JPH01546A - Image forming method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to an image forming method with improved image sharpness and/or graininess without impairing storage stability.

(Prior Art) Generally, the image quality of silver halide photographic materials is determined by sharpness and graininess.

The image sharpness of photographic light-sensitive materials deteriorates due to scattering and refraction of light in the silver nologenide emulsion layer, reflection at interfaces, etc., and in particular, the thickness of the light-sensitive layer deteriorates to a greater degree. In particular, in color photosensitive materials, in order to separate and record the three primary colors of light (red-sensitive/i, green-sensitive layer, and blue-sensitive layer), the emulsion layer is divided into at least three sections and coated in layers, and the thickness of the recording material is The taste ends up being too thick. For this reason, the lowest 1+
The deterioration of sharpness in the emulsion layer of llt is remarkable.

A number of methods are known to improve this deteriorated image sharpness. In order to reduce the effect of the scattered light, a method is known in which dye is added to absorb the scattering. This method fails with a decrease in sensitivity because it also absorbs light that is originally necessary.

Especially for color photographic materials, so-called DI
A method using a l(- coupler is known.

This is a technology in which a development inhibitor^1) is released from a coupler as a color image is formed during color development of a color photosensitive material, and the difference in concentration of the development inhibitor produces an edge effect to improve sharpness. This method is applicable to color photosensitive materials such as color negatives and color papers because it is effective only during color development, but it is applicable to color reversal photosensitive materials where the main effect of image formation is determined by black and white development. It cannot be expected to be used for black and white photosensitive materials that do not require color development.

Dr rt-hydroquinone, which releases a development inhibitor during development, is known as a technology that utilizes the edge effect during development and can be applied to many color photosensitive materials and especially black and white photosensitive materials without color development processing. There is (US-
i3g Hiro022, US-337 Rij Kota, Tokukai Akira! 0-
jko4t3j, tokukaisho! 10-/33133, Tokukai Akira!
/-j/Y'l/, JP-A-60-//963/, JP-A-Sho! λ-yo71-B. DTt-L-hydroquinone is color 8I! Since it works not only on images but also on black-and-white developers, it can be applied to a wide range of silver halide photosensitive materials.

However, the present inventors found that when L) Tlt--hydroquinone is mixed and coated with the conventionally used emulsion, it decomposes with the passage of time after preparing the liquid solution, causing a harmful effect. 9! If you try to use the photosensitive material you created after storing it for a long time, you will have problems with increased fog and decreased sensitivity.9! , VCl It has been found that this problem has a severe effect on images in photosensitive materials subjected to processing including a black and white development process.

10,000, JP-A-13-20321fiVcu, a scavenger of the oxidized form of the developer or a compound which releases an Ery8iii image suppressor upon reaction with the oxidized form is added to a non-photosensitive l#li layer adjacent to the silver halide emulsion layer. It has been described that a color image forming method in which a photosensitive material added to a photosensitive material is developed using a specific aromatic primary 7-ban developer can improve color fog and color mixture and provide high image density and sensitivity. However, the above-mentioned storage stability is not mentioned at all.

(Objective of the Invention) An object of the present invention is to provide an image forming method with excellent sharpness and/or graininess without deteriorating storage stability.

(Components of the Invention) The object of the present invention is to provide on a support at least one silver halide photosensitive layer and at least one hydrophilic colloid layer that does not substantially contain silver halide,
Image formation characterized by subjecting a silver halide photographic light-sensitive material containing a small amount of the compound represented by (also /fi) in the photographic layer substantially free of silver halide to a process including a black-and-white development step. Method.

General formula ([I A-(Time) t-X The formula chunin means redox mother machine, +T 1 m e + (X
represents all the atomic groups that make it possible for Ti to leave
me is a sulfur element, a nitrogen atom, an oxygen atom or a selenium atom, which is a timing group linked to a human, t is an integer of 01 and 1, and X means a development inhibitor.

The processing including a black-and-white development process in the present invention refers to a black-and-white development process in which the silver image itself is used as an image in the black-and-white development process, or a color reversal process in which an EL dye image is formed in a so-called color development after the black-and-white development process. Further, in the present invention, the term "substantially free of silver halide" means that the amount of coated silver is approximately 0./l/1rL2 or less.

The compound of formula (1) used in the present invention will be explained below.

First, A in general formula (1) will be explained in more detail. A
′″r: The redox nucleus shown is, for example, hydroquinone, catechol, p-aminophenol%0-aminephenol%/, 2-su2talediol, l, ≠
- Naphthalene diol %/.

6-s7talediol, /, J-aminonaphthol,
/, teraminonaphthol or 1. Examples include t-aminonaphthol. At this time, the amino group is preferably substituted with a sulfonyl group having l-carbon atoms or an acyl group having carbon atoms/-Jj. As a sulfonyl group, [
Examples include substituted or unsubstituted aliphatic sulfonyl groups and aromatic sulfonyl groups. Also, the acyl group may be substituted or unsubstituted! T! lI! The hydroxyl group or I7 group forming the redox nucleus of A, which may be an aliphatic acyl group or an aromatic acyl group, may be protected with a protective group that can be removed during development. An example of a protective group is 1-2 carbon atoms! For example, an acyl group, an alkoxycarbonyl group, a carbamoyl group, and JP-A-Sho-J et al. 7037, JP-A-Sho! Examples include the protecting groups described in Ter. 2010!7. Furthermore, this protecting group is bonded to the A(2) substituent described below, and! ,
A 6- or 7-membered ring may be formed.

The redox nucleus represented by A may be substituted with an appropriate substituent at an appropriate position. Examples of these rjIt substituents include 2 carbon atoms! The following examples include alkyl groups,
Aryl group, alkylthio group, arylthio group, alkoxy group, aryloxy group, amine group, amide group, sulfonamide group, alkoxycarbonyl group, vano group, ureido group, carbamoyl group, alkoxycarbonyl group, sulfamoyl group, sulfonyl group, cyano group, a halogen atom, an acyl group, a carboxyl group, a sulfo group, a nitro group, a heterocyclic residue, or +Time±X. These Il groups may be further substituted with the above-mentioned substituents. In addition, these substituents are
They may be bonded to each other to form a saturated or unsaturated carbon ring or a saturated or unsaturated heta@.

Preferred examples of A include hydroquinone, catechol, p-aminophenol, 0-aminophenol, /,
! -Naphthalenediol, /, Hiro-aminonaphthol, etc. can be used. More preferred A is hydroquinone, catechol, p-aminophenol, and 0-aminophenol, and most preferred A is hydroquinone.

An example of a person's preferred appearance in general formula (1) is shown below. Note that +Time+tX is bonded to each structural formula (with a break in the middle).

(ko) H H H 0su (j) H H H H H H O)i (lkot (l hron) (/ri (/6) H H H (20λ * (λkoJ H H H (-Time + tX is It is a group that is released as +Time+X only when the redox mother nucleus represented by A in general formula (1) undergoes a cross-oxidation reaction during development and becomes an oxidized product.

Time is a sulfur atom, nitrogen atom, oxygen atom, or selenium atom, and is a timing group that connects A, and is a group that is released to X after one step or more reaction steps from θ+Time+X released during development. can give. As for Time, for example, U.S. patent 弗μ,
λdat, ri No. 42, same number hiro, hiro 0ri.

3 Co. 3, British Patent No. 713, U.S. Patent No. 44. /4! J, jPg issue, published Show No. j/-tut,
Examples include those described in No. r, No. 2r, Publication Showa $Sj7 No. 16.137, etc. The time may be a combination of two or more selected from those listed in %h.

X means a development inhibitor. Examples of development inhibitors include:
Examples include compounds having a mercapto group bonded to a heterocycle or heterocyclic compounds capable of producing iminosilver. Examples of compounds with a mercapto group bonded to a heterocycle are 11. For example, ht or unsubstituted mercaptoazole mtp+t is l-phenyl-yo-mercaptotetrazole, l-broby-j-mercaptotetrazole, l
-Butyl-! -Mercaptotetrazonyl, 2-methylthio-! -Mercapto/,! , 4L-guadiazole, 3-methyl-phenyl-ohmercapto-1,λ
, dartriazole, /-((I-ethylcarbamoylphenyl)-komelkabutoimitasole, komelkabutobenzoxazole, komelkabutobenzimidazole, λ-mercazotohenzotheazole, λ-phenyl!-mercap) -/, 3. II-Oxadiazole, /-(3-(J-methylureido)phenyl)-! −
Mercaptotetrazole, l-(≠-nitrophenyl)
-! -mercaptotetrasol, j-(2-ethylhexanoylabanofucomercabutobenzimidazole, etc.), substituted or unsubstituted mercaptoasaignens (e.g., 6-methyl-≠-mercapto/, 3,3
a, 7-tetrazaindene, ≠, 6-dimethyl-comelkabuto/, 3.3a, 7-tetrazaindene, etc.)
, substituted or unsubstituted mercaptobi IJ midines (
Examples include Komelkabutovirimidine, Komelkabutohiro-methyl-6-hydroxyvirigodine, etc.).

Examples of peterocyclic compounds capable of forming imino'@ include substituted or unsubstituted triazoles (for example, %'l
Co, 4A-+-riazole, benzotriazole,! −
Methylbenzotriazole! - Nitropenzotriazole,! -Bromobenzotriazole, yo-n-butylbenzotriazole! , t-dimethylbenzotriazole, etc.), substituted or unsubstituted indazoles (e.g. intasole, !-nitrointasole, 3-nitroindazole, 3-chloro-yo-nitroindazole, etc.), substituted or unsubstituted Benzimidazoles (
For example, Nitrobenzimidazole! , 4-dichlorobenzimidazole, etc.).

In addition, X separates from the general formula (1) Time and once becomes a compound that has development inhibiting properties, and furthermore, it causes a chemical reaction with the developer component to substantially no longer have development inhibiting properties. Alternatively, it may change to a significantly reduced compound. Examples of 'B functional groups that undergo such chemical reactions include ester groups, carbonyl groups,
Examples include an imino group, an immonium group, a microadduct acceptor group, and an imide group. Examples of such deactivated development inhibitors include /-(J-phenoki7carponylphenyl)-yo-mercaptotetrazole, /
-(4C-phenoxy7carbonylphenylene-yo-mercaptotetrazole, /-(J-maleinimidophenyl)-!-mercaptotetrazole, j-phenoxy7carbonylbenzotriazole, yo-(≠-cyanophenoxycarbonyl)benzotriazole, -monophenoxycarponylmethylthio-j-mercapto-1,3,≠-
Thiadiazole, j-nitro-3-phenoxycarbonylimidazole, t-(2,3-dichloropropyloxycarbonyl)benzotriazole, / -(benzoylokylephenyl-!-mercaptotetrazole, 1-(comethanesulfonyl) Ethoxycarbonyl J-
λ-mercaptobenzothiazole, j-cinnamoylaminobenzotriazole-/-(J-vinylcarbonylphenyl)-yo-mercaptotetrasol,! -succinimidomethylbenzotriazole, co(≠-succinimidophenyl)-j-mercap)-/, J, II-
Examples thereof include oxadiazole, bu-phenoki7carbonyl-comelkabutobenzoxazole, and the like.

In order to more clearly explain the content of the present invention, specific examples of the compound represented by the general formula (I) are shown below, but the compounds that can be used in the present invention are not limited to these.

(1-/) (I-con (I-J) (I-≠) (1-j) C3H7 (I-7) H (l-ta) H (1-/　/　) H (1-/J) H (I-/ reference) nC3)t7 (I-/4) OH (I-/7) OH c3H7 (1-/f) (1-/ri] (l-koo) OH (1-,2/J (l-23) clear ci4. .

(1-, z4A) OH (I-kot) (I-J(7) (I-323 2H5 (I-3≠) (1-JjJ c3H7 (1-Jr) CH3 (l-≠O) (I -Hiro1) (■-Hiro, 2) (I-133 (I-Hiro4t) (I-Hiroyo) (I-≠t) (l-≠7) H (l-μr) (1-j4' ) (I-jj) H3 (I-j7) (1-sr) Q)i <I-jri) (I-40) OH (I-Otl) General formula (The compound represented by H is generally It can be synthesized in the following two ways. First, Time is a simple bond (i-
aQ), %' means chloroform or 1. Benzoquinone, orthoquinone, quinone monoimine, quinone diimine in λ-dichloroethane, carbon tetrachloride, tetrahydrofuran without catalyst or in the presence of an acid catalyst such as Itsp-toluenesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, methanesulfonic acid, etc. This is a method in which a derivative and a development inhibitor are reacted at a temperature between room temperature and 10Q0C. The second is substituted with chlorine, bromine or iodine in the presence of a base such as potassium carbonate, sodium bicarbonate, sodium hydride or triethylamine in an aprotic polar solvent such as acetone, tetrahydro7rane or dimethylformamide. benzoquinone, orthoquinone, quinone monoimine, quinone diimine derivative and development inhibitor -J
This is a method in which a quinone compound obtained by a reaction between 0°C and 100'C is reduced with a reducing agent such as diethylhydroxylamine or sodium hydrosulfide. [
References: Re5earchDisclosure
/ 1227 (/ri7ri): Liebige An
n, Chem, 74p, /3/(/P7con) Then the type (t=/
) can also be synthesized in almost the same way as above. In other words, instead of the above development inhibitor (X), ']"ime-
or XVceIL exchangeable groups (e.g. halogen atoms, hydroxyl, or precursors thereof)
After first introducing Time having
This is a method of linking X through a substitution reaction.

The amount of the compound represented by general formula (1) of the present invention is:
Color reversal photosensitive material - 10 mol/m to 10'E: to/
n&2, preferably from 10 mol/m to 10-'
In black-and-white negative light-sensitive materials and X-ray light-sensitive materials, it is 10-7 mol per mol of silver.
mol, preferably from to-6 mol to 10-2 mol, more preferably from 1x10 mol! The range is ×10 moles.

The compounds represented by the general formula of the present invention may be used alone or in combination of two or more.

The compound represented by the general formula can be added as an emulsion obtained by dissolving in a high-boiling oil and stirring at high speed, or dissolved in a water-based organic solvent such as alcohol or cellosolve and finely dispersed in a gelatin solution by stirring. It may also be added.

Furthermore, Tokuko Shoj/-32! ! No. 3 workman j-1-3!
The dispersion method using a polymer latex described in the Koda issue may also be used.

Examples of high-boiling organic bath agents suitable for dissolving DrEt--hydroquinone used in the photographic material of the present invention include phthalic acid esters (dibutyl phthalate, dicyclohexyl 7-talate, di-ethylhexyl 7-talate, phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-λ-ethylhexyl phosphate, tridotesyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, sheath-ethylhexylphenyl phosphonate (tx), benzoic acid esters (λ-
Ethylhexylbenzoate, dotesylbenzoate,
Coethyl hequinyl p-hydroxybenzoate), amides (diethyldodecanamide, hetetradecyl pyrrolidone, etc.), alcohols and phenols (isostearyl alcohol, λ, 4C-diter)
t-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-dibutylucoptoxy-j-tcrt- Examples include octylaniline, hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), etc.As the auxiliary solvent, the boiling point is about 300C or higher, preferably !06C.
An organic Fj agent having a temperature of about 1 to 0°C or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ether ketone, cyclohexanone, coethyl acetate, and dimethyl formamide.

) Phosphate esters such as ethylhexyl phosphate and tridodecyl phosphate, and amides such as ethyldodecane oxide are particularly preferred.

The amount of oil to be used is 0 to 20 times, preferably l/j-10 times, in terms of X product ratio, relative to DIR-hydroquinone.

The hydrophilic colloid layer adjacent to the silver halide emulsion layer of the present invention that does not substantially contain silver halide is, for example, a layer containing gelatin or a hydrophilic polymer as a binder, such as a coupler, a color mixing inhibitor, or a fading prevention agent. It may contain emulsions such as agents, and may also contain various chemicals such as dyes, development inhibitors, stabilizers, development accelerators, p)i regulators, film quality improvers, etc. It's very difficult. Further, it can be provided on any tablet in the sensitive material emulsion layer.

Next, the processing including the black and white development process used in the present invention will be explained.

The black-and-white development process is a process that reduces silver halide particles that have formed a latent image due to exposure to light to form a silver image.
This differs from the formation of an EL dye image by coupling a phenylenediamine rust conductor with an oxidized coupler, as used in so-called force-2 development.

The black-and-white development process used in image formation of the present invention contains at least one developer represented by the following general formula (II) and/or general formula (Ill). These developing agents may be salts of inorganic acids or organic acids. In the general formula (n), R1 to R4 may be the same or different,
Hydrogen atom, aliphatic group, aromatic group,...rogen atom, hydroxyl group, sulfo group or salt thereof, chloride. However, when X' is a hydrogen atom, R1 or R4 and R5, R may be the same or different (represents a hydrogen atom, an aliphatic group, an aromatic group, an acyl group, or a sulfonyl group. R
6 may have a substituent or form a ring if possible.

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

The aliphatic group represented by R1 to R has a carbon number of 1 to /J.
Examples include an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group. Examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, or 7-chlorohexyl group. As an alkenyl group, an allyl group,
Examples include butenyl group. Examples of the alkynyl group include proA/I/gyl group and pentynyl group. Examples of the aralkyl group include a benzyl group, l.

Examples include l-dimethylbenzyl group and 7-enethyl group.

The aromatic group of R1 to R4 has a carbon number of 2 to 1
Examples of these include phenyl group, p-tolyl group, and cafthyl group.

The halogen atoms of R1 to R4 include chlorine, bromine,
Such as fluorine or iodine.

For R5 to R6 aliphatic groups and aromatic i groups, R1
Or the one mentioned in R4 can be mentioned.

The acyl group of R5 to R6 has 1 to 1 carbon atoms.
0, such as an acetyl group or a benzoyl group.

R57'! :I L; As the sulfonyl group of R, the number of carbon atoms is t.
to 1O, such as a methanesulfonyl group, a benzenesulfonyl group, or a toluenesulfonyl group.

As substituents for X' and R1 to R6, R1 and R
In addition to those mentioned above, examples include a cyano group, an alkoxy group, an aryloxy group, a carbamoyl group, an alkylthio group, and an arylthio group.

X'E1. HR1 (9 When forming a ring in R6, each alone or R1 and R2, FL2 and X'%X
' and R3 or I (3 and R4 combine to form a ring- or r-membered carbocyclic ring or a ring containing oxygen or nitrogen).

Preferably, R1 to R4 are a hydrogen atom, an alkyl group, an aryl group, a rogen atom, a hydroxyl group, or a sulfo group (or a salt thereof), and more preferably a hydrogen atom, an alkyl group, a halogen atom, or a sulfo group ( or its salt)
and most preferably a hydrogen atom or a sulfo group (or a salt thereof).

K' is preferably a hydroxyl group or group, -N)t
2, -N)IC)t3 or -NHC2H5,
Most preferred is a hydroxyl group or -N)IC)i3.

Examples of media for general formula (11) are shown below, but are not limited to these.

(II-/) (1-ko) (n-j
) (n-4') (n-j)
(II-4)Ql-10)t (II-7) (n-4)(■-y
) (II-tO)0)i
0)t(1-//)
(II-/2)0)i
0H (■-13) (
■-1 Hiron OH0H (1-tz) (II-/&)0)
t 0H (1-77)
(u-II) (■-7ri)
(■--〇) (■-kot)
(II-22) (■-23) (II
-λ1) (1-2z) (11-26
) (11-, 27) (II--24
') (I-2ri) (■-30) (u-
3/ ) (u-J-2) (If-7
3) + 1-34') (If-j
j) (It-34) (n-373
(If-3r) (■-32) (■-≠〇) General formula (1
) In the formula, R21 is an aryl group, 1 (22 to R25 may be the same or different, and R21 to R25 representing a hydrogen atom, an aliphatic group, or an aromatic group may have a substituent, The general formula (I) which may form Vc will be explained in more detail.

The aryl group for R21 has a to io carbon atoms, such as a phenyl group, a naphthyl group, and the like.

As the aliphatic group and aromatic group of R22 to R25,
aliphatic group of the general formula (Ntt'' and aromatic@7c, respectively)
The following can be cited as a basis.

((21 to R25 as the tM samurai group, general formula +1
) as the i1 substituent of R1.

In addition, R21 to [(25) may be used alone or with R22 and R23, or R22
R21 is preferably a phenyl group, -tolyl group, m-)lyl group or p-methoxyphenyl group, more preferably phenyl group, p-tolyl group or m-tolyl group, Nt
Also preferably a phenyl group.

R22 and R are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom, a methyl group, or a hydroxymethyl group, and most preferably R22 is a methyl group.
or hydroxymethyl group.

R24 and R25 are preferably a water atom or an alkyl group, more preferably a hydrogen atom or a methyl group,
Most preferred is a hydrogen atom.

Good examples of general formula (II) are shown below, but the invention is not limited thereto.

(If-/) (Ill-ko) (I
n-//) ([1-t2)(I[1-
ti) (1-/4') These developers may be used alone or in combination of two or more to produce 8i
It can also be added to the image solution or incorporated into the photosensitive material.

When these developing agents are added to the developer, - general formula (n
) Compound v4 d, 0.3 to 10&/l, preferably o, zg to 60F//l, preferably 0,
r-4109/l, and the compound represented by general formula (Ill) has a range of 0.02 to lo! l/ls like FIo, 0! -19/l, preferably 0.
07! ~Ag/l.

Next, silver halide grains used in the present invention will be described.

The silver halide grains used in the present invention may be any of silver bromide, silver iodide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, and silver chloride. Silver iodobromide is preferred, and silver iodobromide having an iodide content of 0 to 30 sol is particularly preferred.

These silver halide grains may be so-called regular grains having regular crystal shapes such as cubes, octahedrons, and dodecahedrons (and also grains having irregular crystal shapes such as spherical shapes, and flat grains). The particles may have a crystal defect such as a twin plane, or a composite form thereof.Also, a mixture of particles of various crystal forms may be used.

The grain size of these silver halides is about 0. The emulsions may be fine grains with a diameter of tt chron or less or large grains with a projected area diameter of about toi chron, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution.

The silver halide odorant emulsion used in the present invention can be produced by a known method, for example, Research Disclosure, 77
Volume 4, 4/7bu≠7
Page, @1. Emulsion F'repa
The method described in Ralion and Types et al., Vol. 17, /16/17/l (January 1979), +pr can be followed.

The photographic emulsion used in the present invention is published by Graffkide, "Physics and Chemistry of Photography", published by Ball Seven Intel Publishing Co., Ltd. (P.

Glafkides, Chimie et Phy
siquePhotographique Paul
Montel, t47), Duffin, "Photographic Emulsion Chemistry", 7, published by Cal Press (G, F, Duffin)
, he to PhotographicEmulsion
Mistry (Focal Press.

``Production and Coating of Photographic Emulsions'' by Zelikman et al.
, 7 Oichi Cal Press (V, L, Zelikmane
tal, Making and Coating
Photographic Emulsion Fo
calPress, tWAu), etc. In other words, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be one-sided mixing method, simultaneous mixing method, or a combination thereof. It's okay. It is also possible to use a method in which the particles are formed under an excess of particle bride ions (so-called back mixing method). As one form of the simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, the so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Further, tabular grains include, for example, British national license number/, 3J! ,ri2! No., U.S. Pat. No. 47, No. 00, J.
, 610.7j No. 7, Mukai'I$hiro, 2 octopus, visit! issue,
Tokukai Akira! ! -74JJJP issue, same! ! -7tri Koda No. 11-//Jri No. 27, same II-tti Octopus! issue,
Same It-///ri 3rd issue, same 11! -///ri3 can be produced with reference to the method described in No.

Additionally, known silver halide solvents (for example, ammonia, ammonia,
Rodan Kali or US Patent Ka3. core/.

No. 117, JP-A-J/-/Ko-340, JP-A-J 3-1
No. 24401, JP-A No. 13-744 $3/F, JP-A No. 4 cm 1007/7 Moshiku is JP-A No. 74 cm/1l.
Physical ripening can also be carried out in the presence of thioethers and thione compounds described in No.-12r and the like. This method also yields a silver halide emulsion with a regular crystal shape and a nearly uniform grain size distribution.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling pAg and p)i during grain formation. For more information, please see Photographic Science.
and Engineering (Photographic
5science and Engineer in
g) Vol. 1, pp. 132-761
nal ofPhotographic 5cien
ce);
．． Da/J, No. 711r.

A representative example of a monodispersed emulsion is an emulsion in which the average grain diameter is approximately 0.1 micrometer larger than the halogenated steel grains, and at least the thbks of the grains are within 0% of the average grain diameter. Average particle diameter is o, sz-, 2t
It's a clone, and at least it's ri! Social welfare% or (number of particles)
An emulsion having a small number of silver halide grains within a range of average grain diameter ±λθ can be used in the present invention.

This emulsion method is described in U.S. Pat. Nos. 3,57, 62 and 6J! , Jri μ-engineered British Patent No./,
It is described in ≠13.7≠r. Also, Tokukai Sho ttr
-rtoo issue, same j/-jri number 027, direction 17-130
No. 27, No. 13-737/33, Same! ≠−4t♂jJ
No. 1, same j4t-4P4t/ri No. 1, same! lll-374
Monodisperse emulsions such as those described in No. 3j and No. 5r-ayyit can also be preferably used in the present invention.

The crystallization tank 1'# may be of a similar type, or may have a layered structure in which the inside and outside have different halogen compositions. 2
7. /4'B, U.S. Patent No. 3. ! oj, otr issue, 44. $44 Hiro, r77 and patent application Shojt-Koda l≠
It is disclosed in No.

In addition, it can be used even if silver halides of different compositions are bonded during epitaxial bonding.
It may be bonded with a compound other than silver halide, such as lead oxide. These emulsion grains are disclosed in U.S. Pat. ≠
, +rμ issue, 44. /412, P2O issue, 4μ,
Hiro! ? , No. 353, British patent cylinder 2,03! r, 7Pλ
No., US patent tube≠, 3≠? , No. 622, 4μ, 311.
No. 7, same ≠.

≠33. jOI, Dohiro, 11, 3.0?7, 4J
, Ate, No. 962, No. 3,132,067, and Japanese Unexamined Patent Application Publication No. 1983/42j-410.

During the process of silver halide grain formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts are allowed to coexist. Good too.

These various types of emulsions may be of either a surface m-image type, which is formed mainly on the surface, or an internal latent image type, which is formed inside the grains.

To remove soluble silver salts from the emulsion before and after physical ripening, Nudel water washing, flocculation sedimentation method, ultrafiltration method, etc. are used.

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization.

The additives used in this process are based on the research mentioned above.
Disclosure & 176 Hiromu! (December 1971)
The known photographic additives that can be used in the present invention are also listed in the table below. It is described in two Research Disclosures (R, D,), and the locations are shown in the table below.

Additive type RD/74113 RD/, 1'
7/7/ Chemical sensitizers, page 23, 6 hiro, right column, sensitizer, double sensitizer, same as above 3, spectral sensitizer, page 23--μ, page 6, right column, supersensitizer, Otsu≠, right column Hiro Brightener
Page 2j! Antifoggant Pages 2j to Jj 6≠? Right column of page Stabilizer Otsu Light absorber, Fui Pages 2j-26 Otsuhiro? Page right column ~ Luther dye ultraviolet Otsu page 10 left column Line absorber 7 Snine inhibitor Page 11 right column Page 120 left ~ left column t Dye image stabilizer Page 2j? Hardening agent 26 pages left column/Q
Binder Copper page Same as above // Plasticizer, lubricant Core page T, ro page right column 12 Coating aid, surface Pages 26-27 Same as above Activator 13 Static prevention Page 27 Same as above agent Various color couplers are used in the present invention can do. The term "color coupler" as used herein refers to a compound capable of producing a dye by reacting with an oxidized product of an aromatic primary amine developer. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are given in Research Disclosure (RD)/74, Vol.
/month).

It is preferable that the color coupler incorporated in the light-sensitive material is 19 diffusion-resistant because it has a pallast group or is polymerized. A four-equivalent color coupler J:'-9 in which the coupling active position is a hydrogen atom is also preferably a two-equivalent color coupler in which gL is substituted with a leaving group. Couplers in which the coloring dye has an appropriate diffusivity t1°, non-coloring couplers, or DIR couplers that release a development inhibitor during the coupling reaction, couplers that release a development accelerator, and fermentation-reduction reactions with oxidized developing agents. Couplers that release compounds that perform are also conveniently available.

Yellow couplers that can be used in the present invention include:

A typical example is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No.
．． Reference 07.2104+, same number -, r7j, 0/? It is described in No. 7, No. 3.2tz, and No. jot. The use of two-equivalent yellow couplers is preferred for the present invention, as described in U.S. Pat. ≠or, /ri code, same No. J, 44$
7. Pλr No. 3.2JJ, 101 and ≠
, Oko 2゜6ko No. 0, etc., and the trIRIIt atomic detachment type atomic detachment force puller, and Tokkosho 1r-10.
No. 739, 'U.S. Patent No. DA, DA 0/, 712, Hiroshi Mukai, 3λ6.02 Hiroshi, RD/1013 (IP72 μ month), British Patent Department 7. Reference 22.0koO, West German Application Publication No. 2.2/? , No. 9r7, No. 2. λA/, 31s1
No. 4, Part 2.329. ! J No. 7 work same No. 2゜≠33.
Typical examples include the nitrogen atom separation type yellow couplers described in r/co. The .alpha.-piparoylacetanilide coupler has an excellent color fastness, especially light fastness, while the .alpha.-benzoylacetanilide coupler provides a high color development of 111 degrees.

The magenta coupler that can be used in the present invention is preferably an oil-protected type, indacylon type or cyanoacetyl type! - Pyrazoloazole couplers such as pyrazolone and pyrazolotriazoles are mentioned. ! -Pyrazolone couplers are those in which the 3-position is substituted with a γ-arylamino group or an acrulamino group,
It is preferable from the viewpoint of the hue and color density of the coloring dye, and representative examples thereof include U.S. Pat.
iJ, No. 703, No. 2,400.7tr, No. 2
．． No. 901.17J, No. 3. Otko, t' No. 33,
Same No. 3.112.126 Work No. 3゜236.01
It is written in number 1 etc. Two equivalents! - Pyrazolone couplers are preferable because they can provide high color development and high sensitivity with a small amount of coated silver, and the leaving group may be the nitrogen atom leaving group described in US Pat.

3! Particularly preferred are the arylthio groups described in No. 1, No. 197. Also, the ballast group described in European Patent No. 73.436! -Color development # degree r for pyrazolone couplers
It has a enhancing effect. As a pyrazoloazole coupler, US Patent No. 3゜J4? , r? Pyrazolobenzimidazoles as described in US Pat. No. 3,7, preferably US Pat. No. 3,7! , pyrazolo (j, /-c, l
(/.

J, 4C)) lyazoles, pyrazolotetrazoles described in RD Kohiro λkoo (Itt year is month) and pyrazolopyrazoles described in RD Kohiro 230 (/91 year June). I get kicked. European Patent No. 175F, 7! in terms of the low yellow side absorption of the coloring dye and its optical properties. Imidazo L/ as described in / issue.

[lambda]-b] pyrazoles are preferred, as described in European Patent No. 1/9.
Pyrazolo (z, 't-b) [i, z
, Hiroshi] triazoles are particularly favorable.

The uncoupler for I/C use of the present invention includes oil-protected naphthol-based and phenol-based couplers, and is disclosed in US Patent No. λ, ≠7 Hiro.

Naphthol couplers described in 2-layer No. 3, preferably US Pat.

/Hiroj, JP No. 4, @Hiroshi, 2co1.23J Okodo No.≠, 27Otsu, and the oxygen atom-eliminating type naphthol couplers described in No. 200 are representative examples. . Further, specific examples of phenolic couplers are shown in U.S. Pat.
．． Jl, No. 9.927, No. 2. roi, /'yi issue,
Same @λ, 772. /z No. 2, same No. 2. ryz, r2ip
It is written in the issue etc. Humidity and temperature robust cyan couplers are preferably used in the present invention, typical examples of which include the phenolic cyan couplers described in U.S. Pat. No. 3,772.00λ, U.S. Pat.
77λ, /Aλ No. % Same No. 3, 711.

No. 301r, 11! ] No. 41. /26.396, same No. Hiroshi.

3311t, No. 0//, No. 3 Core, No. 173, West German Patent Publication No. J, j2'/, No. 722! ?
- 2, which was written in Hiroshi λ67/issue etc. -Cyafluamino-substituted phenolic coupler U.S. Patent No. 3. Hiro≠
t, No. 622, same No. ≠, 33J, ? P? Phenyl couplers having a phenylureido group kWL at the λ-position and an azilamino group at the first position, etc., are described in No. 7.747, etc. be.

These color couplers can also be used to form two or more superimposed bodies. Typical examples of polymerized couplers are described in U.S. Patent No. 3. ur/, No. 120 work same No. u, oro,, 2ii
listed in the number. Specific examples of polymerized magenta couplers are described in British Patent No. 2.102.173 and US Pat.

In addition, granularity can be improved by using color-forming dye-diffusing couplers in combination, and such couplers are described in US Patent No. '1.
Jt&, 237 and British Patent No. 2, t2z, z7
Specific examples of o7 layer fC magenta couplers are Maku European Patent No. 9t and IVJ Patent Publication (OLS) 3.3.
Specific examples of yellow, magenta and cyan are described in 2 Hiroshi, jJJ).

The silver halide recording material of the present invention includes black-and-white photographic materials, color reversals, color reversal papers, etc., black-and-white photographs, reversal color photographic materials containing a coupler in a photosensitive material, and color reversal materials containing a coupler in a current solution. It is extremely useful in mold reversal color photosensitive materials that contain color particles and form color bands in the photosensitive materials during processing.

Among the silver halogenide materials of the present invention, the silver halogenide color reversal photosensitive material has at least one layer each of red-sensitive, green-sensitive, and blue-sensitive emulsions of 1111 KM, but the order of these photosensitive layers is , there is no particular restriction, and it is determined depending on the purpose.

As described later, a dye-forming coupler is used in the silver halide color reversal light-sensitive material of the present invention, and usually a cyan dye-forming coupler is used in the red-sensitive layer and a magenta dye is used in the green-sensitive layer. A yellow dye-forming coupler is used in the blue-sensitive layer, but different combinations can be used depending on the purpose.

In the processing of the color reversal photosensitive material of the present invention, black and white development@(@
l development) → stop → washing with water → reversing → washing with water → color development → stop →
Washing with water → Conditioning bath → Washing with water → Bleaching → Washing with water → Fixation → Washing with water → Stabilization →
A drying step is used. This process also includes a pre-bath,
A predural bath, intermediate bath, etc. may also be provided. Washing with water after bleaching may be omitted.

The inversion may be performed in a fogging bath, or it may be performed again in a bath. It is also possible to omit adding a fogging agent to the color developing bath. You can also omit the adjustment tower in history.

In addition, the black and white developer used in the present invention may include preservatives (e.g., sulfites, bisulfites, etc.), buffers (e.g., carbonates, boric acid, borates, alkanolamines),
Alkaline agents (e.g. hydroxides, carbonates), solubilizing agents (
(e.g., polyethylene glycols, esters thereof), pH adjusters (e.g., organic compounds such as acetic acid), sensitizers (e.g., quaternary ammonium salts), development accelerators, surfactants, toning agents, antifoaming agents. , a hardening agent, a viscosity imparting agent, etc. may be contained.

The first developer used in the present invention must contain a compound that acts as a silver halide solvent, and the above-mentioned sulfite added as a preservative usually plays this role. Examples of the sulfite and other usable silver halide solvents include KSCN, Na5ON, 2SOa, N
a2SO3, K2S2O5, Na252Q5, K2S2
O3, Na2S2O3, etc. can be mentioned.

Further, a development accelerator is used to impart a development accelerating effect, especially in JP-A-77-4J! The compound of the following general formula (A) described in the specification of No. 110 may be used alone or in combination of two or more, and the above-mentioned silver halide solvents may be used in combination.

General formula (A) R'-(-8-R)d' -S -It There is a preferable amount to be used in order to produce silver oxide emulsion K, but the amount can be easily determined by those skilled in the art.

For example, 5CN- is developer/ll comb 0.0! ~ o, o
Comol, especially I/C is preferably 0.01 to 0.01j mole, and SO□ is 0.0! ~1 mol, %Ko,
i~0. Preferably it is j moles.

When the compound of general formula (A) is added to the black and white developer used in the present invention, the amount added is preferably
The range is from 11 x/'0' mol to j x 10' mol, more preferably from Fil x/Q mol to co x 10' mol.

The pH value of the developer thus adjusted is selected to be sufficient to provide the desired density and contrast;
Approximately 1. j~about//,! It is desirable that it be within the range of .

To carry out sensitization using such a seventh developer, usually,
The time can be extended up to three times longer than the standard processing time.

If the treatment temperature is raised at this time, the extension time for the sensitization treatment can be shortened.

The fogging bath used for processing the light-sensitive material of the present invention may contain a known fogging agent. That is, stannous ion-organophosphate complex salt (U.S. Patent No. J, A/7..2
g2 specification), stannous ion organic phosphonocarboxylic acid complex salts (IWP Publication No. 1997-32416), stannous ion/-aminopolycarboxylic acid complex salts (British Patent No. 1,
stannous ion complex salt borohydride compounds (U.S. Pat. No. 2.2F≠, No. 747 specification) such as 20, orO), heterocyclic amine borane compounds (British Patent No. 1.0),
//, boron compounds such as No. 000 Specification II), and the like. The pH of this fog bath (reversal bath) ranges over a wide range from acidic to alkaline, with pH λ~/-
2, preferably 2. The range is from 10% to 10%, preferably from 3% to 10%.

The color developer used in the present invention has the composition of a general color developer containing an aromatic primary amine developing agent. Preferred examples of aromatic primary amine color developing agents are p-phenyl diamine derivatives as shown below. N,N-diethyl-p-7enylenediamine, λ-amino! -diethylaminotoluene, λ-amino-7-(N-ethyl-
N-Laurylamino)Toluey, 4C-(N-Ether-
N-(β-hydroxyethyl)aminocoaniline, -1methylruder [N-ethyl-N-(β-hydroxyethyl)aminecoaniline, N-ethyl-N-(β-methanesulfamidoethyl)-3-methyl -Hiro-aminoaniline, N-(2-amino-!-diethylaminophenylethyl)methanesulfonamide, N,N-dimethyl-p-
722 Diamine, U.S. Pat. No. 3.6J-6,210
No. Specification, No. J, Arr, rλ! Bi-amino-3-methyl-N-ethyl-N-methoxyethylaniline, Hiro-amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline and Hiro-amino-
3-Methyl-N-ethyl-N-β-butoxyethylaniline and salts thereof (e.g. sulfate, hydrochloride, sulfite,
p-toluenesulfonate, etc.) are preferred representative examples.

When the photographic material of the present invention is a black and white silver halide photographic material, Research Disclosure Vol. 174 A/
7j4! xr~λ pages of j, volume 1t7 &/r7/l
6j/page, left column, right column.

When the photographic material of the present invention is a color sensitive material, examples include color reversal film and color reversal paper, and color reversal films are preferably used.

When the photographic light-sensitive material of the present invention is a black-and-white light-sensitive material, specifically, a black-and-white negative light-sensitive material, a light-sensitive material for X-ray, a light-sensitive material for printing,
Examples include black and white photographic paper, but black and white negative photosensitive materials are preferably used.

(Examples) The present invention will be explained in more detail by examples below.
It is not limited to these.

(Example/) Silver halide photosensitive materials having various compositions as shown below were prepared on a triacetate film base, and sample 10/
And so.

7th layer Gelatin layer Gelatin layer 2nd layer containing gelatin o, 7zy/ln2
Emulsion layer Silver iodobromide emulsion Silver amount i, oy/m2 Iodity content Hiromorti Average grain size o, rμ Sensitizing dye
S-/i, oq/m2S J
/ , () @gl 7,. 2 Gelatin λ, OP
/ m 2 3rd layer Protective layer Gelatin layer containing gelatin 0.2 y / m 2 In addition to the above composition, a gelatin hardening agent (-J) and a surfactant were added to each of the nine layers.

In sample 10/, the first gelatin layer was made of compound 7-
r/, 1091, oil (N, N-diethyl diurylamide), ethyl acetate j091, surfactant 10P
Gelatin aqueous solution 10005! Sample 102 was prepared by adding and applying an emulsion prepared by stirring with a mixer.

The compound &l-j/ of the 10 samples was changed to the compound Al-! Sample 103 was created by changing the wavelength to λ.

Sample IO≠ was prepared by changing compound M1-rl of sample 102 to compound Al-53.

In sample 101, sample 102 in the second emulsion layer
Sample 10j was prepared by adding and coating an emulsion of the compound used in .

A sample iot was prepared by changing the compound m (-j/ to compound) of sample 101 to I- and λ.

Sample 107 was prepared by changing compound M1-ji of sample 10j to compound Ai-j3.

The obtained sample was passed through a G-turn for sharpness measurement and then subjected to the development process described below to obtain a silver image.

The processing steps used here are as follows.

Processing process Time Temperature development
! 'A-, 200C stop (l, 1% acetic acid aqueous solution) 7 minutes 20'('Fixing
10 minutes 20'C water washing 10 minutes 20°C dry developer water 7J-
Ornl Metol (II-λt sulfate)
Jy anhydrous sodium sulfite 4cjf hydroquinone (II-/) / co1 sodium carbonate l hydrate toy potassium bromide 2F Add water
1000111 Fixer water too
tut Sodium thiosulfate /j7 Glacial acetic acid /3. l Goboric acid
7. jp powder potassium alum
Add ljP water
The density of the 10100O obtained silver image was measured using a microdensitometer, and the sharpness was determined based on the MTF value.

The results obtained are shown in Table 1.

(Storability test #) The coated samples were stored under the following conditions.

l) ≠ 1 0 cJO% 3 days Co) ° μm 0 Cro≠ 3 days 3) After exposing the sample stored in the refrigerator through a wedge in which the amount of exposure light changes continuously, the above-mentioned development process was performed to obtain a silver image.

The density of the obtained silver image is measured, and the density of the part with the least amount of light is [)min and the density of Dmin+0°2 jt
, t, and find Dmin and g under the conditions (3).
I asked for a comparison with strange.

As shown in Table 9, the present invention shows that the sharpness improvement effect of #) DI) t-no-hydroquinone during storage is
It is clear that this can be achieved without the disadvantages of increasing n and decreasing sensitivity.

(Example 2) A multilayer color photosensitive material was prepared by coating each layer with the following composition on a triacetate film base.
/.

1st layer; antihalation layer black colloidal silver o, 2!1 p/m2 ultraviolet absorber [J-/θ, oay/m2 ultraviolet absorber U-,20,/P/interval 2 ultraviolet absorber U-s o, iP/m2
High boiling point organic solvent 0/0. lCC/rn
2 Gelatin Co, 3P/gelatin layer λ layer containing island 2; intermediate layer compound H/ 0,019/rn2 high boiling point organic solvent Q-20,0! Field/shoulder 2 gelatin
o, yz1p/3rd layer of gelatin layer containing door 2; 1st red-sensitive emulsion layer Silver iodobromide emulsion Silver amount: o, zy/m
2 (Iodine content Hiromorchi, average particle size 0.3μ) Sensitizing dye S-J/, 2η7-2 Sensitizing dye S-Hiro θ,! tq/m2 coupler C-/0.2p/m2 coupler C
-20,0jp/rn2 High boiling point organic solvent 0-2 0,0JOc/rn2
Layer containing gelatin o, 7y/rn2 ≠ layer; λth red-sensitive emulsion layer Silver iodobromide emulsion・・・・・・・・・Amount of silver・・・・・・・・・
... o, ry/rn2 (iodine content λ, j morti,
Average particle size Q, jμ) Sensitizing dye S-j
/, 09/m2 Sensitizing dye S-4'
0, 2 Jq/ rn2 Cub”)-C/
0.1jy/rn2 coupler C-20,/HiroP
/rrL2 High boiling point organic solvent σ-20,01■/-2 gelatin
/, the layer containing ≠6 y/m 2! Layer; intermediate layer compound H-/0, /y/m2
High boiling point organic solvent 0-2o, icc/m2 gelatin
1. Gelatin layer containing 1p/m2; 1st green-sensitive emulsion layer Silver iodobromide emulsion Silver amount...o, 7y/m
2 (i-J molar ratio containing iodine, average particle size 0.3μ)
Sensitizing color 1g S 1 o, tw/m2 Sensitizing dye S-4/, Koda/m 2 Coupler C-3o, 3hy/m2 High boiling point organic solvent 6-2 0, Oj cc/ 7
1! ”Gelatin t, 2oy/r
7th layer containing n2; 1st red-sensitive emulsion layer Silver iodobromide emulsion Silver amount: o, 7y/m
2 (Iodine content λ, YoMorti, average particle size 0.tμ
) Sensitizing dye 3-to, Hiroda/m
2 sensitizing dye S 6 0. rq/m2
Coupler C-Hiro 0.2! p/m2asu
r+ point organic solvent σ-20, o ucx/m2 gelatin
/, 0 no/Rth layer containing In2: intermediate layer compound H-/0, Ojj//m
2 High-boiling point organic bath medium Q2o, /F/m2 Gelatin 0, 'fi7 p/
Gelatin layer 2nd layer containing 1rL2; Yellow filter layer Yellow colloidal silver o, ly/m2 Compound H-/ 0, 02 p/rn2 Compound 1 (-20,032/12 High boiling point organic solvent Q-20,0 HiroCc /m2 gelatin
0. Gelatin layer containing Y4f/rn2 1st θ layer; 1st blue-sensitive emulsion layer Silver iodobromide emulsion Silver amount: o, l, 17
m2 (iodine content - 0j morti, average particle size 0.7
μ) Sensitizing dye 5-70. Layer 1/layer containing coupler Cj Q, j P/m 2 High-boiling organic solvent 6-coo, o and 17m2 Gelatin o, ry/m2; λth curve-sensitive emulsion layer Silver iodobromide Emulsion -Amount of silver.../, /y/m2 (Iodine content λ, J-molch, average grain size λμ)
Sensitizing dye S-70, 4cq/m" Coupler C-j/, 27/m"?
ah boiling point organic mmO-2o, i 2cc/m2 layer containing gelatin i, 7oy7m2
゛First λ layer; First protective layer ultraviolet absorption ThJU-/o, o2y/m2
Ultraviolet absorber U-λ o, o3p7m2 Ultraviolet absorber U j O, 0397m2 Ultraviolet absorber [J-10, 22P/Ultraviolet 2 High boiling point organic solvent 0/
0.2rcC/m2 gelatin
73rd layer of gelatin layer containing 002P/-2; fine-grain silver iodobromide emulsion covered with the surface of the second protective layer Silver amount: 0. /li/m2 (Iodine content: 1 mole, average particle size: 0.0 tμ) Polymethyl methacrylate particles (average particle size: /, jμ) 0.
In addition to the above composition, a gelatin hardening agent H-3 and a surfactant were added to each gelatin layer containing 29/rn2 gelatin Q, ri y/m. The compounds used to prepare the samples are as follows. Shown below.

-J C-HiroH3 -j U-/ U-λ U-J U-HiroH-/ H-λ H ■(-3 0-, 2 -J S-≠ -j -A 4L of the obtained sample The sample was exposed to white light through a pattern for measuring sharpness using a light source of 1000 lux at an exposure surface illuminance of 1000 lux, and then developed as described below to obtain a color image.

The treatment steps and treatment liquid used here are as follows.

Processing process Time Temperature First development 6 minutes JJ"C Water washing 2 minutes inversion 2 minutes color development 2 minutes p4 adjustment 2 minutes bleaching 6 minutes fixing ≠ minutes J, r'C water washing
Participation stability 1 minute drying Use the following book for the composition of the drying treatment solution.

No.-Developer water 700
Door l Sodium tetrapolyphosphate Co1 Sodium sulfite -207 Hydroquinone/potassium monosulfonate (If-7) 301 Sodium carbonate (l hydrate) 30P/-phenyl-Hiro-methyl-triple-hydroxymethyl-3-pyrazolidone (1 -J) -Zj' Potassium Bromide Ko,! 1 Potassium thiocyanate /, 29 Potassium iodide (0
, 7% solution) Add cobb water to 100,0 tl (pH
10,/) Inverted liquid water 7oo
ml Nitro N, N, N-) Limeteley Phosphonic acid, 4Na salt 3F Stannous chloride (co-hydroxy acid) 1yp-7 minophenol 0. /l! Sodium hydroxide
ry glacial acetic acid ・
Add teal water 10
0086 Color developer water 700
*1 Sodium tetrapolyphosphate 2F Sodium sulfite 7F Sodium tertiary phosphorus (lλl hydrate) 36F Potassium bromide
ip potassium iodide (0,1
% solution) Sodium hydroxide
3F Citrazine M
/, 19! N-Ethyl-N-(β-methanesul7onamidoethyl)-3-methyl-hiro-amine aniline sulfate ll taethylenediamine 3F Add water
10OORI adjusted liquid water 700
81 Sodium sulfite /29 Ethylenediamine, Sodium tetraacetate (l hydrate) ry Thioglycerin o, 4Iyxl Glacial acetic acid
3- Add water
100θml bleach solution water roo
y Sodium ethylenediaminetetraacetate (dihydrate) 2. op ethylenediaminetetraacetate iron (1) ammonium (l hydrate) /20.0 potassium bromide 100. Add water
1ooorrtt fixer water r o
oy ammonium thiosulfate to, o1p
Sodium sulfite 1.09 Sodium bisulfite J, Ol! add water
iooomt stable water roo
rst formalin (37% by weight)! ,0y
ul Fuji Drywell! , Q1 water was added and the image sharpness of these treated samples was measured.

Table 2/+w hit? )t0% M at frequencies of O
The TF value was shown.

Sample 20/llc was prepared in exactly the same manner as sample 0/, except that the second intermediate layer was coated with the emulsion of the compound A I-j / used in Example 1 and sample 16102.
Sample J7J was obtained.

In sample 02, compound Ml-j / was replaced with compound AI-
! 2 to obtain sample 203.

In sample A 202, compound A[-j/ is replaced by compound m
l-! By changing to rJ, sample ko0≠ was obtained.

In sample 20/, the third layer and first red-sensitive emulsion layer had Example/,
Sample 20j was prepared in exactly the same manner as sample 0/, except that the emulsion of compound m1-4/ used in sample 102 was added and applied.

In Sample 2θj, Compound AI-j/ was changed to Yal-42 to obtain Sample-〇B.

In sample θj, compound m1-j/ was changed to &I-j3 to obtain sample 207.

After placing the sample under the same storage conditions as in Example 1.

After exposing the sample to light through a wedge in which the amount of exposure light changes continuously, Example λ was subjected to the development process described above to obtain a color image.

The a degree of the obtained color image was measured through a red filter.

ΔDmax = (maximum concentration of refrigerated product) - (maximum concentration of sample stored under conditions/fico) ΔS0.5 = (sensitivity of concentration 0.2 of refrigerated product (logE)
) - (Sensitivity (logE) at a concentration of 0.J for samples stored under conditions/or 2) as shown in Table 2.

The smaller the numerical values of ΔI)max, ΔSo, and 5, the better.

Table 1 shows that the samples using the present invention can have improved sharpness without increasing Dmin or decreasing sensitivity during storage.

(Example 3) (1) Preparation of photosensitive silver halide emulsion Potassium bromide, potassium iodide, and silver nitrate were added to an aqueous gelatin solution with vigorous stirring. AgI = reference 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 A.

(2) Preparation of emulsion Compound 1-41. /29, a solution obtained by heating and dissolving oil (N, N-dieterlau, lylamide) zolp, ethyl acetate joy, and surfactant 1011 was added to gelatin aqueous solution 1
The emulsion (A) was obtained by stirring with a mixer.

(3) Preparation of coated samples On a triacetyl cellulose support, compound 1-71 was added to each layer of the following formulation as an emulsion (A) as shown in Table 3, and coated sequentially from the support side. ~307
It was created. However, it is a sample! 0/~307Fi optical density 0.
No. 3 supports were used.

Table 3 Emulsion A was added to the emulsion layer so that the coated silver was 3 p/m 2 .

Additives other than the emulsion emulsion in the emulsion layer and the surface protective layer are as follows.

1st layer (gelatin layer) Binder: Gelatin 0.7F/771
"Coating aid: N-oleoyl-N-methyltaurine sodium salt O6λ da/WL2 second layer (emulsion layer) Binder: Gelatin fil Fabric aid nidodecylbenzenesulfonic acid sodium salt 0./■/m 2 Poly- p-styrenesulfonic acid potassium salt l/rn 2 3rd layer (surface protective layer) Binder: Gelatin o, 7P/m2
Coating aid: N-oleoyl-N-methyltaurine sodium salt O, Koda/m2 Matting agent: Polymethyl methacrylate fine particles (average particle size J/J) o, i3q7m2 (4) Sensitometry These samples were measured at λ ! After application at temperature and humidity of oC4j%RH 7
Stored for days. Coat each sample with the following developer.
After developing for a minute, fixing, washing with water, and drying, the MTF was measured.

Processing process Time Temperature development
7 minutes -200C stop (λ,! Chizu #
I) 30 seconds 200C fixing 1
0 minutes 20°C water washing 5 minutes 2
0”C dry developer Metol (■-col sulfate) xp Sodium sulfite 9m 1oo1p Hydroquinone (II-/) j Tavorax/
1 (add 20 kota water /1 fixer ammonium thiosulfate aao, oy sodium sulfite (anhydrous) /J', 07 acetic acid (21%
) Hiro 1ml sodium metaborate izy potassium alum
/! 1 Add water
/, 01 MTF measurement MTF was measured with a HiroOO×λμ2 a.xi.-ture. The evaluation was quantified using the spatial frequency at which the MTF value was 0.2. Regarding MTF, T. H. James (T.
The Theory of the Photographic Process (ed. H. James)
of the PhotographicProc
ess) (/ri77. Macmilla
n) Co., Ltd., on pages 2-tit.

(5) Preservability test Coated samples 30/~J (77) were stored under the storage conditions shown in (4), and after death, they were further stored under the following conditions.

l) Hiro J 0C30% for 3 daysCo) ≠z 0cro% for 3 days 3) The sample stored in the refrigerator was exposed to no light through a wedge in which the amount of exposure light was changed continuously, and then the above-mentioned development process was performed to obtain a silver image. .

The density of the obtained silver image was measured, and the density of the portion with the least amount of light was determined as 1) min and Dmin+O.

Find the sensitivity from the amount of light that gives the density of
) min and sensitivity were determined.

As is clear from Table μ, the sharpness of the samples using the present invention can be improved without an increase in l) min or a decrease in sensitivity during storage.

The samples of the present invention also had slightly improved graininess.

Example 3 A sample was prepared in exactly the same manner as in Example 3, except that compound I-j≠ was not added as an emulsion, but dissolved in methanol, the amount added was adjusted, and added directly to the gelatin layer. As a result of evaluation, it was found that the sample using the present invention had Dmin during storage.
The sharpness could be improved without an increase in image quality or a decrease in sensitivity.

(In the example, ethyl acrylate was used as the dispersant n'12H25-(OCH2CI(2+i, -8O3N
After stirring and emulsifying with a, potassium persulfate was added as a polymerization initiator to prepare a polyethyl acrylate latex with a dispersed particle size of 0.02 to 0.0 or μm.

On the other hand, after dissolving compound 1-j4c in ethyl acetate and roughly dispersing it in an aqueous gelatin solution, it was mixed and stirred with the above polyethyl acrylate latex to form compound l-! A latex dispersion (A) was obtained by filling and dispersing the liquid into latex. In Example 3, a latex dispersion (A
Samples were prepared and evaluated in exactly the same manner as in Example 3, except that compound ■-74< was added to the gelatin layer in a different amount. Using the present invention, the six samples were stored at ]) min
The sharpness could be improved without an increase in image quality or a decrease in sensitivity.

(Example 6) Sharpness and granularity were determined in exactly the same manner as in Example 3, except that emulsion A was changed to emulsion (B) with the following formulation and the amount of emulsion added was changed as shown in Table 5. When we investigated the storage stability, the results were as shown in the table below.

Preparation of emulsion Compound M1-xi 1oyN,N-
Diethyl laurylamide jOyethyl acetate
toy surfactant
A solution of heating and dissolving ioy was added to a gelatin aqueous solution of 10
009 and a mixer to obtain an emulsion (B).

As is clear from Tables 5 and 6, the sharpness of the sample using the present invention can be improved without an increase in min or a decrease in sensitivity during storage.

(Example 7) (1) Preparation of photosensitive silver halide emulsion Thick plate-like twin grains of silver iodobromide (silver iodide J, j mol %) were prepared in the presence of ammonia and potassium thiocyanate by a double jet method. was formed. The average particle size is 0.7r as the average diameter of spheres with the same volume as each particle (sphere equivalent diameter)
It was μm. Emulsion B was obtained by chemically sensitizing the grains with chlorauric acid salt and sodium thiosulfate.

(2) Preparation of emulsion Compound 41-4' 109L oil (N,N-diethyl laurylamide) toy ethyl acetate toy surfactant
A solution obtained by heating and dissolving 10 ml of gelatin was stirred with 100 ml of gelatin aqueous solution using a mixer to form an emulsion (C
) was obtained. Compound AI-Hiro in emulsion (C)
Emulsion (D) was prepared in exactly the same manner as emulsion (C) except that -jj was changed.

(3) Preparation of coating sample As shown in Table 7 on a polyethylene terephthalate support, compounds AI-Hiroshi and H-sr as emulsions (C) and (D) were added to each layer of the following formulation, and the support was Samples 70/-70jr were prepared by propagating sequentially from the body side.

Emulsion B in Table 7 has a coated silver of 2. It was added to the emulsion layer in an amount of oy/m2.

The emulsion in the emulsion layer, additives other than the emulsion, and the surface protective layer are as follows.

1st layer (gelatin layer) Binder: gelatin 0.7y/m2 Coating aid: N-oleoyl-N-methyltaurine sodium salt 0,2ng/m2 2nd layer (emulsion layer) Anti-fogging after chemical sensitization Yakuhiro-hydroxy-6-methyl-/,! , 3a,7-chitrazaindene is added,
Oron sensitization was carried out by adding λooq of sensitizing dye (I) having the following structural formula per mole of silver halide grains.

(I) 2H5 Furthermore, dodecylbenzenesulfonate as a coating aid and a thickener p-vinylbenzenesulfonate were added to form the basic formulation of the emulsion layer. The weight ratio of silver/gelatin at this time is /.

It was 3.

3rd layer (surface protective layer) 7 containing polymethyl methacrylate fine particles, saponin, polystyrene sodium sulfonate, etc. in addition to gelatin.
A wt% gelatin aqueous solution was prepared and used as a basic formulation.

(4) Sensitometry These samples were stored for 70 days after coating at a temperature and humidity of JtoC, Aj%RH. J using the following developer for each sample.
The film was processed using an automatic processor for j'C seconds, and the KMTF was measured in the same manner as in Example 3.

(5) Preservability test coating sample 70/~70! After storing under the storage conditions shown in (4), further l) shown in (5) of Example 3.
It was stored under the conditions of ~3) and evaluated in the same manner as in Example 3.

As is clear from Table 1, the sharpness of the samples using the present invention could be improved without increasing Dmin or decreasing sensitivity during storage.

The automatic developing machine used was Fuji X-Ray Processor FPM4'000J manufactured by Fuji Photo Film ■.

The developer and fixer had the following compositions.

(Developer) 1, F phenyl-3-pyrazolidone ([1-/) 1. z Tahydroquino/(17-/) JOPj-Nitroindazole 9.219 Potassium Bromide
3. OF Anhydrous Sodium Sulfite 107 Potassium Hydroxide
3091 Boric acid
ioy glutaraldehyde
Add zy water to bring the total volume to /l (pH was adjusted to 10.20) (Fixer) Ammonium thiosulfate 200. Ofsodium sulfite (anhydrous) Co, op boric acid
r, oy disodium ethylenediaminetetraacetate o, i1p aluminum sulfate /j, 07 sulfuric acid
λλ, op glacial acetic acid
/, Add O1 water (adjust the pH to 14).

Claims (1)

[Scope of Claims] At least one silver halide photosensitive layer and at least one hydrophilic colloid layer containing substantially no silver halide are provided on the support, and the support is further provided with at least one silver halide photosensitive layer and a hydrophilic colloid layer containing substantially no silver halide, and further comprising a compound represented by the following general formula (I). An image forming method, comprising processing a silver halide photographic light-sensitive material containing at least one substance in the above-described substantially silver halide-free photographic layer, including a black-and-white development step. General formula (I) A-(Time)_t-X In the formula, A means a redox mother nucleus, and -(Time)_t-X is released only by being oxidized during photographic development processing. Represents an atomic group that makes it possible. Time represents a timing group connected to A through a sulfur atom, nitrogen atom, oxygen atom or selenium atom. t is an integer of 0 or 1. X means a development inhibitor.