materials described in JP-A No. 74, JP-A No. 33, Sho at-≦Data, etc. may be used.

The fixing solution is an aqueous solution containing thiosulfate as a fixing agent.
, pI'iJ, r or more, preferably 11.2 to 7°0. More preferably pH Hong! ~! ,! It is.

Examples of the fixing agent include sodium thiosulfate and thio[2-ammonium, among which ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of fixative can be varied as appropriate, and is generally about 0.1 to about t mol/! It is.

The fixer may also contain water-soluble aluminum salts that act as hardeners, such as aluminum chloride, aluminum sulfate, potassium alum, and the like.

The fixing solution may contain tartaric acid, citric acid, gluconic acid, or their fermented derivatives alone or in combination. These compounds are o, o per liter of constant solution/l.
Those containing more than oz mol are effective, especially 0. O1 mol/l
-0.03 mol/l is particularly effective.

The fixer may optionally contain preservatives (e.g. sulfites, bisulfites, pH buffers (e.g. acetic acid, boric acid), pH!
Jl modifiers (for example, sulfuric acid, chelating agents with water softening ability, and compounds described in Japanese Patent Application No. 1, No. 1, No. 1, No. 2003) may be included.

In processing the existing scratches of the present invention, it is more preferable to reduce the swelling percentage of the photosensitive material (preferably 10% to 10%) and weaken the dura film, since rapid processing can be performed. It is more preferable to have no dura mater, and it is even more preferable to have no dura mater during fixing, but it is possible to weaken the dura reaction by increasing the pH of the fixing solution above ≠. Both the liquid and the fixer can each constitute a replenisher consisting of one liquid, and there is also the advantage that the replenisher can be prepared by simply diluting it with water.

In the above-mentioned method for developing a silver halide photosensitive material of the present invention, the material is treated with washing water or a stabilizing solution after the development and fixing steps. Here, the stabilizing liquid is the same as washing with water, only the name is different.

The replenishment amount of washing water or stabilizing solution is λ per m2 of light-sensitive material.
] The following (including 0, ie, washing with water) are preferred.

By doing this, it is possible not only to save water, but also to make the piping installed in the automatic processing machine free from cracks.

As a method of reducing the amount of replenishment, a multi-stage countercurrent system (1 FII, 1 stage, 3 stages, etc.) has been known for a long time. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing will be processed in a progressively cleaner direction, that is, sequentially in contact with the processing solution that is not contaminated by the fixer, resulting in even more efficient processing. Good washing is done.

In order to make the above-mentioned existing damage treatment of the present invention a water-saving treatment or a piping-free treatment, it is preferable to apply an anti-mildew means to the washing water or the stabilizing liquid.

Anti-mildew methods include the ultraviolet irradiation method described in JP-A No. 4O-243P≠Q, the method using a magnetic field described in JP-A No. 4O-243P≠Q, and the method described in JP-A No. 4O-243P≠Q, J/-/J/13. A method for purifying water using an ion exchange resin described in 1977-
2! No. 1107, same to Kota, try number, same 4/-
4j0jO issue, same 4/-! The method using the antibacterial agent described in the /j Riwo issue can be used.

Furthermore, L, E, West, “Water Qua
Eye Criteria'Photo, Sci, & E
ng, Vol.

P Aid (/9 j j), M, W, Be
ach.

“Microbiological Growth!
￥ inMotion-Picture Process
ssing”SMPTE Journal Vol,r
r + (/Pyt), Roo.

Deegan, “Photo Processing
WashWater Biocides'J, Tma
ging Tecblo, /164 (/Well) and JP-A No. 17-11442, No. 77-111 $3, 1t-iozi Hiroshi! No. 77-/jJ/No. 4, same!
r-1rtri issue, same! 7-27! No. 30, same j7-/
Antibacterial agents, antifungal agents, surfactants, etc. described in R7 Co≠≠ can also be used in combination.

Furthermore, the washing bath or stabilizing bath of the present invention contains RoT, Kr
Inteazoline compounds described in J. Image, Tech / 0°C6) by J. Eiman, Re5earch Disclosure
No. 0! Volume, 46201-2t (May 1911)
Isothiazoline compounds described in Volume λλr of the same,
Microbiocides include inthiazoline compounds, which were published in the 3rd year of the 1990s, and the compounds described in the 3rd issue of the Japanese Patent Application.
) can also be used together.

In addition, "Chemistry of anti-bacterial and anti-mildew" by Hiroshi Horiguchi, Sankyo Publishing (Showa 5)
7), "Handbook of Antibacterial and Antifungal Technology", Japanese Society of Antibacterial and Antifungal Research, Hakuhodo (Showa≦l) may be included.

In the method of the present invention, when washing with a small amount of washing water or stabilizing with a stabilizing liquid, it is more preferable to provide a squeeze roller washing tank as described in Japanese Patent Application Sho A/-/lJ Core No. 7. Further, it is also preferable to adopt a water washing step structure as disclosed in Japanese Patent Application No. 4/1974 (No. 74/P).

Furthermore, in the method of the present invention, a part or all of the over-70-liquid from the washing or stabilizing bath, which is generated by replenishing the washing or stabilizing bath with water treated with anti-mildew means depending on the treatment, is specially treated. As described in Japanese Patent Publication No. 60-231113, it can also be used in a processing solution having fixing ability, which is a processing step before that.

When the silver halide photosensitive material of the present invention is processed with an automatic imager that includes at least the steps of development, fixing, water washing, or stabilization and drying, the steps from development to drying are zero.
The process must be completed within seconds, that is, the time from the time when the leading edge of the photosensitive material begins to be immersed in the developer until the leading edge emerges from the drying zone after undergoing fixing, rinsing (or stabilization), and drying. (so-called DrY to Dry time) is preferably within 2Q seconds, particularly within 70 seconds.More preferably, this Dry t.

Dry (0 time is within 40 seconds.

In the present invention, "developing process time" or "developing time" refers to the time from when the leading edge of the photosensitive material to be processed is immersed in the developing tank solution of the automatic processing machine until it is immersed in the next fixing solution. -1 "Fixing time" is the time from immersion in the fixing tank solution until immersion in the next washing tank solution (stabilizing solution) "Washing time" refers to the time during which it is immersed in the washing tank solution.

In addition, "drying time" means that a drying zone in which hot air of 3j'C-1000C, preferably uo'c-to'c, is blown is installed in the automatic processing machine, and the drying time is within the drying zone. refers to time.

In order to achieve the above-mentioned dry-to-dry rapid processing within 20 seconds, the development time should be within 30 seconds, preferably within 25 seconds, and the development temperature should be around r'C~! 06C
is preferable, and 30°C-4LO°C is more preferable.

According to the present invention, the fixing temperature and time range from about 0'C to about z
o0c is preferably 5 seconds to 30 seconds, and J O0C to aO°
C is preferably 4 seconds to 20 seconds.

The water FC or stabilization bath temperature and time are preferably t seconds to 0 seconds at 0 to to'c, and more preferably 4 seconds to /j seconds at /j'C-dao'C.

According to the method of the invention, the developed, fixed and washed or stabilized photographic material is dried via a squeeze roller which squeezes out the washing water. Drying is approximately ≠ 00C ~ approximately t
The drying time is suitably changed depending on the surrounding conditions, but it is usually about 5 seconds to 30 seconds, and particularly preferably about 5 seconds to 30 seconds. be.

Dry to Dry with the sensitive material/processing system of the present invention
When developing in 2θ seconds or less, in order to prevent uneven development peculiar to rapid processing, Japanese Patent Application Sho J/--Ta 7672
It is possible to apply a roller made of rubber material as described in the specification of the patent to the roller at the outlet of the developing tank, and
As described in the specification of No. 7-λ7t73, the discharge flow rate for stirring the developer in the developer tank should be set at 10 m/min or more, and furthermore, the patent application No. 1977-3/! ! As described in No. 37, it is preferable to use stronger stirring at least during development processing than during standby. Furthermore, for rapid processing as in the present invention, it is particularly preferable that the cooler of the fixing solution tank be configured to increase the fixing speed or to have opposing rollers. By using opposed rollers, the number of rollers can be reduced and the processing tank can be made smaller. In other words, it is possible to make the automatic processor compact.

In the IjA image processing method of a light-sensitive material of the present invention, there is no particular limitation on the photographic light-sensitive material, and general black and white light-sensitive materials are mainly used. In particular, photographic materials for laser printers for medical images, scanner sensitive materials for printing, medical direct photography X-ray sensitive materials, medical indirect photography X-ray sensitive materials, CRT image recording sensitive materials, high contrast sensitive materials for printing, etc. It can be used for.

In order to produce a photosensitive material suitable for rapid development according to the present invention, it can be achieved, for example, by one or a combination of two or more of the following methods.

■ Use silver halide containing little or no iodine. That is, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. are used, and the silver iodide content is 0-j moles.

■ Adding a water-soluble iridium salt to the silver halide emulsion.

(2) Reduce the amount of iron Il applied in the copper halide emulsion layer. For example, l~z9/wind 2 on one side, preferably /-
4ci/shoulder 2. More preferably 1 to 397 ym2
It is.

■ Reduce the average grain size of silver halide in the emulsion. For example, i, oμ or less, preferably. .

It should be 7μ or less.

(2) As silver halide grains in the emulsion, tabular grains, such as aspectral or larger grains, preferably aspectral or larger grains, are used.

(2) The swelling percentage of the silver halide photosensitive material is kept below 0.00%.

The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. They may be grains with crystal defects such as twin planes, tabular grains, or composites thereof.

The tabular grain aspect ratio is given by the ratio of the average diameter of circles having an area equal to the projected area of the grains on the sides of the tabular grain to the average value of the grain thicknesses on the sides of the tabular grain. In the present invention, the preferred powder form in the case of tabular grains is more than or equal to as much as - less than -φ, more preferably! That's it - Mimizo. Further, the particle thickness rXO is preferably 7 μ or less, particularly preferably 0,0 μ or less.

Tabular grains preferably have -I-e-11 amount-1 of all grains
More preferably, it is present in an amount equal to or more than ←weight.

The grain size of the silver halide may be a monodisperse emulsion with a narrow distribution, or a polydisperse emulsion with a wide distribution.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, such as Re5earch Disclos
ure, 16/7 & u J (/P 7 r year/- month 2.12-23 pages, @1. Emulsion production (Emuls
ion preparation and type
s) @ and the same, /I6/17/A (//979//, tar page) can follow Kisoft's method.

The photographic emulsion used in the present invention is described in "Chemistry and Physics of Photography J" by Gura7 Kide, published by Beaumontel (P.

Glafkides, Chimie et Phy
siquePhotographique PauI
Montel, /rit7), "Photographic Emulsion Chemistry" by Duffin, published by Cal Press (G, F, Duffin
.

Photographic Emulsion Ch
emistry (Focal Press, / 5F
t&), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al.
7 Published by Oichi Cal Press (V, L, Zelikman
at al, Maklngand Coati
ng Photographic Emulsion.

It can be prepared using the method described in Focal Press, /5'6u).

When forming the silver halide grains used in the present invention, control grain growth! For ff-ru, silver halide melting axes 1, 1 PII, ammonia, rhodankali, rhodanammonium, thioether compounds (for example, US watch No. 3.
27/,/! No. 7, No. 7, 77 (4゜tar No. 3.7041,130, Reference No.

Kotupu, Tate 32, Doag Hiro, λ7bu, 77 Sango, etc.)
, thione compounds (for example, JP-A No. 11-12.≠Qt, No. 77,777)
No. i, amine compounds (e.g. JP-A-Sho re-ioo,
yt'y number, etc.] can be used.

In the present invention, water-soluble rhodium salts and water-soluble iridium salts as described above can be used.

As a method for reacting the soluble silver salt and the soluble halogen salt in the present invention, any of the single 9m mixing method, the simultaneous mixing method, and the combination of Ueho et al. may be used.

It is also possible to use a method in which particles are formed under an ion holder (so-called back mixing method).

As one type of simultaneous mixing method, a method of keeping the pAg in the liquid phase in which silver halide is produced constant, that is, the so-called Chondrold double jet method, can be used. According to this method, the crystal shape is regular. This provides a silver halide emulsion with a nearly uniform grain size.

The silver halide emulsion used in the method of the present invention is preferably chemically sensitized.

In the case of chemical sensitization, ordinary sulfur sensitization, reduction sensitization, noble metal sensitization, and combinations thereof are used.

Furthermore, as a chemical sensitizer, Allyl thiocarbamide,
Sulfur sensitizers such as thiourea, thiosulfate, thioether and cystine; potassium chlorooleate, aurous, thiosulfate and potassium chloride)
IPotassiumchlor.

Examples include noble metal sensitizers such as tin chloride, reduction sensitizers such as phenylhydrazine, and reductone.

The silver halide emulsion used in the present invention is spectrally sensitized with a known spectral sensitizing dye, if necessary. Spectral sensitizing dyes that can be used include, for example, Hamer, 1. Heterocyclic Compounds, Cyanine Dice and Related Functions, John Quealy and Sons, published in 441-2013 (F, M
, Hamer.

”Heterocyclic Compounds
-TheCyanine Dyes and F
“Related Compounds”, John Wi
ley & 5ons (IP4≠n, by Sturmer, 1 Heterocyclic Compounds - Special Topics in Heterocyclic Chemistry, published by John Wiley & Sons in 1977) (D. M. Sturmer, “Heterocycle
icCompounds -5special Top
ics 1nHeterocyclic Chem
istry + John Wiley & 5on
Cyanine, mero-7anine, rhodacyanine, styryl, hemicyanine, oxonol, benzylidene, holopolar, etc., as described above, can be used, but cyanine and merocyanine are particularly preferred.

Sensitizing dyes that can be preferably used in the present invention include JP-A-60-1331741, JP-A-4/-71332, JP-A-6
Court T, 2ji issue, same! Turco lλt No. 27, same! Q-
/ Coco Taco r issue, same zy-ir.

Examples include cyanine dyes and merocyanine dyes represented by the general formulas described in No. tzzi and the like. In terms of entertainment, Japanese Patent Application Laid-Open No. 4/1973 (No. 7-/1317, pages (r) to (/l), Japanese Patent Application Laid-Open No. 4/71312, pages 13 to (7),
2≠) ~ (-12 pages, No. (1
@
(!) ~ (7) pages, Tokukai Sho! 0-/JJPJr No. (
Pages a) to (2), Tokukai Sho! No. 7 of Tar 1 Rozri
) to (/r) pages etc., which spectrally sensitizes isa silver generator to the blue region, fringe region, red region, or infrared region of the spectrum at °C.

Although these sensitizing dyes may be used alone, combinations thereof are often used, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that substantially absorbs visible light and exhibits supersensitization. For example, an aminostilbene compound which is a nitrogen-containing heteroartic ring nucleus and has a W character (listed in the US %F'N4J, fi3.iyO No. 1,611゜72
No. 1 is Kigeki's J5 aromatic organic acid formalde-)
-4, M'4fn l pi, tha US tn rt'g
j, 7 F J.

110), cadmium salts, azaindene compounds, etc. American clock No. 3 tij, t
ij issue, same: I, tij, 64! / issue, same 3, bu/7.
Jri No. 1, 3. The combination described in tJJ, No. 7, No. 1 is particularly useful as an IC.

The above sensitizing dye contains j x 10-7 per mole of silver halide.
Mol-1xl0'% Le, good! Let'! /X 0 mol to jX10-λ mol, particularly preferably
0-5 mole ~ zxio-” Silver halide copy A¥L in the portrait of mole, owned by the government.

The above-mentioned sensitizing dye 11, direct emulsion! − can be dispersed to In addition, these are commonly understood as f'f suitable mediums such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, viridis/or a mixture thereof, and are added to the emulsion in the form of a bath solution. In addition, you can also use Hi-wave in a casual manner. Further, as a method of adding the sensitizing dye, US Patent No. 3. ≠
≦2. A method in which a dye is dissolved in a volatile organic solvent, the solution is dispersed in an R aqueous colloid, and this dispersion is added to an emulsion, as described in Japanese Patent Publication Sho Glow-Airs No. A method of dispersing a water-insoluble dye in a water-soluble solvent without bathing, and applying this dispersion to an emulsion, as described in Japanese Patent Publication No. 7, No. 4/-17, A method of mechanically crushing and dispersing an X-insoluble dye in an aqueous bath medium and adding this fraction to an emulsion; US Pat. No. 3. l here, 13! As stated in the specification,
A method of dissolving a dye in a surfactant and adding the solution to an emulsion; JP-A-Sho! /-7≠A method of dissolving a red-shifting compound and adding the solution to an emulsion as described in No. 4; JP-A-Sho! A method such as that described in No. 0-rotJt is used, in which a dye is dissolved in an acid substantially free of water, and the solution is added to an emulsion. Other additions to emulsions include U.S. special rod No. 2. Rikoko, 3rd edition, 3rd edition, 3rd edition
゜3 Reference 2. Top issue, No. 2.2, No. 217, No. 3. ≠λ, the method described in No. 131 can also be used.

Furthermore, the above-mentioned sensitizing dye may be uniformly dispersed in the silver halide emulsion (before being coated on a suitable support), but of course it may not be dispersed in any step of 111a of the silver halide emulsion. can.

The above-mentioned sensitizing dyes can be used in combination with other sensitizing dyes. For example, U.S. Patent No. 3°703.377
No., same No. A, try, set No., same No. J, Jri 7,06
No. 0, No. J, t/r, t3j, No. J, 4λt, No. 1, British LjA Special No. 1, No. η-, No. zrr, No. 1.
Rich 3. No. t62, special public Akihiro 3-4I 3-Otsu, Yotsusan Piichi/San 030, same≠3-10773, American watch 3.
Reference lt, P core issue, special public show V3-≠230, US clock issue, t, tz, tti issue, same number 3.61! , 1a3-
No. 3. t/7. Kota! No. 3.63, 7λ
A sensitizing dye used in bookkeeping can be used for No. 1 and the like.

In order to rapidly process the silver halide photosensitive material, it is preferable that the swelling percentage of the silver halide photosensitive material is 200H or less.

However, if the swelling percentage is too low, the speed of development, fixing, washing, etc. will be reduced, so it is not preferable to lower it more than necessary.

The preferred swelling percentage is 200% or less and 30% or more,
Especially /10% or less! 04 or higher is preferable.

A person skilled in the art can easily control the swelling percentage to 200% or less by, for example, increasing the amount of hardening agent used in the photosensitive material.

Percent swelling was determined by (a) incubation of the photographic material at Jf'C% 30% relative humidity for 3 days.

(c) the photographic material was immersed in distilled water for 3 minutes, and (d)
) It can be determined by measuring the percentage change in the thickness of the layer compared to the thickness of the hydrophilic colloid layer measured in step (b).

Examples of hard NX agents that can be used in the present invention include aldehyde compounds, US Clock No. 1.2ft, 77! Compounds containing active halogens described in US Patent No. FF No. 1.6
! ! , No. 7/r, etc. Compounds having reactive ethylenically unsaturated groups, US% FF No. 1. OF/, 13
Organic compounds such as epoxy compounds described in No. 7 and halogenocarboxaldehydes such as mucochloric acid are known. Among these, vinyl sulfone hardeners are preferred. Furthermore, polymer hardeners can also be preferably used.

The polymer hardener is preferably a polymer having an active vinyl group or a group that is a precursor thereof, and among them, JP-A-Sho! Bu-l gukko! A long line like the one described in Kohiro is -
Particularly preferred are polymers in which an active vinyl group, or a group serving as a precursor thereof, is bonded to the polymer main chain by a surfactant. The amount of these hardeners added to achieve the above swelling percentage depends on the type of hardener used and the gelatin/gelatin content.
Varies depending on species.

In the rapid processing of the present invention, it is preferred to contain organic substances in the emulsion layer and/or other hydrophilic colloid layers that will flow out at 0.degree. C. during the storage processing step. When the substance flowing out is gelatin, it is preferable to use a gelatin species that does not involve the crosslinking reaction of gelatin by a hardening agent, such as acetylated gelatin or heptadated gelatin, and preferably has a small molecular weight. On the other hand, as a polymer substance other than gelatin, U.S. Clock No. 3.271°111
Hydrophilic polymers such as polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, etc., as described in No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 2, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, and No. 1, No. 1, No. 1, No. 1, 2, 2, 2, 3, 4, 5, 6, and 1, 1, 2, 3, 3, 3, 3, 2, saccharides, and saccharides such as polyacrylamide, polyvinyl alcohol, and polyvinylpyrrolidone, hydrophilic polymers such as polyvinyl alcohol and polyvinylpyrrolidone can be effectively used. Among these, polyacrylamide and dextran are preferred, and polyacrylamide is a particularly preferred substance.

The average molecule m of these substances is good! L<i is preferably 10,000 or less, more preferably 10,000 or less. In addition to this, Re5earc
h Discl osure 帛 / 74 volumes, /16/
Anti-fogging agents and stabilizers listed in Section 3, Section 7 (February 1977 issue, 1997 issue) may be used.

U.S. Patent No. ≠ for the development processing method of the present invention, Koko Hiroshi.

4AO/issue, same number u, ttr,? No. 77, same No. ≠.

/44.7 No. Ko, No. 31/, No. 71, No. Da, No. 7, ≦ot, No. Da, - Ko/, rj No. 7, No. ≠, λhiro 3, Ultra-high contrast and high sensitivity photographic properties can be obtained using the hydrazine fermentation conductor described in No. 732 etc.)) It can be applied to image forming processing of silver halide sensitive source materials.

Next, examples of the present invention in the form of pots will be shown, but the present invention is not limited thereto.

Example 1 Preparation of emulsion Gelatin io9 and bromide power IJA 9 were added to 1 liter of water, and a silver nitrate aqueous solution (
An aqueous potassium bromide solution containing 1 g of silver nitrate) and iodizing power IJO,/j9 was added over 1 minute using a double jet method. More salt #! Silver aqueous solution (turf as silver nitrate)
A potassium bromide aqueous solution containing Kalig iodide and λI was added by a double jet method. The addition flow rate at this time was accelerated by current flow so that the flow rate at the end of addition 7X was five times that at the start of addition.

After the addition was completed, soluble salts were removed by Jjr'Crc by the sedimentation method, the temperature was raised to ≠00C, gelatin 7!9 was added, and p? lt/4.7Kg! 41! did. The obtained emulsion has a projected area diameter of 0.2 tμ, an average thickness a, /It
In the μ-book tabular grains, silver iodide 11 was present at 3 moles. This emulsion was chemically sensitized using gold and sulfur sensitization.

Preparation of photographic material Ioi As a surface protective layer, in addition to gelatin,
Polyacrylamide, polystyrene sulfonate, polymethyl methacrylate fine particles (average particle size 3)
．． 0 μm), polyethylene oxide, a 70-3 molar methanol solution of the compound of the present invention (see Table 1) 00w1
An aqueous gelatin solution containing /1 mol Ag and a hardening agent was used.

As a sensitizing dye in the above emulsion, anhydrogen a-r, t'-dichloro-? - Ethyl-3.3'-di(3-sul-7opropyl)oxacarbocyanine hydroxide sodium salt at a ratio of lOO■/1 mole Ag, and potassium iodide
It was added at a ratio of 0/1 mole Ag. Furthermore, as a stabilizer ≠-hydroxy-4-methyl-/ lj # J a
* With addition of 7-titrazaindene, t-bis(hydroxyamino)-p-diethylamino-/, J, j-triazine and nitrone, trimethylolpronone as a drying anti-capri agent, -fabric aid and hardening agent. A photographic material was prepared by applying a coating solution to both sides of a polyethylene terephthalate support simultaneously with a surface protective layer and drying. Coating silver IH one side of this photographic material 7
．． It is 2. The swelling ratio according to the above definition was 120%. .

This photosensitive material was exposed to X-rays, and the T-gradient image fixing solution and
Developed using a water washing solution.

Developer solution> Potassium hydroxide, sodium sulfite, potassium diethylenetriamine, 5f! >Acid boric acid kohiro I μoy og λ, suog hydroquinone izg diethylene glycol ii, 11 μm hydroxymethyl-p-methyl-/-phenyl-3-biglidone 3.3I! −
Methylbenzotriazole tO potassium bromide CoI Make up to /l with water (
phi o, roKli4).

Fixer> Ammonium thioEIL/4109
Sodium sulfite /Ill ethylenediaminetetraacetic acid, dithorium, dihydrate Ko! (Adjust the pH to 0 with acetic acid.) <Stabilizing liquid> (Also used for squeeze roller cleaning layer) Ethylene thiabanetetraacetic acid ditrilam salt. Dihydrate salt (antifungal agent) 0. Processed in seconds using rll/1 automatic scratch machine Dry to Dry.

Developing tank 7.3! iz'cxtt, z seconds (opposed roller) fixing tank 7
．． ! ! zz”cxtJ, z seconds (opposed A-Learn stabilization tank
6j 20°C
J drying (jO'c) described in No. 217
/! Total processing time in seconds
! ! However, although a heater was used to maintain the temperature of both the developing and fixing tanks, cooling water was not used.

When the photosensitive material is being processed, the amount of circulating and stirring developer is set to λoty, and when the photosensitive material is on standby before being processed, the amount is set to 417.
It was set to minutes.

The transmitted optical density of the non-image area was measured and expressed using residual green light after processing.

The results are shown below.

Table 1 It can be seen that the sensitive materials to which the compounds of the present invention were added had little residual color after processing.

Example 2 In the same manner as in Example 1, a sensitive material with a swelling ratio of 0 was prepared and processed with the following developer solution.

The automatic developing machine and the time of each step were the same as in Example 1.

<Developer concentrate formulation> ar for zrl
t A Part B Part C Starter [Glacial acetic acid core 09 Developer solution preparation method] Put water λ04 into a replenisher stock tank of about 101, then add and dissolve the above Part A, Part B% Part C sequentially with stirring, and finally add water. So 31! This was used as a developer replenisher (pl-1/a, !0).

After first filling the EiA image processing tank of an automatic developing unit with the developer replenisher solution/l and adding the above-mentioned starter solution at a ratio of 0d (pH 10,/j), the photosensitive material is processed. The developer replenisher was replenished at a cost of $717/1 sheet (/7 inch x/1 inch) each time.

<Fixer concentrate formulation> Part A III Par
tB <Fixer Preparation Method> Pour 01 water into a replenisher stock tank of about 100 ml, then add and dissolve the above) 'artA%PartB' while stirring, and finally make 311 with water and replenish the fixer. It was made into a liquid.

The same fixer replenisher was first filled into the fixer tank of the self-pulling machine (see pH!).

Thereafter, each time a photosensitive material is processed, add 60% of the above fixer replenisher.
d/1 piece cut into quarters (10 inch x 1 inch) was replenished.

The results of measuring the transmitted optical 11 degrees of the non-image area using green light, which remains a color after processing, are shown below.

Table 3 It can be seen that the residual color after processing of the photosensitive materials added with the compound of the present invention is reduced.

Example 3 A sensitive material was prepared by adding the same amount of various compounds of the present invention to an emulsion in the same manner as in Implementation Project 1, and exposed to X-rays. , and developed using a water washing solution formulation.

The results of measuring the transmitted optical density of the non-image area using green light, which remains a color after processing, are shown below.

It can be seen that the sensitive material containing the compound of the present invention has less residual color after processing.

Example 4 (1) Preparation of silver halide emulsion (i) Preparation of tabular silver halide emulsion (A) (aspect ratio 13) The following types of solutions were prepared, and a tabular silver halide emulsion was prepared. was prepared.

B KSCN (2N) cc To solution A stirred at 75°C, a solution and H were added by a double jet method. Thereafter, solutions E and I were added using the same double jet method over 28 minutes.

Solution B was then added. Then, at the start of addition of solution F, 0
．． The addition rate was gradually increased from 96 cc/min and the addition took 60 minutes. Solution C was then added, followed by solutions G and K by double jet method.

After the addition was completed, desalting was carried out by a conventional method. After that, chemical sensitization was carried out by a gold/sulfur sensitization method using chloroauric acid and sodium thiosulfate, and silver bromide emulsion A with photosensitive properties (outside high
A triple-structured particle distribution) was obtained. Sensitizing dye 1 was added before chemical sensitization.

Sensitizing dye-1 *The amount added is shown in Table-4.

(ii) Preparation of silver halide emulsion (B) (aspect ratio 2.7) Potassium bromide, potassium iodide, and silver nitrate were added to an aqueous gelatin solution with vigorous stirring to form a thick plate-like iodine with an average grain size of 1 μm. Silver oxide (average iodine content 6 mol%) was prepared. Thereafter, it was washed with water by a conventional precipitation method, and then chemically sensitized by a gold/sulfur sensitization method using chloroauric acid and sodium thiosulfate to obtain a photosensitive silver iodobromide emulsion B. Aggravating dye-1 is added before chemical sensitization! 4.8X10-
'mol/Ag mole).

(2) Preparation of coated samples Samples 8 to 21 were prepared by sequentially providing each layer of the following formulation on a triacetyl cellulose support from the support side.

(Bottom layer) Binder: Gelatin 1 g/n1 Dye elution accelerator: Listed in Table 5 0, 16 g/rd Dye: (CHx) tsOsK (CHz)*5OJ 10-4 mol/d (C1h) tsoK ( CHx) tsOsK 10-4 mol/d (middle layer) Binder: Gelatin 0. 4 g/rd Coating aid Coating aid: Sl p-styrene sulfonic acid potassium salt 8 ■/d (Emulsion layer-1) Coating silver amount: (Emulsion B) 1.3 g/nf
Binder: Gelatin 1.9g/n (Dextran (MW approx. 150, Goo) 0.'Ig/rd Additive: C+
,H! sO") CHtCHtO+ zJ5, 8*/Ag
1 g Coating aid: Poly p-styrene sulfonic acid potassium salt
0.2■/d (Emulsion layer-2) Coated silver amount: Emulsion (listed in Table-4) 4.2g/n (Binder: Gelatin 7.8g/rd dextran (MW approx. 150.000) 1.5g/n rlr additive: C+
5H3sO+CHOChO÷meaning. H5,8■/Ag1g Trimethylolpropane 400■/rrr Coating aid: Poly p-styrene sulfonic acid potassium salt
0.7■/n ((Surface protective layer) Binder: Gelatin 0.7g/rd Coating aid: Antistatic agent: C5FtySOtNCHxCOOKcs
l'1. r 2■/d Hard 111g: 1.2-bis(vinylsulfonylacetamido)ethane 2,3 X 10-' mol/nr Matting agent: Polymethyl methacrylate fine particles (average particle size 3μ) 0.13■/n? (3) Sensitometry These samples were stored at 25° C. and 65% RH for 7 days after coating. Each sample was exposed to 400 lux tungsten light for 1/10 second through an optical wedge and then processed as follows.

(a) Automatic developing machine Developing HPD developing machine (manufactured by Fuji Photo Film Co., Ltd.) is installed in Persamat 5AN automatic developing machine manufactured by Kodak, USA.26.
Development processing was performed at 5° C. and 4 ft/min.

However, the fix liquid used was Super Fuji Fix (manufactured by Fuji Photo Film ■).

(b) Measurement of sensitivity The sensitivity value was determined as the common logarithm of the reciprocal of the exposure amount required to obtain a transmission blackening density of Capri+0.1.

(c) Evaluation of residual color The sample is processed according to the method of (a) (without exposure), and the amount of sensitizing dye (residual color) is visually evaluated.

○: Good Δ: Slightly bad (but within the practical range) ×: Bad (outside the practical range) Table 4 Sample 9.10.12.13.1 using the compound of the present invention
Table 5 shows that samples Nos. 5 to 21 can improve residual color without reducing sensitivity.

However, in Sample 9.10, which contains a small amount of sensitizing dye, the residual color of Comparative Example 8 was not so bad to begin with, so the effect was small.

Claims (1)

[Scope of Claims] At least one silver halide emulsion layer is provided on a support, and at least one compound represented by the following general formula (I) is contained in the emulsion layer or other hydrophilic colloid layer. A silver halide photosensitive material characterized by containing: General Formula (I) A-B In the formula, A represents a blocking group capable of releasing a dye elution promoter upon treatment, and B represents a dye elution promoter bonded to A via a heteroatom.