JPH02266347A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a both-sided photosensitive material easy in a coating step and high in sharpness by forming a silver halide photosensitive emulsion layer on both sides of a substrate, forming a layer containing a dye only on one side, and reducing light crossing over the photosensitive material to <= 10%, and decoloring the dye by a treatment within 90sec. CONSTITUTION:At least one silver halide photosensitive emulsion layer is formed on each side of the substrate, and the layer containing the dye is formed only on one side of the substrate, resulting in reducing the cross-over light to <=10%, and the dye is decolored by treatment within 90sec. It is preferred to use a mordanting layer or a layer containing fine dye crystals dispersed in the layer as the layer for fixing the light-absorbing dye, and the mordanting layer may be formed anywhere between the substrate and the photosensitive emulsion layer, but it is most preferable to use the layer adjacent to the substrate as the mordanting layer, thus permitting the obtained both-sided photosensitive material to be easy in the coating step and high in sharpness.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a double-sided photosensitive material with a simple coating process and high sharpness.

(Prior Art) In recent years, methods for observing the inside of the human body without physically incising the body have made rapid progress and continue to develop. These include methods such as CT, MRI, PET, and ultrasonic diagnostics, and computer image processing continues to develop these methods into systems with higher diagnostic capabilities. In these diagnoses, the primary image is to be observed on a CRT, and either the photosensitive material directly casts a shadow on the CRT, or the information captured as a digital signal inside the computer is printed using semiconductor laser exposure. For this purpose, so-called CRT photosensitive materials and laser imager photosensitive materials are rapidly becoming popular.

However, 80% to 90% of imaging for medical and diagnostic purposes still relies on the so-called conventional system that uses XkIIA/fluorescent screens and silver halide sensitive materials. This method is simple for both patients and doctors, has relatively low implementation and maintenance costs, and provides fairly sufficient information for primary diagnosis, so some systems may be replaced by other systems. Deafness is likely to continue to be a major medical diagnostic method in the future.

Breast cancer among women has been rapidly increasing in the United States in recent years, and mflffi is also seen in Japan. Conventional systems that use X-ray/fluorescent screens and sensitive materials are extremely important as a method for early detection of breast cancer.However, for early detection of breast cancer, it is necessary to identify calcified lesions of several hundred micrometers. For this reason, conventional systems have sacrificed system sensitivity in favor of sharpness, and have irradiated a fairly large amount of XI for diagnosis. It goes without saying that a large amount of X-ray irradiation is harmful to the human body, and for this reason there continues to be a need for means to reduce the exposure dose.

U.S. Pat. No. 4,803,150 discloses that a dye dispersed in a fine solid state is applied as a crossover cant layer below the emulsion layer to virtually eliminate image blur due to crossover, allowing a single-sided screen/sensitive material system to be used. A technique has been disclosed in which the sensitivity is significantly improved by having sensitive emulsion layers on both sides of the support, which have similar sharpness.

However, the provision of dye layers on both sides of the support causes difficulties in the coating process (poor surface condition, cost increase).

(Objective of the Invention) As mentioned above, the object of the present invention is to provide a double-sided photosensitive material with a simple coating process and high sharpness.

(Structure of the Invention) The above object is to have at least one photosensitive silver halide emulsion layer on each side of the support, and to have a dye-containing layer on only one side of the support, so that cross-over The light is extinguished to less than 10% and the dye is
It has been found that this can be achieved using a silver halide photosensitive material that is characterized by decoloring within 0 seconds.

As the fixed layer of the light-absorbing dye of the present invention, a mordant layer or a dispersion layer of the dye in the form of microcrystalline particles is preferably used.

The mordant layer of the present invention may be provided anywhere between the support and the photosensitive emulsion layer, but it is most preferable to use the layer adjacent to the support as the mordant layer.

The mordant layer of the present invention contains an anionic dye with good decolorizing property and a cationic polymer as a mordant as main materials, and the cationic polymer of the following general formula (1) and the anionic dye of the general formula (U) are preferably used. In order to stably apply the combination of dye and mordant, some ingenuity is required. When the mordant layer is used as a layer between the support and the photosensitive emulsion layer and is coated simultaneously with the photosensitive emulsion layer, it is preferable to provide an intermediate layer containing as little unnecessary anions as possible between the mordant layer and the photosensitive emulsion layer.

-Match type (, ■) General formula ('') General formula (N in the formula, A represents an ethylenically unsuitable monomer unit. R1
Represents a divalent crystal in which a lower alkyl group of about 50% is hydrogen or about 1% of hydrogen, and a charcoal of about 1% is added to L. R2, R3 and R4 each have an alkyl group having 1 to about 01 carbon atoms, or an aralkyl group having 7 to about 2016 carbon atoms, respectively.
Alternatively, R2, R3, and R4i may pass through each other to form a ring-shaped structure together with 0, representing a water box. Preferably only one of R2, R3 and R4 is a hydrogen atom.

Q is N or P, and Xe represents an anion other than iodide ion.

The series of ethylenically unsaturated monomers include, for example, olefins (e.g. ethylene, propylene, l-
butene, vinyl chloride, vinylidene chloride, isobutyne, vinyl bromide, etc.), dienes (e.g. butadiene, isoprene, αa-prene, etc.), ethylenically unsaturated esters of fatty acids or aromatic carboxylic acids (e.g. vinyl acetate, allyl acetate, etc.) , vinyl propionate, vinyl butyrate, vinyl benzoate, etc.), ethylenically unsaturated acid esters (e.g., methyl methacrylate, butyl methacrylate, tert-butyl methacrylate, '//mouth acrylate, benzyl methacrylate, Phenyl methacrylate, octyl methacrylate, amyl acrylate, Koederhexyl acrylate, benzyl acrylate, malein K Schiff' thyl ester, diethyl 7-malate ester, ethyl lysate, methylene a7w diy-thyl ester, etc. J, styrenes (
For example, styrene, α-methylstyrene, vinyl, toluene, lyalmethylstyrene, lystyrene, dichlorostyrene, bromustyrene, sodium, etc., unsaturated nitriles (such as acrylonitrile, methacriminitrile,
(allyl cyanide, crotonitrile, etc.). Among these, styrenes and methacrylic acid esters are particularly preferred from the viewpoint of emulsion polymerizability, hydrophobicity, and the like. %1 contains two or more of the above monomers.

R1 is preferably a hydrogen atom or a methyl atom from the viewpoint of polymerization reactivity.

In terms of alkali resistance, etc., R5 in the above formula is 1.7-2-lene, aralkylene (9 m, t (alkylene having a ha atom), R6 is a hydrogen atom, and R2 is a thorny atom. n is/or an integer of -.

From the viewpoint of the harmfulness of the Qfl raw material, etc., it is preferable.

Xe is an anion other than iodide ion, flt is halogen ion (e.g. chloride ion, bromide ion, etc.),
Alkyl sulfate ions (e.g. methyl t[ion, ethyl sulfate ion, etc.), alkyl diarylsulfone ions (and 1tilthanesulfonic acid, ethanesulfonic acid, benzenesulfone rR, p-toluenesulfonic acid, etc.) 1. There are acetate ions, sulfate ions, etc. Among these, chlorine ions and alkyl sulfate ions.

Aryl sulfonate ion, sulfate ion. is particularly preferred,
Yes.

The alkyl groups and aralkyl groups of R2, R3 and R4 include substituted alkyl groups and substituted aralkyl groups.

Examples of the alkyl group include unsubstituted alkyl groups such as methyl, ethyl, propyl, inpropyl, t-butyl, hexyl, cyclohexyl, coethylhexyl, and dodecyl, substituted alkyl groups such as Alcohol dialkyl crystals (e.g., methoxymethyl, methoxybutyl, ethoxyethyl, butoxyethyl, vinyloxyethyl L, etc.), cyanoalkyl crystals (e.g., 2-cyanoethyl, etc.), halogenated alkyl crystals (For example, 2-fluoroether crystal, coke aa ethyl crystal, par 7a a fa pill Todoroki, etc.
Examples include Corptenil Gu and Puno Kir Crystal.

Examples of the aralkyl group include unsubstituted aralkyl groups, such as
Naphthylmethyl and substituted aralkyl groups, such as alkylaralkyl groups (e.g. ψ-methylbenzyl 1
,2. j-dimethyl (dimethyl, ≠-isopropylbenzyl, ≠-octylbenzyl), alkylaralkyl groups (e.g., dermethoxybenzyl, ≠-isopropylbenzyl, ≠-isopropylbenzyl, ], cyanoaralkyl group (such as Hiro-
cyanobenzyl 4, p-(p-cyanophenyl), p-(p-cyanophenyl), aralkyl group (e.g., μ
m-chlorobenzyl group, 3-chlorobenzyl group, Hiro-prosobenzyl group, Hiro-(≠-chlorophenyl) (Njiruj)
jjto17'! There is.

The number of carbon atoms in the aralkyl group is preferably /-71, and the number of carbon atoms in the aralkyl group is preferably 7 to 11.

X is 0 moles, preferably 20 to 40 moles.

y Hari, Rina, Tata, Tamorchi, preferably 1
0-9' is Morchi.

2 is 0. /or 0 mole head, preferably 1 to 317 mole head.

B is a structural unit obtained by copolymerizing a copolymerizable monomer having at least two ethylene unsaturations. Examples of B include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, neointyl glycol dimethacrylate, tetramethylene glycol dimethacrylate, hantaerythritol tetramethacrylate, trimethylolpropane trimethacrylate,
Ethylene glycol diacrylate, diethylene glycol diacrylate, neointyl glycol diacrylate, tetramethylene glycol diacrylate, trimethyl a-pantriacrylate, allyl methacrylate, allyl acrylate, di-allyl 7-thalerate, methylene bisacryl amide , methylene bismethacrylamide, trivinylcyclohexane, divinylbenzene, to.

h bis(vinylbenzyl)-~,~-dimethylammonium quardo, to,hagez f rule 4-(methacryloyloxyethyl)-~-(vinylbenzyl]ammonium quardo)-1~,~N/self '-Tetraethyl-auto, he'-bis(vinylbenzyl)-p-xylylene diammonium dichloride, N, r'l'-bis(
[vinylbenzyl]-triethylenediammonium dichloride a
lido, N, N, IN'be'-tetrabutyl, yen'
-bis(vinylbenzyl J-ethylenediammonium cycloa 17 )Tz. Among these, divinylbenzene and trivinylcyclohexane are particularly preferred from the viewpoint of hydrophobicity, alkali resistance, and the like.

The compound fFij of BoIJv-, which is expressed by the general formula (1), is shown below.

Compound example ■-/) x:y:z=≠7. j:4c7. j: yo■-2ノ x:y:z=Hiroj:Hiror:i.

[-3) I-! ) ■-Horin y:z=rij:yo1-+2 y:z=IO:20 e CR2-yen-(t-i3 (h3 x:y:z-μyo=Hiro?:10 t-t3 x:y=!0:10 Φ CJl+1-N-CJ+I J1m These polymers are preferably used in the form of a so-called polymer latex, and the preferred amount added is 5 to 5 per layer.
1000 .mu./d, preferably 10 to 500 .mu./d.

Next, the dye of general formula (■) will be explained.

In the general formula (U), R1 is an aryl group or alkyl group having at least one carboxylic acid group or sulfonic acid group,
represents an aralkyl group or a heterocyclic group, R8 is -CONR
3R4 or -NR,COR.

(Rs here represents a hydrogen atom or an alkyl group, R4
represents an alkyl group whose hydrophobic substituent complete loss π is in the range of 1.60≦π≦3.90, L, , t, g
, t, and * each represent a methine group, and n is 0. / It is also displayed.

Specific examples of the six groups in general formula (II) are shown below.

The carboxylic acid crystal or sulfonic acid group possessed by the aryl group, alkyl group, aralkyl group or multicyclic group represented by R) is an aryl group, alkyl group, aralkyl group or heterocyclic group.
In addition to directly bonding to the group, it also binds to the linked crystals of Jiii (for example, alkoxylic acid crystals (cocarboxyethoxy, 3-sulfopropoxy, dasulfo7') chrysanthemum), alkylene acylamino ll5 (for IPIJ, β-carboxy Pua Pionil Ami/) 7! = tzn1-(fltbao-sulfophenyl, p-carboxyphenyl), alkyleneaminocarbonyl (e.g. cosulfoethylaminocarbonyl J, alkylenesulfonyl 1(lFIJ)
ttf! -sulfopropylsulfonyl, etc.].

Aryl crystal, alkyl group, aralkyl crystal represented by R, or #:C complex m vapor or carbo:/! l! % Sulfone II
l! Other than (l exchange crystals), halogen atoms (for example, chlorine, bromine, yokusumi), aryl crystals (for example, phenyl,
Naphthyl;, Mizu A, Alkyl with carbon number β-hiro iNM: methyl, ethyl, propyl, butyl, isobuvir)
, alkoxy M having 1-1 carbon atoms (ethoxy,
Ethoxy, cohedo axyethoxy, comethoxyethoxy J1 aryloxy crystals (e.g. phenoxy), amino acids (e.g. dimethylamino, diethylamino), acelamino crystals (acetylamino for fII), cyano group,
Nitro crystal, etc.] may also be M.

Alkyl crystals represented by R, at least %/(number of carbon atoms having carbon a crystal or sulfone a crystal in It) -1 alkyl group (for example, sulfomethyl, carboxymethyl, cosulfoethyl, cocarboxyethyl , 3-sulfobutyl, 3-sulfo-comethylp-a-pyr, J-sulfo-co, kodimethyl-p-a-pyl, Hiro-sulfobutyl,
See-Calhokitbutil! -sulfothyl, 6-sulfohexyl,! -carboxylic acid is methyl, Δ-carboxytahexyl] is preferred.

The aralkyl compound represented by R1 contains at least one carbon atom or sulfonic acid having a carbon number of 7 to 1. j aralkyl & (91Jt, a-sulfobenzyl, λ-sulfobenzyl, !, 4!-disulfobenzyl, co(Hiro-sulfomethylo-)benzyl, coumetelucose sulfobenzyl, dasulfo-7enetel, -carboxybenzyl., 2.≠-cy(3-sulfopropyloxy)benzyl, and cohydroxy-hiro-(cosulfoethoxy7nobenzyl) are preferred.

The aryl crystal represented by R1 is at least /+'l carboxylic acid crystal or the sulfone is a phenyl group (Nt
, Hiro-sulfophenyl, ≠-carbo-diphenyl, -
1-methyl-μm sulfo-7enyl, 3-sulfophenyl,
21 Hiro-disulfophenyl, J, j-disulfophenyl, λ-chloro-Hiro-sulfophenyl, comethoxy V
-Sulfo-7enyl, Hiro-chloro-3-sulfophenyl,
Cometoxie! -sulfophenyl, cohydroxy≠
-sulfophenyl%co,! -Dikua Luhiro-Sulfophenyl, Gouphenoxy-3-sulfophenyl, San-(
2. t-diethyl-hiro-sulfophenyl 1 or 7 tyl Is <
flItba3. t-disulfo-a-f7thyl, r-hydroxy-J, J-disulfo-α-naphthyl,! -Human alpha-xy7-sulfo-beta-naphthyl, A,r-disulfo-beta-su7thyl J is preferred.

The compound ring crystal represented by R1 is at least 1%! It has elementary atoms! In addition, t-membered nitrogen-containing complex fi crystals (for example, yo-sulfobiridine-coyl, !-carboxypyridine-2
-yl, t-sulfoquinoline-koyl, b-sulfoquinoline-koyl,! -Sulfo(nzothiazole-coyl, !-carboxybenzotheazole-coyl, t
-Sulfobenzoxyl-1-yl, O-carboxybenzoxazol-2-yl, t-sulfomethylpyridine-coyl,! -sulfobyrimidine-coil)
is preferred.

R3 represents a hydrogen atom or an alkyl crystal (preferably an alkyl crystal having 1 to 3 carbon atoms, such as methyl, ethyl, n-propyl, or improvil); R3 preferably represents a hydrogen atom;

R4 represents an alkyl group having a hydrophobic substituent constant in the range of /, tO≦π≦3, and RI;

If it is within the range of 1Q≦π≦3.20, substituents (for example, hydroxyl crystal, carbon 1L fluorine atom, chlorine atom, bromine atom,
Cyano group, alkoxy group (e.g. methoxy, ethoxy)
, amino group (the list is dimethylamino, diethylaminone, amide vapor (e.g. acetylamino, meta/sulfonamide J1 carbamoyl crystal (e.g. methylcarbamoyl,
ethylcarbamoyl) or sulfamoyl group (fFlt+lsulfamoyl, ethylsulfamoyl]).

The value of the above hydrophobic substituent constant is C, tiansch.

A, Leo l'-3ubstituent Co
n5tants for Correlation A
Analysis in Chemistry and
BiologyJ Tohn Wiley
& 5oz.

Inc(/77ri)≦! page -/page 47, and the substituents not described in the same publication are:
The same publication also tZc, Hansch et al. Journal
of Medicinal ChemistryJ
Volume 2Q, pp. 30-30 can be calculated by the method described in 1977, 2. For example, in the hydrophobic substituent constant π of substituent Partition coefficient log PX of grand conductor (X-C6)1・5)
-Distribution coefficient of benzene from C, H, txlogP
(Here, we use l o g P (, H, intestine, llH6 3).) It can be calculated by subtracting.

Note that logPz-66H5 is based on the above publication (“5ubst
ituent Con5tonti for Cor
relationship analysis in Chem
istryand BiologyJ) / 1 page ~
It can be determined by the method described on page 37.

In the general formula tUt, particularly preferably, R3 represents a hydrogen atom and R4 represents an unsubstituted alkyl group having a hydrogen atom number of -5 (for example, n-butylene, Ln-intyl, nτhexyl, inobutyl, 5ec-butyl, tert-butyl, l -ethylpropyl, l-methylbutyl, comethylbutel, 3-methylbutyl, /, /-dimederp apyr, λ,
λ-dimethylpropyl) or ≠-butyl group, 7-
hydroxyheptyl crystal, -carboxyhexyl crystal, l
- Human mixture octyl crystal, coedylbutyl Todoroki,! - Cyano is a word that represents ``Nichiru Gu'', 6゜Ll, R2,
The methine crystal represented by R3 may have a substituent (for example, methyl vapor, ethyl crystal, cosulfoethyl group, cyano crystal, oxygen atom, etc.).

In the above general formula (IN, carboxylic acid crystal or sulfone a
The group can be used as a free acid or as a salt (e.g. Na salt, K salt, (CzHs
) 3-d salt, pyridinium salt, ammonium salt, etc.) may be formed.

Particularly preferred in the above general formula (ill) are those in which R represents a 7-enyl crystal having at least 1 sulfone group, an alkyl crystal with carbon li/-p, a benzyl group or a 7-enethyl group. It is.

Specific examples of dyes represented by general formula (II) are shown below, but the present invention is not limited thereto.

As the dispersion layer of the dye of the present invention in the form of microcrystalline particles, the general formula (II/) or (V) or (Vl) or (■) or (
A filter dye layer of a microcrystalline dispersion of the compound represented by (2) is used.

General formula (rV) R1 I'll General formula (N) R3 General formula (I A=L 1'+L2 =L 3S A General formula (■) A+LI Lzsr hunting B General formula (■) The person in the formula is It represents a substituted or unsubstituted acidic nucleus having a carboxyphenyl group, sulfamoyl group, or sulfonamidophenyl group.The acidic nucleus is copirazoline!
-one, adanine, hydantoin, thiohydantoin,
2. (1-oxazolidinedione, isoxacillinone, barbic acid, thiobarbic acid, indanedione,
selected from hydroxypyridone. B represents a substituted or unsubstituted basic nucleus having a carboxyl group, sulfamoyl crystal or sulfonamide crystal. Basic nuclei include pyridine, quinolineindolenine, autoxol,
selected from benzoxazole, naphthoxazole, and virol. R is a hydrogen atom, alkyl% of carbon x number z-h
R1 and R2 are each a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and R1 and R4t R
2 and R5 are carbon atoms! ~ may form a member ring. R
3 is a hydrogen atom, an alkyl group, an alkoxy group, R4, R
s is hydrogen atom% R1 and R4 or R2 and R5, respectively, 5
-jjll may be formed. Ll, R2, and R3 each represent substituted or unsubstituted methine. X and Y each represent an electron-withdrawing group, and either X or Y has a carboxyphenyl or sulfonamidophenyl group. m represents O or /Y, and n represents 0. /or 2.

Next, specific FP3 of the dye used in the present invention is listed.
The present invention is not limited to these.

■-t ■-1 V-J ■-Hiro■-Yoshi 1-13 UW2H5 ■-Δ ■-10 1'11/-7 OOH ■-// ■-r ■-/2 ■-ta ■-/ l it/-77 V-/ -x Fi3 -J ■-Hiro-r y-+ H3 ■-r ~1-7 ■-70 INI-4s2S2H3 ■-// ■-/ λ ν1- 73 ■-/≠ C0OH OOH M-/j ■-/ Otsu + (00C OOH ■-g H3 ■-I k-1n ■-7 ■-/ ■-ko ■-3 2H5 OOH ■-! Shiti3 [C2 )'i5 ■-/l ■-/, 2 OOH ■-7 ■-2 ■-3 ■-μ C(JL)H ■-1 Hiro2H5 ■-/4 2H5 ■-! ■-4 ■-7 The dye used in the present invention is patented under international patent worr70II7.
European Patent EP (7 Kotsuhiro 72IAI, JP-A-Sho! 2-Tako 7/J, !!-/1!310, !r-/!!31/, 6l- 20jri 3rd issue,
1it-41623, U.S. Patent No. 2527583, U.S. Patent No. 3486897, U.S. Patent No. 3746539, U.S. Patent No. 393
It can be easily synthesized by the method described in No. 3798, No. 4130429, No. 4040841, etc., and according to that method.

The photographic composition of the present invention can be used, for example, in black and white, monochrome, multicolor, d
Useful in photographic elements.

The dyes useful in this invention can be used in any amount useful to filter or absorb light, but it is important to use them in amounts and locations such that they are solubilized and washed out during the development process. Particularly advantageous. If it is desired to absorb only a small amount of light, only a small amount of dye is needed. If it is desired to absorb more light, larger amounts of dye can be used as long as the coloration level remains acceptable for the particular photographic element. The dye is preferably present in the photographic element in an amount from 1 to 1000 cm/ft''.

The dyes useful in this invention are in the form of solid particulate microcrystalline dispersions for inclusion in layers, such as hydrophilic colloid layers, coated on photographic elements. Microcrystalline dispersions can be formed by precipitating the dye in the form of a dispersion and/or by conventional milling, such as ball milling, sand milling or colloid milling, in the presence of a dispersant. The particles have an average diameter of less than 10 μm, more preferably less than 1.17 m. Dye particles can conveniently be manufactured to sizes of 0.01/jm or less.

The silver halide grains in the photographic emulsion used in the photographic light-sensitive material of the present invention may have regular crystal bodies such as cubic, octahedral, rhombidodecahedral, and tetradecahedral, and may also have spherical, Irregular (ir
It may have a regular (regular) crystal form or a composite form of these crystal forms.
Research Disclosure
They may be tabular grains having an Asbek I ratio of 5 or more as described in Vol. 225, pp. 20-58 (Mon. 1983).

Further, the particles may have an epitaxial structure, or may have a multilayer structure in which the inside and the surface of the particle have different compositions (for example, halogen composition).

The average size of the particles is preferably 0.5μ or more, more preferably 0.7μ or more and 5.0μ or more.
It is less than μ.

The particle size distribution may be wide or narrow; the latter is known as a so-called monodisperse emulsion, and the dispersion coefficient is preferably 20% or less, more preferably 15% or less. The coefficient is the standard deviation divided by the average grain size.
que Photographique (published by Paul Montel, 1967)
Photography Ink Emulsion Chemistry (G, F, Duffin)
photographic emulsion chem
istry) (The Focal Press (The F
Making and Coating Photographic Ink Emulsion (Makin (and CoaLing Photo) by V, L, Zel 1lvan et al.
raph'rc emulsion) (The Focal Press, 19
64). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. .

These photographic emulsions may be any combination of silver chloride, silver bromide, silver iodide, silver iodobromide, silver chloroiodobromide, and silver chloroiodide.

Cadmium salts, zinc salts, lead salts, thallium salts, iridium salts, or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof, etc. may be present in the stage of silver halide grain formation or physical ripening. .

Binders for the emulsion layer and other layers of the silver halide photographic material of the present invention include proteins such as gelatin and casein; cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose; sugar derivatives such as agar, dextran sodium alginate, and starch derivatives; Synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N
-Vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide, or derivatives and partial hydrolysates thereof, etc. can also be used.

Gelatin referred to herein refers to so-called lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin.

Further, the photographic material of the present invention may contain an alkyl acrylate latex described in U.S. Pat. No. 3,411,911, U.S. Pat. I can do it.

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

For chemical sensitization, the Glafkides or Zel i
kman) et al. or Etch Freezer (tl
, Die Grundlagen der Fotographie, edited by Friteser.
Photography Prozess
e mitSilberhalogeniden)
Akademirafuko・fuxt-f,<gezeb'/ya7to(A
kademiscbeVerlagsgesellsc
The method described in Haft ) 1 (/ritr) can be used.

That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. are used alone or in combination. be able to. As the sulfur sensitizer, thiosulfur cod, deiorine compounds, thiazoles, rhodanines, and other compounds can be used. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, sila/compounds, etc. can be used. For noble metal sensitization, in addition to total complex salts, complex salts of metals in group I of the periodic table, such as platinum, iridium, and noradium, can be used.

The light-sensitive material of the present invention can contain various compounds as stabilizers. That is, azoles such as benzothiazolium salts, nitrobenzyl-LIJ azoles, benzotriazoles, benzimidazoles (
Heterocyclic mercapto compounds such as analogous captothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially l-phenyl-! -mercaptotetrazole), mercaptopyridines; the above-mentioned hetea-ring mercapto compounds having a water-soluble group such as a carmexyl group or a sulfone group; thioketo compounds such as oxacyly/thione; azaindenes such as tetraazaindenes:
(Especially 7-substituted (/, j, ja, 7) tetraazaindenes in ≠-human c!); Many known stabilizers such as benzenethiosulfone (!a; benzene nitsulfinic acid; compounds can be added.

The photographic emulsion layer or other constituent layers of the photosensitive/photographic material of the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (for example, development acceleration, high contrast, sensitization, etc.). ) may also contain a surfactant for practical purposes.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene (e.g. glycolalkylamides or amides, polyethylene oxide adducts of crecone), glycidol derivatives (e.g. alkenylsuccinic acid polyglyglypeptides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Ionic surfactants; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl tauric acid, sulfosuccinic acid esters, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.
Anionic surfactant containing acidic groups such as chrysanthemum group, sulfo group, phosphor group, sulfate ester group, phosphate ester group; amino acids, aminoalkyl sulfo/acids, aminoalkyl sulfate case 7? :Fi phosphate esters, alkyl betaines,
Amphoteric surfactants such as amine oxides; alkyl amine salts, aliphatic or aromatic bromine ammonium salts, multicyclic bronchial ammonium salts such as pyridinium, imidazolium, and aliphatic salts include complex flI. Cationic surfactants such as phosphonium or sulfonium salts can be used. Among these surfactants, polyoxyethylene surfactants and fluorine-containing surfactants are particularly preferably used.

The amount of the polyoxyethylene surfactant used in the present invention varies depending on the type, form, coating method, etc. of the photographic material used, but in general, the amount used is 7 moles of Ag in the photographic material. , owg or more, especially toη
The above is preferable.

The polyoxyethylene surfactant of the present invention is preferably added to a light-sensitive emulsion layer of a photographic light-sensitive material, but it may also be added to a non-light-sensitive layer.

As a hardening agent, for example, JP-A-ShojΔ-/≠2! It may be a polymeric hardening agent with diffusion resistance such as those described in Cog, or it may be a low-molecular hardening agent as shown below. Typical examples include mucochloric acid, mucobromic acid, formaldehyde, dimethylolurea, trimethylolmelamine, glyoxal, co, J-dihydroxy'/-1-methyl-
72 μm dioxane, aldehyde compounds such as glutaraldehyde; cyhinyl sulfone, methylene bismaleimide,! -acetyl/,3-diacryloyl-hexahydro-5-)riazine,/,! , j-triacryloyl-hexahydro-5-)riazine, /13. ! - Trivinylsulfonyl-hexahythro$-triazine, bis(vinylsulfonylethyl) ether, /, 3-bis(vinylsulfonyl)-coprobanol, /, J-bis(vinylsulfonylacetylamide) propane, etc. Compound; x, 4t-dichloro-bu-hydroxy-S-)rian sodium salt, 2. goojichloro
! -Methoxy5-triazine, '+μm dichlorobu-(cousulfoanilino)-5-triazine sodium salt, 2. Active rogen compounds such as II-dichloro-Δ-(2-sulfoethylamino)-S-)riazine, N,N/-bis(2-lyaloethyllupamyl)piperazine; bis(co,3- Epoxy compounds such as epoxyglopyl) methylpropylammonium-p-)luenesulfonate; Ko, Hiroshi, Futriethyleneimino S
- Ethyleneimine compounds such as triazine; l, metal sulfonic acid ester compounds such as cop(meth/sulfonoxy)ethane; calphosiimide compounds such as dicyclohexyl carmediimide; Examples include inoxazole compounds such as dimethyl isoxazole perchlorate; inorganic compounds such as alum alum and chromium acetate.

Particularly preferred among these compounds are vinyl sulfo/group-containing compounds and active nitrogen compounds.

The photographic emulsions of this invention are spectrally sensitized with meden dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioquinonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. Namely, pyrroline nucleus, oxazoline nucleus, thiacillin 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 these An aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a nucleus having a ketometidi2 structure, such as a pyrazoline-yone nucleus, a thiohydantoin nucleus, a cortioxazolidine nucleus, a kudione nucleus, a thiazo-lysine-1, lI-dione nucleus, a rhodanine nucleus, J-J membered heterocyclic nuclei such as deoparbituric acid nuclei can be applied.

The amount of the sensitizing dye used in the present invention is preferably from X10@-6 to Z.times.10@-3 mol/mole of silver.

The photographic emulsion of the present invention may contain a color image-forming coupler, that is, a compound (hereinafter abbreviated as coupler) that reacts with the oxidation product of an aromatic amine (usually a primary amine) developing agent to form a dye. The coupler is preferably a non-diffusible coupler having a hydrophobic group called a pallast group in its molecule. The coupler may be either μ-equivalent or λ-equivalent to silver ions. It may also contain a colored coupler that has a color correction effect or a coupler that releases a development inhibitor upon development (so-called DIR coupler).The coupler may be a coupler in which the product of the coupling reaction is colorless.

As the yellow coloring coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide-based and piparoylacetanilide-based compounds are advantageous.

As the magenta coupler, pyrazolone compounds, indacylon compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous.

As the cyan coupler, phenolic compounds, naphthol compounds, etc. can be used.

The protective layer of the silver halide photographic light-sensitive material of the present invention is a layer consisting of a hydrophilic colloid, and the hydrophilic colloid used is one described above.

Further, the protective layer may be a single layer or a multilayer.

A matting agent and/or a smoothing agent may preferably be added to the emulsion layer or protective layer of the silver halide photographic material of the present invention. Examples of matting agents include polymethyl methacrylate with a suitable particle size (the particle size ratio of 0.J to jμ is preferably at least 1 times the thickness of the protective layer, especially at least 1 times the thickness of the protective layer). Organic compounds such as water-dispersible vinyl polymers, and inorganic compounds such as silver halide and barium strontium sulfate are preferably used. Smoothing agents are similar to matting agents and are useful in preventing adhesion failures, as well as improving the frictional properties of motion picture films, especially those related to camera compatibility during filming or projection; a specific example is liquid paraffin. , waxes such as esters of higher fatty acids, polyfluorinated hydrocarbons or their derivatives, polyalkylbilisiloxanes, polyalline poly70xane, polyalkylarylpolysiloxanes, or their fullylene oxide addition derivatives. Silicones such as the like are preferably used.

The silver halide photographic material of the present invention may also be provided with an intermediate layer, a filter layer, etc., if necessary.

Specific examples of the silver halide photographic material of the present invention include Fixls light-sensitive materials, Lith light-sensitive materials, black-and-white photographic light-sensitive materials, color negative light-sensitive materials, color reversal light-sensitive materials, and color photographic paper.

Preferably, a negative photosensitive material is used.

Various other additives may be used in the photographic material of the present invention, if necessary. Examples include development accelerators, fluorescent whitening agents, color antifoggants, and ultraviolet absorbers. Specific research disclosure (RES)
EARCHDISCLO8URE)/7j No. 21-3
The one described on page 0 (几D-/7Aguj, /978) can be used.

Also, regarding the development processing of the photosensitive material of the present invention, RD-17
643, pages 28 to 3o, can be referred to.

The present invention will be illustrated below with reference to Examples, but the present invention is not limited thereto.

Example - A corona discharge treatment was performed on an axially stretched polyethylene terephthalate film having a thickness of 175 μm and dyed blue, and a coating amount of the 101st undercoating liquid having the following composition was 5.
．． The 201st undercoat layer was applied in the same manner on the opposite side of the 0th layer, which was coated with a wire bar coater at a rate of 1 cc/n and dried at 175° C. for 1 minute.

101,201st undercoat layer■ 27.45g of emulsion with the following composition per 100g 0 3.2g of gelatin A second undercoat liquid (102,202) having the following composition is applied on the first undercoat layer on both sides of the above. The amount is 8.5cc/n (
The undercoated films 1 to 9 were completed by coating and drying to give the following results.

No. 102.202 Undercoating liquid composition ■ Gelatin 40 g ■ Mordant: Listed in Table 1 ■ Dye: Listed in Table 1 ■ C,, lI□0(CHtCHxO)+, H1% aqueous solution 100 ec ■ Mantle agent average particles 4.0g of polymethyl meta with a diameter of 2.5μm 0.4g Acrylate 0.3g or more Φ~■
Add water and adjust to 11.

1 Ton 11 Gokyu Zao Seisui 11 contains 5 g of potassium bromide, 0.05 g of potassium iodide, 30 g of gelatin 1 thioether lo(Cut)ms(Cut)ms(Cut)golf
Add 2.5 ee of a 5% aqueous solution of nitric acid! into the solution kept at 75°C while stirring! 18.33g of aqueous solution,
An aqueous solution containing 5.94 g of potassium bromide and 0.726 g of potassium iodide was added in 45 seconds using a double jet method. Subsequently, after adding 2.5 g of potassium bromide, 8.33 g of silver nitrate was added.
An aqueous solution containing g was added over a period of 7 minutes and 30 seconds so that the flow rate at the end of addition was twice that at the start of addition. Subsequently, an aqueous solution of 153.34 g of silver nitrate and an aqueous solution of potassium bromide were added,
It was added over 25 minutes using a controlled double jet method while maintaining the potential at pAg 8.1. The flow rate at this time was accelerated so that the flow rate at the end of addition was eight times the flow rate at the start of addition. After the addition is complete, 2N potassium thiocyanate solution 15
cc was added, and then 50 cc of a 1% aqueous potassium iodide solution was added over 30 seconds. After that, lower the temperature to 35℃,
After removing soluble salts by the sedimentation method, the temperature was raised to 40°C, 68 g of gelatin, 2 g of phenol, and 7.5 g of trimethylolpropane were added, and the pH was adjusted to 6,552 and pAg to 8.10 with soluble soda and potassium bromide. did.

After raising the temperature to 56°C, a sensitizing dye having the following structure was added in the amount shown in Table 1. After 1 a minute, sodium thiosulfate pentahydrate 5.5 #potassium thiocyanate 16:1 v and chloroauric acid 3.6 μl were added, and after 5 minutes, it was rapidly cooled and solidified. In the resulting emulsion, 93% of the total projected area of all grains consists of grains with an aspect ratio of 3 or more, and the average projected area diameter of all grains with an aspect ratio of 2 or more is 0.83μ.
m, standard deviation 18.59A, thickness average 0.161μ
m and the aspect ratio was 5.16.

S03''5OJa The following chemicals were added to this emulsion per 111 moles of halogen to prepare a coating solution.

・2.6-bis(hydroxyamino)-4-diethylamino-123゜5-triazine 94.5■ ・Sodium polyacrylate (average molecular weight 4,10,000) 2.7gH ・Ethyl acrylate/acrylic acid/methacrylic acid - 24.8 g of copolymerized plasticizer with a composition ratio of 95/2/3/potassium bromide 77 It was applied to both sides of ~9. (Structure A) At this time, the coating amounts of the emulsion layer and surface protective layer per side were as follows.

(Emulsion layer> Coated silver amount 2.1 g/n (- Coated gelatin 1 1.7 g/n (- Polyacrylamide (average molecular weight 45,000) 0.47 g/my surface protective layer) - Gelatin 1.4 g/n rd・Polyacrylamide (average molecular weight 45,000) 0.23g/rr?・Cloak agent (average particle size 3.5μm) Co-electropolymer of polymethyl methacrylate/methacrylic acid = 9:1 0.05g/n (・Sodium polyacrylate (average molecular weight 4.41 million) 23 ■/M ・4-hydroxy-6-methyl-1,3,3a,7-titrazaindene 21.7 ■/M Hardener is 1
．． 2-bis(sulfonylacetamido)ethane was coated at a rate of 51 curvature/rd per side.

In this way, photographic materials 1 to 9 were produced.

Crossover Evaluation A G-4 screen from Fuji Photo Film Co., Ltd.'s GRENEx series was used as the screen for exposure of photographic materials 1 to 17. In accordance with a conventional method, one sheet of G-4 screen was superimposed on the surface protective layer-1 side of photographic materials 1 to 17, and xtan light was applied through a 10 cm water fan dome.

It is expressed as the ratio of the sensitivity on the front side and the sensitivity on the back side.

○: No problem Δ: There is some residual color, but there is no practical problem. ×: Problem.

(iii) MT F's above 04
The MTF was measured when a photographic material was sandwiched tightly between two screens and processed in an automatic processor. Measured with an aperture of 30 μm x 500 μm,
The spatial frequency was 2.0 cycles/Uro's MTF value. Optical density post-exposure processing was carried out at 35°C using Fuji Photo Film's RD-III as the developer and Fuji F as the fixer. The film was processed using an automatic processor using FPM-4000 manufactured by the same company. (Processing time is dry.

dry for 90 seconds) (ii) Evaluation of residual color It was processed in the same manner as in (i) and residual color was evaluated.

<Configuration-A) Surface protective layer-1 Emulsion layer-1 Undercoat layer-102 Undercoat layer-101 Support undercoat layer-201 Undercoat layer-202 Emulsion layer-2 Surface protective layer-2 <Configuration-B) Surface protective layer -1 Emulsion layer-1 Dye fixing layer-1 Undercoat layer-102 Undercoat layer-101 Support undercoat layer-201 Undercoat layer-202 Emulsion layer-2 Surface protective layer-2 (Configuration-C) Surface protective layer-1 Emulsion Layer-1 Dye fixing layer-1 Undercoat layer-102 Undercoat layer-101 Support undercoat layer-20! Undercoat layer-202 Dye fixing layer-2 Emulsion layer-2 Surface protective layer-2 First surface dye F4-2 Compound-1 'ASOtte x:y:z=20:4:16 (molar ratio) (b) - +CHICH)-0OH (a) : (b) =57°1:42°Dye-1 Table 2 As can be seen from Table 2, the sample having the structure of the present invention was Comparative Example 9.
The sharpness has improved significantly, compared to the comparison example! , 2.5.6, the coating process was simple, and the surface variation was small.

Example 2 1. Undercoated film Primed film 9 of Example 1 was used.

2. Preparation of photographic material Structure and structure C (comparative example) The emulsion layer and surface protective layer were applied in the same manner as in Example 1, and the dye fixing layers -1 and -2 were applied by the method described in Table 3. Materials IO-13 were created. (However, gelatin was coated at 2g/rrr) 3. Evaluation of photographic performance (i), (ii) (in) As can be seen from Table 3, which is the same as in Example 1, the sample with the structure of the present invention is a comparative example. The coating process had the same sharpness as the previous one, but the cost was reduced.

Claims (1)

[Claims] The support has at least one photosensitive silver halide emulsion layer on each side, and only one side has a layer containing a dye, and the cross-over light is reduced to 10% or less, and the dye is 1. A silver halide photographic material which is decolorized by processing within 90 seconds.