JPS63142344A - Silver halide black-and-white photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a fine tone by incorporating a polymer providing a cation site. CONSTITUTION:When a silver halide emulsion layer is formed on a support to obtain a silver halide photographic sensitive material for forming a silver image, a polymer providing a cation site is incorporated into the emulsion layer or a layer adjacent to the emulsion layer. An anion transformed polymer such as a known ammonium or phosphonium salt polymer is preferably used as the polymer providing a cation site. A silver halide photographic sensitive material contg. a toning agent which changes the tone of a silver image especially to a warm tone without lowering the sensitivity, deteriorating the shelf stability of the image or increasing fog is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide black-and-white photographic material for observing silver images, and particularly to a silver halide photographic material with excellent color tone.

(Prior Art) Conventional methods for controlling the color tone of silver images include using compounds that contain sulfur atoms and are easily adsorbed to silver (for example, mercapto compounds,
Thiazoline-thione compounds) were famous. However, these compounds easily adsorb to halogenated planes, so
It has drawbacks such as interfering with the M absorption of the sensitizing dye, causing shine, lowering sensitivity, and promoting yellowing during image storage.

Also, when the halogen composition of the silver halide emulsion is changed, the color v1
It is known that 4W control is possible. For example, if a silver halide emulsion with a high chloride ion ratio is used, a warm-toned image can be obtained, but if the chloride ion ratio is high, the capri tends to increase and the sensitivity is low. In the first silver decagenide photographic light-sensitive material for obtaining a silver image, it is possible to change the tone of the silver image without lowering the sensitivity, deteriorating the image storage stability, or increasing fog (especially at high temperature). ) A photographic material containing a toning agent and made of halogenated steel is provided.

(Structure of the Invention) The above-mentioned object of the present invention is to provide a silver oxide film having at least seven halogenated milling layers on a support. l! lN1I! In a silver halide photographic light-sensitive material for obtaining
Alternatively, this could be achieved by including in the adjacent layer a polymer that provides cation sites. Since the color tone of a support having a white reflective layer is evaluated unfavorably, the present invention is particularly effective in a halogenated photographic light-sensitive material having a white reflective layer and using a secondary support. It is.

(9) Although the silver halide in the emulsion layer does not substantially contain iodine, it is preferable that the silver halide grains contain no iodine at all. This is because in silver halide grains containing substantially iodine (ie, 0.01 mol % or more of silver iodide), the effect of controlling color evenness by the polymer providing cation sites is small.

As the polymer providing cation sites used in the present invention, anion conversion polymers are preferred.

As the anion conversion polymer, various known ammonium salt (or phosphonium salt) polymers can be used. Ammonium salt (or phosphonium salt) polymers are widely known as mordant polymers and antistatic polymers from the following publications.

Tokukai ShojF-/JJ, ri4! O1 US Patent 3. It is,
Tata! , JP-A Showa zz-iaa33y, % Kai-Sho jμ-/ko4, 027, JP-A Show J≠-/13°t3! , Tokukai Akira!
! -30321. Water-dispersed latex described in Japanese Patent Application Laid-Open No. 1996-411227; US Patent No. 2. jllr! t
41-, same! , /4Lr, OJ/, same! , 7! t, r/
Polyvinylpyridinicum salts described in US Patent J
, 70'? Water-insoluble ammonium salt polymers as described in U.S. Patent No. 3, Rye, orr.

A preferred anion conversion polymer has the general formula % where % represents one unit of an ethylenically unsaturated monomer.几、
is a hydrogen atom or a lower alkyl group having carbon number/~t,
L represents a divalent radical having / to about lλ carbon atoms.

R2, 几, and 几. are the same or different/~
an alkyl group having about 0 carbon atoms, or from 7 to
An aralkyl group having about 20 carbon atoms represents a hydrogen atom, and R2, 1t3 and 几 are interconnected to form Q.
A cyclic structure may be formed together with the above. Preferably, from the viewpoint of residual color, only/of 几2, 几3, and 几 are hydrogen atoms. Q represents N or P, and Xe represents an anion other than iodide ion. X is θ to about 0 mol%, and y is about IO to 100 mol%.

Examples of human ethylenically unsaturated salts include olefins (e.g. ethylene, propylene, /-
butylene, vinyl chloride, vinylidene chloride, isobutyne, vinyl bromide, etc.), dienes (e.g. butadiene, isoprene, chloroprene, etc.), ethylenically unsaturated esters of fatty acids or aromatic carboxylic acids (e.g. vinyl acetate, acetic acid esters of ethylenically unsaturated acids (e.g. methyl methacrylate, butyl methacrylate, tart-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, octyl methacrylate, amyl acrylate, monoethyl acrylate, benzyl acrylate, manin-related dibutyl ester, fumaric acid diethyl ester, ethyl crotonate, methylene malonate diptyle ester, etc.), styrenes (e.g., styrene, α-methylstyrene/, vinyltoluene) , chloromethylstyrene, chlorstyrene, dichlorostyrene, bromustyrene, etc.), unsaturated nitriles (such as acrylonitrile, methacrylatetrile, allyl cyanide, crotonitrile, etc.). Among these, styrenes and methacrylic acid esters are particularly preferred from the viewpoint of emulsion polymerizability, hydrophobicity, and the like. A may contain two or more of the above monomers.

ltl is preferably a hydrogen atom or a methyl group from the viewpoint of polymerization reactivity.

In the formula, 几 represents alkylene (for example, methylene, ethylene, trimethylene, tetramethylene, etc.), annelene, aralkylene (for example, alkylene with), and 几 represents a hydrogen atom or R2. n is an integer of 1 or -.

N is preferable from the viewpoint of the toxicity of the QFi raw material.

X9 is an anion other than iodide ion, such as halogen ion (e.g., salt ion, bromide ion, etc.), argyl sulfate ion (e.g., methane ion, ethyl sulfate ion, etc.), alkyl or aryl sulfonate ion (for example, Methanesulfonic acid, ethanesulfonic acid, benzenesulfo/L p-toluenesulfone e
Among them, chlorine ion, alkyl sulfate ion, arylsulfonate ion, and sulfate ion are particularly preferred.

The alkyl groups and aralkyl groups of 2, R+3 and 几 include substituted alkyl groups and substituted aralkyl groups.

Examples of alkyl groups include R-substituted alkyl groups, such as methyl, ethyl, propyl, isopropyl, t-butyl, hexyl, cyclohexyl, -monoethyl, dodecyl, etc. Substituted alkyl groups, such as alkyl groups (for example, methoxymethyl group, methoxymethyl group, ethoxyethyl group, ethoxyethyl group, vinyloxyethyl group, etc.), cyanoalkyl groups (for example, cocyanoethyl group, 3- cyanoalkyl group, etc.)
, halogenated alkyl group (for example, -1fluoroethyl group, cochloroethyl group, perfluoropropyl group, etc.), alkoxycarbonyl alkyl group (for example, ethoxycarbonylmethyl group, etc.), allyl group, coptenyl group, There are zolopagyl groups, etc.

Aralgyl groups include unsubstituted aralkyl groups, such as be/zyl groups, phenethyl groups, diphenylmethyl groups, and naphthylmethyl groups;
2. ! -dimethylbenzyl group, μm isoglobilbenzyl group, ≠-octylbenzyl group, etc.), dialkyl group in alkoxy (9, for example, ≠-methoxybenzyl group, μm pentafluoropropenyloxybenzyl group, ≠-ethoxybenzyl group, etc.) , cyanoaralkyl group (e.g. μm
cyanobenzyl group, ter(≠-cyanophenyl)benzyl group, etc.), halogenated aralkyl group (7?, e.g.,
l-chlorobenzyl group, J-chlorobenzyl group, ≠-promobe/zyl group, $ -(e-chlorophenyl]benzyl M, "z etc.) 6.

The number of carbon atoms in the alkyl group is preferably 7 to /λ, and the number of carbon atoms in the aralkyl group is preferably 7 to 1 μi.As an example in which R2, 几, and R4 are interconnected to form a cyclic structure with Q, has the following.

An example of an aliphatic polycyclic ring (representing the atomic groups necessary to form a bare ring) is Nentobage 几. n is an integer of λ to 12), (CR2 (ZH each represents a hydrogen atom and a lower alkyl group with carbon number/~), W2 represents an atomic group required to form a ring), and R2
represents. When there are two R2s, they may be the same or different. ) etc.

In the above example, 1t2, 4, 6, CJ &X'' have the same meanings as in general formula (1).

Of course, the y component may be a mixture of one or more components.

X is preferably in the range of 0-4θ molar, and y is preferably in the range of 0-40 molar percent.

Furthermore, in order to prevent undesirable photographic effects from being transferred from the desired layer to other tMs or into the processing solution, at least one ethylenically unsaturated group (preferably one to one group) is added.
It is particularly preferable to copolymerize the monomers and use the resulting crosslinked polymer latex.

The structure of the crosslinked aqueous polymer latex is preferably a structure represented by the general formula (n).

In the formula, A, R1, R2, R3, 几, , L, and X are the general formula (
It has the same meaning as in 1). y in general E(II)
is 10 to 22.7 mol%, preferably 70 to 22.7 mol%
The content is 4 mol%.

Z is 0. / to 30 mol%, preferably / to 20 mol%.

B is a structural unit obtained by copolymerizing a copolymerizable heptamer having at least two ethylenically unsaturated groups. Examples of B i-j: such as ethylene glycol dimethacrylate, diethylene glycol diacrylate, neopentyl glycol dimethacrylate, tetramethylene glycol dimethacrylate, pentaerythritol tetramethacrylate, trimethylolpropane trimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate , neopentyl glycol diacrylate, tetramethylene glycol diacrylate, trimethylolpropane triacrylate, allyl methacrylate, allyl acrylate, diallyl phthalate, methylene bis acrylamide, methylene bis methacrylamide, trivinylcyclohexane, divinylbenzene, di-N-bis(vinyl benzyl)-N,N-dimethylammonium chloride, N,N-diethyl-N-(methacryloyloxyethyl)-N-(vinylbenzyl)
Ammonium chrome 17)", N, N, N'.

N/-tetraethyl-N, N/-bis(vinylbenzyl)-p--? silylene diammonium dichloromethane IJ)”
,N,N/-bis(vinylbenzyl)-IJethylenediammoniumcycloIJ)",N,N,N;N
'-Tetrabutyl-N,N'-bis(vinylbenzyl)
- Examples include ethylenediammonium dichloride. This 1
Among them, divinylbenzene and trivinylcyclohexa/ are particularly preferred from the viewpoint of hydrophobicity, alkali resistance, etc. =≠! = Hiro! Near 01 [1) y:z=+2j:j ■) x:y:z=447: ≠!=10 y:z=70', 10 Vl) x:y=+at O:r O ■) N':6)'i13 0e x:y=tloHλO As a polymer latex, the particle size is 10 to 1000 n.
m, preferably 70~! 00 nm.

The amount of the polymer that provides cation sites of the present invention varies depending on the type, form, coating method, etc. of the photographic material used, but generally the amount used is 0.12 or more per mole of Ag of the photographic material. Well, 9/, JP
That’s all/j! ? The following are preferred.

The polymer providing cation sites of the present invention may be added to the base of the photosensitive emulsion of the photographic light-sensitive material or may be added to the non-photosensitive layer, but it is preferably added to the non-photosensitive layer. .

The method for applying these polymers that provide cation sites into the layer of a photographic light-sensitive material is to add these compounds in their pure state to a coating solution for forming the layer, or to add water to methanol, After dissolving in an organic solvent such as ethanol, acetone, or a mixed solvent of water and the above-mentioned organic solvent, the coating solution is applied with a knife, dried, or sprayed onto the surface of the support.
Coating or e! What is necessary is just to immerse it in I solution and dry it.

(9) When added to the emulsion layer, it may be added to the emulsion during the emulsion manufacturing process (such as a chemical ripening process) or after the process is completed.

In the present invention, the support is preferably a water-impermeable support. A water-impermeable support refers to a support through which water does not permeate at all or only slightly. Such a support can be made by coating a transparent plastic film such as cellulose triacetate or polyethylene terephthalate with a white pigment such as titanium white dispersed in a binder such as gelatin, or a highly hydrophobic plastic film such as polyethylene. Molecules include double-sided laminated paper supports.

The silver halide in the halogenated photosensitive material used in the present invention has high solubility in the developer, and develops quickly, such as silver chloride and chlorobromide! ! The invention is made of a silver halide containing no or substantially no iodine (less than 0.81 mol%) such as silver bromide, and in particular, the present invention has a silver bromide content of 30 mol% or more, and furthermore 70 mol% or more. A remarkable effect is produced in emulsions containing silver chlorobromide or silver bromide in a mole % or more. The average grain size of the silver halide grains is not particularly limited, but μμ
Preferably not a good dog.

The particle size distribution may be broad or narrow. The latter is classified as a so-called monodisperse emulsion, and has a dispersion coefficient of 20% or less, more preferably 73% or less. (
Here, it represents the dispersion coefficient standard deviation divided by the average particle size. ) Known silver halide solvents can be used during grain formation.

As the silver halide emulsion, a so-called prIrnitive emulsion which is not chemically sensitized can be used, but it is usually chemically sensitized. For the purpose of chemical sensitization, the above-mentioned Gla fkides or Zelikma
Written by n et al. edited by jiF Ruiha H, Freser, DieGr.
undlagen der Photography
chenProzesse mit Silberha
Logeniden.

(Akademische Ver1agsgeSI
911schaft.

The method described in /R) can be used.

Namely, sulfur sensitization using compounds such as thiosulfates, thioureas, thiazoles, and rhodanines and activated gelatin, and reduction using stannous salts, amines, hydrazines, formamidine sulfinic acids, silane compounds, etc. It can be used alone or in combination with a sensitization method, a noble metal sensitization method using complex salts of metals of Group I of the periodic table, such as platinum, iridium, palladium, etc. in addition to total complex salts.

In addition, for the purpose of increasing sensitivity, increasing contrast, or promoting development, for example, thioether compounds, thiomonophores, urethane derivatives, urea derivatives, imidazole conductors,
J-pyrazolidones and the like may also be included.

Although it is advantageous in the present invention to use gelatin as the binder or protective colloid in the photographic emulsion, other hydrophilic colloids can also be used.

For example, proteins such as gelatin derivatives and graft polymers of gelatin and other polymers; sugar derivatives such as heptalulose derivatives such as hydrodiethyl cellulose, carboxymethyl cellulose, etc., starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, polyvinyl alcohol, etc. −
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of N-vinylzerolidone, polyacrylic acid, polyacrylamide, and the like.

In addition to lime-treated gelatin, acid-treated gelatin may be used as the gelatin, and gelatin hydrolyzate and gelatin enzymatically decomposed product may also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention include coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (for example, development acceleration,
Various known surfactants may be included for various purposes such as high contrast, sensitization, etc.

For example, nonionic interfaces such as saponin, polydiethylene compounds, grindol derivatives (such as alkenylsuccinic acid polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, and urethanes or ethers. Activator: triterpenoid saponi/, alkyl carmenates, alkylbenzene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl hollyoxyethylene alkyl Anio/surfactants such as phenyl ethers; amphoteric surfactants such as amino acids, aminoargylsulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine imides, amine oxides; alkyl amine salts, fats Cationic surfactants such as phosphonium or sulfonium salts containing polycyclic groups or aromatic fluorinated ammonium salts, pyridinium, imidazolium, etc., and phosphonium or sulfonium salts containing heterocycles for aliphatic compounds may be used. I can do it.

Fluorine-containing surfactants are preferably used for the purpose of preventing static electricity.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, a polymer containing as a monomer component alkyl (meth)acrylate, glycidyl (meth)acrylate, etc. alone or in combination, or a combination of these with acrylic acid, methacrylic acid, etc. can be used.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts, aldehydes, N-methylol compounds, active vinyl compounds ('t3,!-triacryloyl-hexahydro-S-triazine, bis(vinylsulfonyl)methyl ether, etc.), active/'% rogen compounds (
, 2, Il, -dichloro-4-hydrochemicals, 8-) riazine, mucohalogen acids, etc. can be used alone or in combination.

The photographic emulsions of this invention may be spectrally sensitized with methine dyes. The dyes used include cyanine dyes,
Included are merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. It is a pigment useful for brooms, belonging to merocyanif pigments and complex merocyanine pigments. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus,
Oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and aromatic in these nuclei Nuclei in which hydrocarbon rings are fused, namely, indolenine nucleus, pensindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinolite nucleus etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyania dyes include a pyrazoli/-3-off nucleus, a thiohydantoin nucleus, and a corchioxazolidine-2 nucleus with a ketomethylene structure.
．． ≠-dio/nucleus, thiazolidi/-2, ≠-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, etc.! ~ can be applied to the member heterosegmental ring nucleus.

The photosensitive material of the present invention contains water-soluble dyes (such as oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes) as filter dyes in the hydrophilic colloid layer or for various purposes such as preventing irradiation. .) may be contained.

The silver halide photographic material of the present invention may contain a known antifoggant or stabilizer. Examples of antifoggants or stabilizers that may be contained include mercapto compounds, benzothiazolium salts, nitroindazoles, nitrobenzimitazole fJ4, dimidazoles, bromobenzimidazoles, aminotriazoles, and benzene. Triazoles, nitrobenztriazoles, benzenethiosulfonic acids, benzenesulfinic acids, benzenesulfonic acid amides, azaindenes [e.g. triazaindenes, tetraazaindenes (especially μm hydroxy-substituted (/, J, Ja, 7) tetra azaindenes)]
and so on.

For photographic processing of the non-inventive light-sensitive material, any known development processing method for forming a silver image can be used. A known treatment liquid can be used. Processing temperature is normal/r'c! The developer used in black-and-white photographic processing may contain known developing agents. Developing agents include dihydroxybenzenes (e.g. hydroquinone), !-pyrazolidones (e.g. /-phenyl-3-pyrazolidone), aminephenols (e.g. N-methyl-P-
aminophenol), /-7enyl-3-pyrazolines, ascorbic acid, and U.S. Patent U, O67, R7.2
No. ノ/, J, j.

Heterocyclic compounds formed by condensing a Hiro-tetrahydroquinoline ring and an indoleno ring can be used alone or in combination. In particular, it is preferable to use pyrazolidones and/or amine phenols together with dihydroxybenzenes. In addition to this, the developer generally contains a known preservative 41. Contains alkaline agents, pH buffering agents, anti-fogging agents, etc., and further contains solubilizing agents, color toning agents, development accelerators, surfactants, antifoaming agents, water softeners, hardening agents, viscosity imparting agents, etc. May include. The photosensitive material of the present invention usually contains sulfite ions as a preservative at O1/! Processed with a developer containing mol/1 or more.

Further, a part of the developing agent may be included in the sensitive material.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanate/acid salts, organic sulfur compounds which are less effective as fixing agents can be used.

The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

Example 1 (1) Preparation of photosensitive silver halide emulsion An aqueous solution consisting of potassium bromide and sodium chloride was vigorously stirred with a silver nitrate solution into an acidic aqueous gelatin solution (p)l=μ) by the double jet method. While adding the average particle size O
, 4tμ cubic monodisperse emulsion (silver bromide 70 mol%, dispersion coefficient //%) 1=prepared. After that, it is washed with water by a normal precipitation method, and then sulfur sensitized to form a photosensitive chlorobromide image emulsion A.
I got it. Similar to silver halide emulsion A, however, by adjusting the amounts of beautifying potassium and sodium chloride in the preparation and the temperature during precipitate formation, a cubic monodisperse photosensitive chlorobromide emulsion B (odor silver oxide (30 mol%) and photosensitive silver chlorobromide hole i￥
Prepare IIc (30 mol% bromide complex).

(2) Preparation of coating samples Samples 1 to 7 were prepared by sequentially applying each layer as described above from the support side onto a paper support laminated on both sides with polyethylene.

(Emulsion layer) Binder: Gelatin, 7y/m2
Coated silver amount: i, zt7m2 sensitizing dye:
0.2η/m2 Fluorescent brightener*
Q, /? / m2 Polymer latex: Polyethyl acrylate 217m2 (surface protective layer) Binder: Gelatin /, 2ff/m"6 Fabric aid: Sodium dodecylbenzenesulfonate to? / m2 Colloidal silica (average 0.0!μ) o , 3y7m2 Hardening agent: Pi-dichloro-t-hydroxyne, 3°!-triazine sodium salt o, ort7m” (3) Sensitometric analysis of these samples. After application, it was stored for 7 days at a temperature and humidity of C4!%H.Each sample was evaluated using the following method.

The results of photographic properties are shown in Table 1.

(People) Color tone evaluation Sample 1 NIO was exposed to light through a continuous wedge using an L-based photometer using a tungsten bulb, and then each sample was exposed to water using Fuji Papitol developer (manufactured by Fuji Photo Film). /2/ diluted and used λo'C.

After developing for 20 seconds and stopping, use Fuji Fix (manufactured by Fuji Photo Film ■)! The color tone was evaluated by fixing for a minute, washing with water, and drying.

Note that the r value of these samples is all below 3, and the reflection image's degree is 2! Atsushi below.

(B) Silver lI! l113! Deterioration over time (yellowing)′
Measurement of # property The process from fog light and development to drying was carried out in the same manner as in (A).

Each processed sample was transferred to the UK Patent (Publication) No. λ, oi, 02.
≠Nitrogen dioxide gas (as described in Specification A)
After being left for 20 minutes in a φ millet with a 3000 ppm) atmosphere, it was left outdoors (under sunlight) for λ days. After standing, the degree of deterioration of the silver one-sided image that occurred in the image area was observed and evaluated as follows.

O: There is no deterioration of the silver image at all Δ: There is some deterioration of the silver image (practical limit) Then, the density was measured, and the relative sensitivity was calculated from the exposure amount that gave a high optical density.

As can be seen from Table 1, emulsions with a high molar percentage of silver bromide have high sensitivity, but the color tone becomes cold.

However, it can be seen that even in emulsions with a high molar percentage of silver bromide, the color tone can be made warmer without impairing sensitivity by adding the compound of the present invention. At that time, the stability of the silver + uil image had not deteriorated.

Example 2 (1) Preparation of photosensitive silver halide emulsion Same as Example 1 (2) Preparation of coated sample Laminate both sides with polyethylene and apply each layer of the following formulation sequentially from the support side on a nine paper support to prepare sample r. ~/l was created.

(Nyume 11 Noji 1)) Binder: Gelatin 3t7m”-Coating S
Amount: 10 milk to emulsion B (/:/) / , j 97m2 Sensitizing dye: 0.3"9/m2 color Y4 agent: Fluorescent brightener: (same as Example-1) 0, /, tf!/m2 Polymer latex: Polyethyl acrylate t/m” (surface protective layer) Binder: Gelatin, or/m2 Coating aid: Dodecylbenzene sulfo/sodium acid jfQ〃da/m2 Matting agent: Polymethyl methacrylate (Average/, j μ) o, it7m2 Hardener: Durge Chlorob-Hydroxy-1,3°! - Triazine sodium salt o, ort/m'' (3) Sensitometry As can be seen from the same table as Example 1, the color tone can be made warmer without impairing the stability of the silver image.

Example 3 (1) Preparation of photosensitive silver halide emulsion Same as Example 1 (2) Preparation of coating sample (emulsion layer) Binder: Gelatin j f / m 2
Amount of silver: Emulsion B, zf/m sensitizing dye:
0- j my/ 1'rL '已
Adjustment: Fluorescent brightener: (same as Example-/) o, 2f/m" Polymer latex: Polyethyl acrylate f/m2 (surface protective layer) Binder: Gelatin colloidal silica o, 3t7m2 Hardener: /, 2-bis(vinylsulfonylacetamido)ethane r ov47m 2 (3) Sensitometry Same as Example 1. Same as Example 1. When the compound of the present invention is added, the color tone is 1 without decreasing the sensitivity. The temperature can be adjusted.

At that time, the stability of the silver image does not deteriorate.

A preferred embodiment of the present invention is as follows.

A photosensitive material according to claims, characterized in that the t support has a white reflective layer and is a t support.

2. A photosensitive material according to the claims, characterized in that the support is a paper support laminated on both sides with polyethylene.

3. The polymer providing cation sites has the general formula (1
) Preferred embodiment 3.0 of the photosensitive material according to preferred embodiment 2, characterized in that in general formula (1), only seven of 几2, R3, and fL4 are hydrogen atoms
Sensitive material.

The polymer providing the cation site tWe has the general formula ((
The photosensitive material according to preferred embodiment 2, which is a latex represented by 1).

Claims (1)

[Claims] A halogen halogen compound comprising at least one photosensitive silver halide emulsion layer on a support, the silver halide emulsion being an emulsion substantially free of iodide ions and containing a polymer providing cation sites. Silver chemical black and white photographic material.