JPH03211542A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To make it possible for an automatic processor to easily detect the position of a sensitive material by specifying the total amt. of silver applied to the sensitive material and incorporating at least one kind of specified compd. CONSTITUTION:The total amt. of silver applied to a sensitive material having a photosensitive silver halide emulsion layer is regulated to <4.0g/m<2> and a compd. represented by formula I is incorporated into the sensitive material. In the formula I, each of R1 and R2 is alkyl, alkenyl or aryl, each of R3 and R4 is H or a monovalent group, each of Z1 and Z2 is a group of nonmetallic atoms required to form a 5- or 6-membered N-contg. hetero ring, L is a combining group formed by combining five, seven or nine methine groups by conjugate double bonds, X<-> is an anion and each of l1 and l2 is 0 or 1. A film detector can always detect the position of the sensitive material without affecting the photographic properties.

Description

Detailed Description of the Invention [Field of Industrial Application] This FIA relates to silver halide photographic light-sensitive materials, particularly for black and white halogen/kasen photographic material pr fully automatic developing machine C and below.
The present invention relates to a technique for making it easier to detect the position of a photosensitive material when processing it by self-imaging.

[Prior Art] In recent years, there has been a strong need for rapid processing of photosensitive materials, and systems that can complete the processing process in aS seconds are beginning to become popular, especially for photosensitive materials that use X-rays. There is also a growing need to reduce replenishment of secondary processing liquid. This trend to reduce the amount of silver coated is a major trend. At this time, the light-shielding performance of the infrared sensor installed in the transport system, including the automatic processor (automatic processor), decreases, making it impossible to detect the position of the photosensitive material and causing transport failure. .

Tokukai Showa 6 Coco 22 Ri! No. 2 discloses a method for improving detection defects by using an infrared expansion absorption color It is necessary to carry out the processing process (
4? In addition, the dye itself has absorption in the visible range, which poses a problem as residual color in black-and-white photosensitive materials in which toned images are observed. As described in Japanese Patent Application Laid-open No. 43-31/36, a method for improving detection defects using light-scattering particles such as silver halide particles is disclosed, but refractive yIIA? : Since it is only used, the effect of interlocking on the sensor is small, and in the case of silver halide grains, it puts a burden on the Fix (fixing solution), so it is very important to reduce the amount of replenisher and to perform quick processing. It's getting tough.

[Purpose of the invention]

The purpose of the present invention is to use a silver halide source material with a small amount of silver coated, to enable rapid processing in a processing system that requires little replenisher, and to detect film without affecting photographic properties. It is an object of the present invention to provide a photographic material made to eliminate undetectability of the apparatus.

[Structure of the invention]

The object of the present invention is to provide a photographic light-sensitive material having at least seven light-sensitive silver halide emulsion layers on at least one side of the support, in which the total coating amount of the II & optical material is at least 7 or 7 layers.
m less than 2, and the following general formula (I) or It
It has been found that the following can be achieved by a silver halide photographic light-sensitive material characterized by having at least seven types of compounds represented by /).

General formula (I) In the formula, R1 and R2 each represent an alkyl group, an alkenyl group, or an aryl group, and R3 and R4 each represent a hydrogen atom or 7
Value base f: Ujiwashi, Zl, Z2Fi each! Or the non-gold Ij necessary to form a 4-membered nitrogen-containing biplane ring! 4 atomic groups, LFij, 7 or 2 methi/groups are connected by a conjugated double bond to form a linking group, X- represents an anion, 11.12 represents O or l, respectively. I am.

General formula (It) In the formula, Q and Q□ each represent an oxygen atom or an ion atom, R5, R6, R7, and R8 each represent a water atom or a Fi/valent group, and L is 3 or ! Y#'
i cycloba/represents a nonmetallic atom group necessary to form a tenyl ring or a cyclohexenyl ring, and X- represents an anion/.

General formula (I111) In the formula, RR and R□□ each represent a hydrogen atom or g~10 represents a monovalent group, '12Vi each represents an alkyl group, an alkenyl group, or an aryl group, and Z3 represents a six-membered represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle, n represents co or all 3, 13 represents O or /,
X- represents an anion.

General formula (IV) In the formula, 几, 3, 几□4, R13, fL16 represent hydrogen or a lower alkyl group, X- represents an anion, m is 0. / or 2, and may be substituted with all the aromatic nuclei Fi/valent groups present as L2tj.

One of the characteristics of the light-sensitive material of the present invention is that the total amount of coated silver is less than 0.097 m2, particularly preferably 0.09 m2 or less.
2~J, js'/ff12, S also known as KS. Here, "total" refers to all of these silver halide emulsions when there are multiple layers of silver halide emulsion layers, or when there are seven or more layers of silver halide emulsion layers on both sides of the support. Calculate the total amount of silver coated in the layer.

The alkyl group represented by R and R2 in general formula (I) preferably has carbon atoms/~! lower alkyl group (e.g. methyl group, ethyl group, n-propyl group, n-butyl group, isopropyl group, n-:methyl group, etc.), substituent group (e.g. several sulfone groups, carbo/acid group, hydroxyl group) etc.). More preferably, R1 and R2 have a nurphonic acid group and have a carbon number/~! lower alkyl group (
For example, Fi cornulfoethyl group, 3-nurfoprovir group,
≠-nurphobutyl group, etc.).

Nurho group is a nurpho group or its salt, which is a primary carme/
The acid group means a carboxyl group or a salt thereof. Examples of salts include alkali metal salts such as Na, monium salts, triethylamine/, tributylamide/,
Mention may be made of Vacetic acid/moniwaum salts such as pyridine/etc.

The aryl group represented by R1 and R2 includes substituted or unsubstituted phenyl groups (eg, phenyl, p-sulfophenyl, p-carboxyphenyl, p-hydroxyphenyl, etc.).

Examples of the alkenyl group substituted by R1 and R2 include &-substituted or unsubstituted lower alkenyl groups (with a maximum number of carbon atoms).

More preferred among the groups represented by R1 and 72 is a lower alkyl group having 1-1 carbon atoms and having a sulfonic acid group. (Synonymous with the above) The heptavalent group represented by It3 and R4 includes an alkyl group with carbon number/~r (e.g., methyl, ethyl, t-butyl), an alkoxy group with °carbon number/~t (e.g., Methoxy, ethoxy, phenethyloxy, butoquine 7, octoquine, carboquine ethoxy]
, phenoxy group (e.g., unsubstituted phenoxy, p-chlorophenoxy), aryl group (e.g., carboxyl group, sulfo group, phenolic hydroxyl group, -NH802-
(substituted or unsubstituted phenyl, naphthyl), cyanide group, halogen atom (e.g., F, CIX Br, I
), carbo/acid group, 7 to ho/acid group, hydroxy group, sulfo/amide group (e.g., methanulphonamide, be/
Sulfamoyl groups (eg, unsubstituted nulfamoyl, methylnulphamoyl, ethylnulfamoyl, phenylnulfamoyl), etc. are preferred.

Z□, Z2 hits you six! Alternatively, f'i 6-membered nitrogen-containing heterocycle may be a fused ring, such as an oxazole ring, benzoxazole ring, inoxazole ring, naphthoxazole ring, thiazole ring, benzothiazole ring, naphthothiazole ring, indolenine ring, be/ Diindolenine ring, imidazole ring, be/shiimidazole ring, naphthoimidazole ring, quinoli/ring, pyridi/ring, imidazoquinoli/ring,
Examples include rings such as imidazoquinolyl/ring/ring and benzimidazole ring.

The linking group represented by L is a linking group Kl formed by linking 7 or more substituted or unsubstituted methy/groups via a conjugated double bond, and is particularly represented by the general formula (a) to e). Preferably.

General formula (a) -CH=CH-CH=C-CH=CH-CH.

General formula (b) General formula (C) General formula (d) ,,=CH-CH=CH-CH=C-CH=CH-CH
=C) 1-Heat general formula (e) In general formula (a) or e), Ye-! Navy atomic or heptavalent fund people. In this case, the heptavalent group is
Lower alkyl groups such as methyl groups, substituted or unsubstituted phenyl groups, aralkyl groups such as benzyl groups, lower alkoxy groups such as methoxy groups, dimethylamino groups, diphenylamine groups, methylphenylamino groups, morpholino groups, imidazolidiano groups The ethoxy carbonylbi group is preferably a di-substituted amino group such as a radino group, an alkylcarbonylokyne group such as an acetoxy group, an alkylthio group such as a methylnao group, a cyano group, a nitro group, or a halogen atom such as FSceSBr.

The acid ion represented by X- is a heptavalent or divalent ion that supplies all the negative charges necessary to neutralize the charge of the cation moiety.

Examples of anions represented by X- include α-Br-I
-etc. Nohalogen/ion, 5(J4”-H2O-1CH
3 (JS (J3-, etc., alkyl sulfate ion/, para-toluene-nulphonate ion, naphthalene-/, !-dinurpho/acid ion, methanulphon rR ion, trifluorometa/sulfonate io/, octane sulfonate ion/, etc.) Sulfo/acid ion, acetate ion/, p-chlorobenzoate ion, trifluoroacetate ion, oxalate ion/,
Carboxylic acid ions such as succinate io/, PF, -1B
F -1αU I(j, -1ta/Gnute/W!
! .

4 ion, heteropolyacid ion/ such as ta/gnutric acid ion, and phenolate ion/ such as HPU-1N (J3- picric acid ion).

The preferred anion containing X- is α-
1Br l-1CHUS(J3CH(JS(J3-
, para-toluene-nulphonate ion, p-chlorobenzene-nurphonate ion, meta/nurphonate ion/, butane-nurphonate ion, naphthalene 7
perfluoronurphonate ions such as −/, j-dinulfo/acid ions, trifluorometa/sulfo/acid ions,
PF, -1BF4α04-, etc., preferred in %, trifluorometa/sulfo/acid ion, PF.

α04-, and among these, trifluoromethane nulphonic acid io/ and PF,- are the most preferred since there is no risk of explosion.

Particularly preferable formulas (I) are those in which Z□ and z2 each represent a quinol/ring, and L is a tri- or tetracarbocyani/linking group necessary to form a total of X, and It contains at least two sulfo/acid groups in the dye molecule.

In general formula (I[), monovalent groups represented by R5, R6, R7, R8 include R3, R4 in general formula (I)
is synonymous with Furthermore, a fused ring may be formed.

The methi/group represented by Ll is 3 or! All linking groups formed by linking two substituted or unsubstituted methine groups via a conjugated double bond are included. As a substituent, general formula (I)
Some of the friends I mentioned are:

The anion represented by X- has the same meaning as X- in general formula (I).

Among the compounds represented by the general formula (II), more preferred are those containing at least one Nurho yrj11 group in the dye molecule.

In the general formula (III), Ro, a heptavalent group represented by "10%" 11, an alkyl group, an alkenyl group, an aryl group represented by R1, a j- or t-membered group represented by z, 9 The anion represented by the eleven ring and X- is,
It has the same meaning as the general formula CI) described above.

More preferred among the compounds represented by formula (III) are those containing at least two sulfo/acid groups in the dye molecule.

According to the general formula (I1/), R13, 几, 4, R□5,
The lower alkyl group represented by R16 has a carbon number of 1 to 6 (more preferably a sulfo/acid group, a carbo/acid group,
Hydroxyl group, -NH8 (J2R23 (R23 is the same as above)
Examples of heptavalent groups include
It has the same meaning as those listed in general formula (I).

General formulas (I) and (II) used in the present invention are shown below.
), ([1) and (fV)], but the scope of the present invention is not limited thereto.

1-/I-Co[[-/ 1[1-J ■-Suffering6''5 /-1\ ≧ /-1\ ≧ The dye of general formula (I) of the present invention is JP-A-Sho≠t- l≠13
No. 0, same! λ-//(77λ7, same t call l-3≠j
Da No., F.M. Barmer (F.

“The Ciani/Soybeans & Related Co./Pounds” (“Thec.
yaniae dies and related
Inter 5science Pu
"Heterocyclic Compounds/Zoo Special Tobitsukunu" published by D. M. Sturmer
-8special topics in hetero
ocyclic cberr++5try -) show/
・Quiley & S/s (John Wiley &
It can be synthesized according to the method described in 8ons), published in 1977.

The dye of general formula (If) is disclosed in U.S. Patent No. 3,4117° or
, y, (In) dye ti% open fif3jtO-9!
The dye No. 32da and (■) can be synthesized by referring to the method described in Japanese Patent Publication No. 3-2!335.

Gelatin is a typical hydrophilic colloid used in the present invention, but any other conventionally known hydrophilic colloids that can be conveniently used for photography can be used.

The organic color chips useful in this invention can be used in a defined amount to absorb infrared element fR, but not all of them in an amount and location such that they are solubilized and washed away during the development process. It is particularly advantageous to use If it is desired to absorb only a small amount of KFi, only a small amount of dye is needed. If absorbing larger amounts of dye is burdensome, 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 of /~1000 η/f12.

Photographic processing of the light-sensitive material of the present invention includes, for example, Lipuchi Disclosure 7F No. 6, pp. 21-30 (RD-1
Any of the known methods and known processing solutions for black-and-white photographic processing, such as those described in US Pat. No. 7,643, can be applied. The processing temperature is usually selected between 18°C and 50°C, although temperatures below 18°C or above 50°C may also be used, although processing in an automatic processor at temperatures between 20°C and 40°C is preferred for the present invention. In this case, the processing time (time from loading the photosensitive material until it comes out after drying) is 10 seconds to 5 seconds.
Up to 1 minute is preferred, and 15 seconds to 3 minutes and 30 seconds is particularly preferred.

The developer used in black-and-white photographic processing can contain known developing agents. As the developing agent, -dihydroxybenzene R (e.g. hydroquinone), 3
-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-
p-aminephenol, etc.) can be used alone or in combination. The developer generally contains a preservative, an alkaline agent, a pH 1L buffer agent, an anti-fogging agent, etc., as well as a solubilizing agent, a toning agent, a development accelerator (
For example, quaternary salt, hydrazine, benzyl alcohol),
It may also contain development inhibitors (eg, iodides, bromides, mercapto compounds, triazoles, etc.), surfactants, antifoaming agents, water softeners, hardeners (eg, glutaraldehyde), tackifiers, and the like.

As a special form of development processing, a developing agent is added to the light-sensitive material.
For example, among the developing agents that are contained in the emulsion layer and may be developed by processing the light-sensitive material in an alkaline aqueous solution, hydrophobic ones are disclosed in Research Disclosure No. 169 (RD16928) and US Pat. 2,739
, 890, British Patent No. 813,253 or West German Patent No. 1.547.763. Such development treatment may be combined with silver salt stabilization treatment with thiocyanate.

As the constant i solution, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

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

Also, JP-A-61-230135 and JP-A-63-25653
The effect of the present invention becomes even more favorable when a compound that releases an inhibitor during development is used in combination, as described in .

As the silver halide in the photosensitive silver halide emulsion used in the present invention, silver chlorobromide, silver bromide, silver iodobromide, and silver chloroiodobromide can be used, but silver iodobromide is preferably used. It will be done. Here, the content of silver iodide is preferably 30 mol% or less,
In particular, it is preferably within a range of 10 mol% or less. The distribution of iodine in the silver iodobromide grains may be uniform or different between the inside and the surface, and the average grain size is 0.4 μm.
The particle size distribution is preferably 0.5 to 2.0 μm or more, and may be narrow or wide.

The silver halide grains in the emulsion may have regular crystal shapes such as cubic, octahedral, tetradecahedral, rhombic dodecahedral, or irregular crystal shapes such as spherical, plate-like, potato-like, etc. It may have an irregular crystal form or a composite form of these crystal forms, it may consist of a mixture of particles of various crystal forms, and it may be a flat plate with a particle diameter of 5 times or more the particle thickness. Particles are preferably used for the present invention (in particular, RES
EARCHDrSCLO5UIIE225t'1ten
22534P, 20-P, 58. January issue, 1983, and JP-A No. 58-127921, No. 58-1139
(described in Publication No. 26).

In the present invention, the photosensitive silver halide emulsion may be a combination of two or more types of silver halide emulsions, or the emulsions to be mixed may differ in grain size, halogen composition, sensitivity, etc. substantially non-photosensitive emulsion (
(The surface or interior may or may not be covered) may be mixed and used, or may be separated into separate layers (for details, see U.S. Pat. No. 2,996,382, No. 3, 3
97.987, etc.) 0 For example, in the same layer as a photosensitive silver halide emulsion consisting of a spherical or potato-shaped photosensitive emulsion and a tabular grain with a grain size of 5 times or more the grain thickness, or in JP-A No. 97.987, etc. When used in different layers, the light-sensitive silver halide emulsion consisting of tabular grains may be on the side closer to the support, or vice versa, as described in Japanese Patent No. 58-127921. It may be on the far side.

The photographic emulsion used in the present invention is P, GIafkides.
AuthorChtmie et Physique Photo
graphique (Paul l'1onte1, 1967), Pho by G. F. Duffin
tographic Emulsion Chem
istry (The Focal Press, 19
1966), V, L, Zelikman eta
1 AuthorMaking and Coating Photo
Graphic Emulsion (The Foca
1 Press, 1964), Japanese Patent Publication No. 1983-127
It can be adjusted using the methods described in No. 921 and No. 58-113926. 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. .

A method in which silver halide grains are formed in an excess of silver ions (so-called back mixing method) can also be used. As one type of simultaneous mixing method, a method of keeping I) Ag in the liquid phase in which silver halide is produced, ie, a so-called Chondrald double jet method, can also be used. According to this method, a silver halide emulsion consisting of silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained.

Even if the crystal structure of silver halide grains is similar to the inside, there are also those with a layered structure with different inside and outside, British Patent No. 635,841, US Patent No. 3,622.3
In the process of silver halide grain formation or physical ripening during silver halide production, cadmium salt, zinc salt, lead salt, thallium salt, which may be of the so-called conversion type as described in No. 18. , an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together.

Further, during grain formation, grain growth may be controlled by allowing so-called halogenated wire solvents such as ammonia, thioether compounds, thiazolidine-2-thione, tetrasubstituted thiourea, rhodanpotash, rhodanammonium, and amine compounds to be present.

The silver halide emulsion used in the present invention may or may not be chemically sensitized. Chemical sensitization methods include known methods such as sulfur sensitization, reduction sensitization, and gold sensitization. A number of methods can be used, used alone or in combination.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a gold complex salt. There is no problem in containing complex salts of noble metals other than gold, such as platinum, palladium, and iridium.
No. 618.061, British Patent No. 618.061, etc.

As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used.

As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles (e.g. benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.); mercapto compounds (e.g. mercapto Tothiazoles,
mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially l-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, etc.; thioketo compounds such as oxadorinthion; azaindene (e.g. triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (I, 3, 3a, 7) tetraazaindenes), pentaazaindenes, etc.); benzenethiosulfonic acid, benzenesulfinic acid, benzene A number of compounds known as antifoggants or stabilizers can be added, such as sulfonic acid amides.

In particular, nitrone and its derivatives described in JP-A-60-76743 and JP-A-60-87322, JP-A-60-8
Mercapto compound described in Publication No. 0839, JP-A-57
The heterocyclic compound described in Japanese Patent No. 164735, and the complex salt of a tetracyclic compound and silver (for example, 1-phenyl-5-mercaptotetrazole!) can be preferably used.

The photosensitive silver halide emulsion of the present invention may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using a sensitizing dye. Dyes such as complex cyanine dyes, complex merocyanine dyes, holophoradianine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, and hemioxonol dyes can be used.

The aggravating dye can be present in any step of the photographic emulsion manufacturing process, or can be present at any stage up to immediately before fabrication. Examples of the former include a silver halide grain formation process, a physical ripening process, and a chemical ripening process.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention includes coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast, sensitization). Various surfactants may be included for various purposes.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene oxide adducts of silicones), alkyl esters of sugars. Nonionic surfactants such as; alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates,
Anionic surfactants such as N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers;
Amphoteric surfactants such as alkylbetaines and alkylsulfobetaines; cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, pyridinium salts, and imidazolium salts can be used. Of these,
saponin, dodecylbenzenesulfone 1lNa salt, di-
2. Ethylhexyl α-sulfosucci fljNa salt, p
-Anions such as octylphenoxyethoxyethoxyethoxyethanesulfone rlINa salt, dodecyl sulfur 12Na salt, triisopropylnaphthalenesulfonic acid Na salt, N-methyl-oleoyl taurine Na salt, dodecyltrimethylammonium chloride, N-oleoyl-N ',
Cations such as N',N'-trimethylammoniodiaminopropane bromide and dodecylpyridium chloride, betaines such as N-dodecyl-N, N-dimethylcarboxybetaine, N-oleyl-N, and N-dimethylsulfobutylbetaine, poly( Average degree of polymerization n = 10) oxyethylene cetyl ether, poly(n-25) oxyethylene p-nonylphenol ether, bis(I-poly(n-15) oxyethylene-oxy-24-di-t
-Pentylphenyl)ethane and other nonions can be particularly preferably used.

As an antistatic agent, perfluorooctanesulfonic acid salt, N-propyl-N-perfluorooctanesulfonylglycine Na salt, N-propyl-N-perfluorooctanesulfonylaminoethyloxypoly (n=3)
Oxyethylene butanesulfone aNa salt, N-perfluorooctanesulfonyl-N',N',N'-)limethylammoniodiaminoprobane chloride, N-perfluorodecanoylaminopropyl N',N'dimethyl-
Fluorine-containing surfactants such as N'-carboxybetaine,
JP 60-80848, JP 61-112144,
Nonionic surfactants, alkali metal nitrates, conductive tin oxide, zinc oxide, vanadium pentoxide, or composite oxides doped with antimony or the like, as described in Japanese Patent Application No. 61-13398, No. 61-16056, etc. can be preferably used.

In the present invention, fine particles of a homopolymer of polymethyl methacrylate or a polymer of methyl methacrylate and methacrylic acid, an organic compound such as starch, or an inorganic compound such as silica, titanium dioxide, etc. can be used as the capping agent. It is preferably 1.0 to 10 μm, particularly 2 to 5 μm.

The surface layer of the photographic light-sensitive material of the present invention may contain silicone compounds described in U.S. Pat. No. 3,489,576 and U.S. Pat. In addition, paraffin wax, higher fatty acid esters, starch derivatives, etc. can be used.

Polyols such as trimethylolpropane, bentanediol, butanediol, ethylene glycol, and glycerin can be used as plasticizers in the hydrophilic colloid layer of the photographic material of the present invention. Further, the hydrophilic colloid layer of the photographic material of the present invention preferably contains a polymer latex for the purpose of improving pressure resistance. Examples of the polymer include a homopolymer of an alkyl ester of acrylic acid or a copolymer with acrylic acid; Styrene
Butadiene copolymers, polymers or copolymers consisting of monomers having active methylene groups can be preferably used.

The photographic emulsions and non-photosensitive hydrophilic colloids of the present invention may contain inorganic or organic hardeners.

For example, chromium salt, aldehyde 1! (Formaldehyde,
(crytalaldehyde, etc.), N-methylol compounds (
dimethylol urea, etc.), active vinyl compounds (I, 3,
5-Triacryloyl-hexahydro-S-triazine, bis(vinylsulfonyl)methyl ether, N,N'
-methylenebis-[β-(vinylsulfonyl)propionamide], etc.), active halogen compounds (2,4-dichloro-6-hydroxy-3-triazine, etc.), mucohalogen acids (mucochloric acid, etc.), N-carbamoylpyridinium salts 1! ((I-morpholinocarbonyl-3
-pyridinio)methanesulfonate, etc.), haloamidinium salts (I-(I-chloro-1-pyridinomethylene)pyrrolidinium, 2-naphthalenesulfonate, etc.) can be used alone or in combination. Among them, JP-A No. 53-41220, No. 53-57257, No. 5
Preferred are the active vinyl compounds described in US Pat. No. 9-162546 and US Pat. No. 60-80846 and the active halides described in US Pat.

When the photosensitive material of the present invention is used as an X-ray photosensitive material, the hydrophilic colloid layer should be hardened with these hardening agents so that the swelling ratio in water is 200% or less, particularly 150% or less. preferable.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

A variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of dextran, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polyacrylamide, and polyvinylimidazole.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin may be used, and hydrolysates of gelatin may also be used.

Among these, it is preferable to use dextran and polyacrylamide together with gelatin.

Regarding the development process of the present invention, the description in the above-mentioned Research Disclosure magazine can be referred to.

Next, the present invention will be explained in more detail with reference to Examples.

Example-1 (I) Preparation of silver halide emulsion A mixture of gelade/potassium bromide and water is heated to rz'c, and then a liquid equivalent amount of ammonia is put into a container, and the GIAg value f7 in the reaction container is Monodisperse silver bromide emulsion grains having an average grain size of 0.9 μm were prepared by adding an aqueous solution of silver nitrate and an aqueous solution of potassium bromide at a temperature of 0.40 μm by double jet method. The emulsion grains are ±4LO% of the average grain size.
The total number of particles was within f%. After desalting this emulsion, the pH was adjusted to 6.2, the PAg was adjusted to f and A, and the desired photograph was obtained by sensitizing the emulsion with gold and sulfur using sodium thiosulfate and chloroauric acid.

The <1oo) plane/(///) plane ratio of this emulsion was measured by the Kubelkamunk method and was found to be t/-. This was named Emulsion A.

(3) Preparation of emulsion coating liquid Emulsion Ai/f was weighed, dissolved in Hiroo'C by heating, and a methanol solution of near-infrared sensitizing dye structural formula 8-/<9×10
'M/I ratio 70d, ≠-Hydroxy-6-methyl-/, 3.3a, 7-chitrazainde/aqueous solution, coating aid aqueous solution of dodecylbenzene nulphonate, thickener polyvinylbe/zenulphonate An emulsion coating solution was prepared by adding the entire aqueous solution of the compound.

8-/r- 4AOoCK heated fc/Owt% Zea f7 aqueous solution, thickener polyethylene Nulfo: 4R soda aqueous solution, matting agent polymethyl methacrylate fine particles (average particle size 3.0 μm), hardening agent N, N /-ethylene vinyl (vinylsulfonylacetamide), a coating aid t-octylphenoxyethoxyethoxyeta/Nurfuo/ly! sodium aqueous solution, an aqueous polyethylene surfactant solution as an antistatic agent, and an aqueous solution of a fluorine-containing compound having the following structure. Add it to make a coating solution.

C3F17SCJ2N (C3H7) CH2CUCJK
Oyo UC8F1,5 (J2N (C3H,) (CH2C
It is heated to H2-usu□5Htao'c f/Ow
Add the following dye-7 to gelatin aqueous solution Ikg/73?
, Thickener Polyethylene Nulfonate Sodium Aqueous Solution, Hard [
rlN.

N/-ethylene bis-(hinyl sulfonylacetamide) aqueous solution, coating aid t-octylphenoquine ethoxylate 7
A pack coating solution was prepared by adding the ethaneurfluoro/sodium powder aqueous solution. However, the dyes of the present invention shown in Table I were added.

[Dye-/]

(6) Preparation of surface protective layer coating solution for pack layer 4'OoCV
Cmm and fc/owt % Zela f7 water fg liquid, thickener polyethylene fluoride/acid soda aqueous solution, matting agent polymethyl methacrylate fine particles (average particle size 3.0
μm), an aqueous solution of sodium t-octylphenoxyethoxyethoxyethoxyethane-7-ionate as a coating aid, an aqueous solution of a polyethylene surfactant as an antistatic agent, and an aqueous solution of a fluorine-containing compound having the structure shown below to prepare a coating solution.

C3F178CJ2NCC3H,)C1-12CO(J
K and C8F, 7S (J2N(C3H7) (
CH2Cl-12-(J+0.H) Apply the above pack coating solution to one side of the following polyethylene terephthalate support together with the pack's field protective layer coating solution to a gelatin coating amount of 4.
Coating ratio so that it becomes tf/m. Subsequently, on the opposite side of the support, first, an emulsion coating solution of emulsion A containing a near-infrared sensitizing dye and a surface protective layer coating solution for this were coated.
Coat it so that it becomes jf/m2, prepare a sample, and prepare it.

A corona discharge treatment was performed on a biaxially stretched polyethylene terephthalate film having a thickness of 775 μm, and a first undercoating liquid having the following composition was applied at a coating amount of j,/cc/m.
Apply with a wire percoater so that /y
Dry for 7 minutes at 0c, then apply the first undercoat layer on the opposite side in the same manner.

0.0% relative to latex solid content. Contains t1wt%.

On the undercoat layer on both sides of the above, apply the undercoat liquid having the following composition in a coating amount of 1. Rcc/m, apply on one side and both sides and dry to complete the primed film.

Second base coat liquid 0 gelatin 30? Evaluation of residual color Dmin was visually observed and residual color was evaluated.

O: No practical problems x 2 Practical problems Each of these samples was subjected to the following exposure, development, fixing, water washing, and drying processes using an image exposure/automatic development device.

Scanning exposure of IQ-7 seconds is performed using a semiconductor laser having a wavelength of 710 nm.

For development and fixing after jIyt, the following developer and fixer were used. The entire process, including fixing, washing, and drying, takes 70 seconds at a standard developing temperature of 3R 0C.

Developer solution Potassium hydroxide / 4, ? If ice vinegar @ i, r Sodium sulfite tOP Potassium carbonate
r, o y boric acid
3.0? diethylene glycol
/2. Of diethyl/triami/pentaacetic acid, Q
? ! -Methylbenzotriazole 0.62 Hydroquinone -! , Ofei-Hydroxymethyl-der-methyl-7-phenyl-3-pyrazolide/l・tst Potassium bromide λ, o by adding water/
I can finish it in l.

(Adjust to pHHIO2λj.) Fixer Ammonium Thiosulfate /4! Ofsodium sulfite (anhydrous) /j fethylenediamine/
Tetraacetic acid disodium dihydrate 0.0 ml Adjust pk to 4j with glacial acetic acid.

Add water to make total volume +it.

<Sensor Detectability> Ten samples each were inserted into an automatic developing film insertion slot and tested to see if they were detected.

This automatic developing machine has a pair of infrared light-emitting elements (see Figure 1) and light-receiving elements (see Figure 2) in the film insertion slot, and the inserted sample is infrared! ! By sufficiently shutting off the il, the insertion of the sample is detected, and the transport rollers are thereby activated to transport the film to the current tank.

Fixing performance with fixer replenishment f3/41> The level of run/grey constant layering was evaluated by reducing the fixer replenishment f3/41.

O: No practical problems! Sample base: A dye was prepared according to % Kaishot Kokotatata j2 (Comparison with a silver iodobromide emulsion (Ag amount: 0#7f/m2) with an average size of o, iriμ that has not been chemically ripened)
ye-/(7.1 WIg/"") was preliminarily mixed and then added to the dye layer coating solution and applied.

Hiku dye-/ Sample 7: % Kaisho AJ-/3//3! Simply prepared light scattering particles. (A silver iodobromide emulsion with an average grain size of 0.72 μm that has not been chemically ripened was coated at a rate of 7 tons) As can be seen from Table 7, the samples of the present invention had excellent sensor detectability, residual color, and fixation. You can see that you are satisfied with your sexuality and are excellent. Sample 6Fi uses a dye with low water solubility, so residual color is a serious problem.

[Brief explanation of drawings]

Figures 7 and 2 show the spectral sensitivity characteristics of the infrared light-emitting element (Figure 1) and the light-receiving element (Figure 2) in the film insertion slot of the automatic processing machine used in Example-/. The axis represents the wavelength range, the vertical axis in FIG. 1 represents the sensor relative brightness, and the vertical axis in FIG. 1 represents the sensor relative sensitivity.

Claims (1)

[Scope of Claims] A photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on at least one side of a support, wherein the total coated silver amount of the light-sensitive material is less than 4.0 g/m^2, A silver halide photographic material comprising at least one compound represented by the following general formulas (I) to (IV). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 and R_2 each represent an alkyl group, alkenyl group, or aryl group, R_3 and R_4 each represent a hydrogen atom or a monovalent group, and Z_1 , Z_2 each represent a group of nonmetallic atoms necessary to form a 5- or 6-membered nitrogen-containing heterocycle, and L represents a linking group formed by linking 7 or 9 methine groups via a conjugated double bond. , X^- represents an anion, and l_1 and l_2 each represent 0 or 1. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Q and Q_1 represent an oxygen atom and a sulfur atom, respectively, and R_5, R_6, R_7, and R_8 each represent a hydrogen atom or a monovalent group, L_1 represents a linking group formed by connecting 3 or 5 methine groups via a conjugated double bond, Y represents a group of nonmetallic atoms necessary to form a cyclopentyl ring or a cyclohexynyl ring, and X^ - represents an anion. General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_9, R_1_0, and R_1_1 each represent a hydrogen atom or a monovalent group, R_1_2 represents an alkyl group, alkenyl group, or aryl group, and Z_3 represents a It represents a nonmetallic atomic group necessary to form a 5- or 6-membered nitrogen-containing heterocycle, n represents 2 or 3, l_3 represents 0 or 1, and X^- represents an anion. General formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1_3, R_1_4, R_1_5, R_1_
6 represents hydrogen or a lower alkyl group, X^- represents an anion, m is 0, 1 or 2, and L_2 has a numerical formula, chemical formula, table, etc. (l_4 is 1 or 2) or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (provided that m is 2), and all aromatic nuclei present may be substituted with monovalent groups.