JPH03168739A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the photosensitive material which has a high sensitivity to IR light, does not degrade the sensitivity during preservation and decreases fogging by incorporating specific silver halide particles into this material and incorporating at least one of hardening agents therein. CONSTITUTION:The photosensitive silver halide emulsion layer contains the silver halide particles which are spectrally sensitized by at least one of the sensitizing dyes having >=5 (100) face/(111) face ratio and expressed by formula I or at least one of the sensitizing dyes expressed by formula II and contains at least one of the hardening agents expressed by formula III. In the formulas I, II, Y11, Y12 and Y22 respectively denote the nonmetal atom group necessary for forming a 5- or 6-membered nitrogenous heterocycle; R11, R12, R21 and R22 respectively denote substd. or unsubstd. alkyl groups, etc.; R13 to R15, R23 to R26 respectively denote a hydrogen atom, etc. In the formula III, L denotes a bivalent org. group; n31, n33 denote a positive integer; n32 denotes 0 or 1. Thus, the photosensitive material which has the high sensitivity to the IR light, does not degrade the sensitivity during preservation and decreases the fogging is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application J] The present invention relates to a silver halide photographic material having high sensitivity to infrared light, low fog, high contrast, and excellent storage stability.

[Prior Art] One of the exposure methods for photographic light-sensitive materials is to scan an original image and expose the silver halide photographic material based on the image signal to create a negative image or a positive image corresponding to the image on the original image. An image forming method using a so-called scanner is known. There are various recording devices that use a scanner-only image forming method, and glow lamps, xenon lamps, mercury lamps, tungsten lamps, light-emitting diodes, etc. have traditionally been used as recording light sources for these scanner-only recording devices. . However, all of these light sources have practical problems of low output and short lifespan. To solve these problems, there is a recording apparatus that uses a coherent laser light source such as a helium-neon laser, an argon laser, or a helium-cadmium laser as a scanner-type recording light source. These devices can provide high output, but the equipment is large, expensive, requires a modulator, and since they use visible light, the safe light of photosensitive materials is limited, making them difficult to handle. There are various problems.

On the other hand, semiconductor lasers are small, inexpensive, easy to modulate, and have a longer lifespan than the lasers mentioned above. Furthermore, since it emits light in the infrared region, a bright safelight can be used, which has the advantage of improving handling efficiency.

Even if a semiconductor laser with such excellent performance is used as a recording light source, a photosensitive material with high photosensitivity in the infrared region and excellent storage stability that can take full advantage of these characteristics can be obtained. The current situation is that this is not the case.

Furthermore, since infrared sensitized photosensitive materials generally have unstable sensitivity, special considerations such as refrigerated storage or frozen storage are required for storage of the photosensitive materials.

It is known that spectral sensitization technology is applied as one of the manufacturing technologies for photographic materials, which involves adding a certain type of cyanine dye to silver halide photographic emulsions to extend the sensitive wavelength range to longer wavelengths. It is being This spectral sensitization technology is applied not only to the visible region but also to the infrared region. For spectral sensitization in the infrared region, sensitizing dyes that absorb infrared light are used.
T heoryor the Photography
hic Process, 3rd Edition” (MacMilla
Published by n company in 1966) p. 198-p. It is described in 201. In this case, it is desirable that the emulsion has high spectral sensitivity, that is, high sensitivity to light in the infrared region, and that the change in sensitivity is small even during storage of the emulsion. For this purpose, many sensitizing dyes have been developed. These include, for example, U.S. Pat. No. 2,095,854;
856@, No. 2,955,939, No. 3,482
, No. 978, No. 3,552,974@, No. 3,57
No. 3,921, No. 3,582,344, etc. Further, many studies and reports have been made on supersensitization, which improves spectral sensitivity by using two or more types of sensitizing dyes together, or by using a sensitizing dye and a certain type of compound in combination. For example, U.S. Pat.
, No. 592,657, No. 3,635,721, No. 3,
No. 649,288, No. 3,669,672, No. 3,
Examples include JP-A No. 674,499, No. 3,695,888, No. 3,994,733, JP-A-63-89838, and JP-A-63-318544.

However, with such conventional spectral sensitization techniques using sensitizing dyes, it has not been possible to obtain light-sensitive materials with sufficient sensitivity and storage stability.

[Problems to be solved by the invention] The present invention has been made to solve the above problems,
An object of the present invention is to provide a silver halide photosensitive material that has high sensitivity to infrared light, does not suffer from a decrease in sensitivity during storage, and has low fog and high contrast.

[Means for Solving the Problems 1] The object of the present invention is to provide a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, in which the light-sensitive silver halide emulsion layer ( 100)
The plane/(111) plane ratio is 5 or more, and at least one sensitizing dye represented by the general formula [Ia 3 and the general formula [Ib
] A halogen characterized by containing silver halide grains spectrally sensitized with at least one sensitizing dye represented by the formula [II] and at least one hardening agent represented by the general formula [II]. This can be achieved using silver oxide photographic materials.

General formula [Ia] General formula [Ib] [In the formula, Y11, Y+2* Y21 and Y22 each represent a group of nonmetallic atoms necessary to form a 5- or 6-membered nitrogen-containing heterocycle, and R+1. R12. R21 and R2
2 represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group, respectively.

R13. R14, R+s, R23, R24, R25 and R26 are each a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a phenyl group, a penzyl W2 substituted or unsubstituted 7-alkyl group (the alkyl portion has 1 to 1 carbon atoms) 18, preferably 1 to 4), represents an aryl group, and W1 and W2 can also be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle.

Further, R+3 and R+s and R23 and R25 can be linked to each other to form a 5-membered ring or a 6-membered ring. ×
11 and X21 represent anions. n11, n12
, n 21 and n 22 represent O or 1. ]
General formula [I] CH2=CHS 02(CH.)n,,O+L-OqC
H2). ,,SO. CH=CH2 [wherein, ] represents a divalent organic group. b31, n33 represents a positive integer,
n32 represents O or 1. ] The present invention will be explained in more detail below.

The silver halide grains used in the present invention have the following general formula [
Ia ] and the following general formula [Ib
It is spectrally sensitized with a sensitizing dye represented by ].

General formula [Ia] General formula [Ib] In the formula, Y++ . Y+2. Y21 Ill5 and Y
22 each represents a nonmetallic atomic group necessary to form a 5- or 6-membered nitrogen-containing heterocycle, such as a penzothiazole ring, a naphthothiazole ring, a penzoselenazole ring, a naphthoselenazole ring, a penzothiazole ring, Examples include an oxazole ring, a naphthoxazole ring, a quinoline ring, a 3,3-dialkylindolenine ring, a benzimidazole nucleus, and a pyridine ring.

These heterocycles include lower alkyl groups, alkoxy groups, hydrooxyl groups, aryl groups, alkoxycarbonyl groups,
It may be substituted with a halogen atom.

Ra1. RI2. R21 and R22 each represent a substituted or unsubstituted alkyl group, aryl group or aralkyl group.

R+3. R+4. R+s, R23. R24, R25 and R26 each represent a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a phenyl group, a penzyl W1/ group, or -N. Here, W1 and W2 each represent a substituted or unsubstituted alkyl group (alkyl moiety has 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms) or an aryl group, and W1 and W2 are connected to each other to form a 5-membered Alternatively, it can also be in the form of a 6-membered nitrogen-containing heterocycle.

Further, R+3 and R+5 and R23 and R25 can be connected to each other to form a 5-membered ring or a 6-membered ring.

X++ and X21 represent anions. When forming an inner salt, l 14 . If 2+ is 0. n1
1,n+2. n 21 and n 22 represent O or 1.

Next, specific examples of the sensitizing dye represented by the general formula [1] or the general formula [I] (hereinafter referred to as the sensitizing dye of the present invention) will be shown, but the present invention is limited thereto to Exemplary Compound 1 -1 1-2 !-3 1-4 D○ 1-5 1-6 1-7 1-8 Ie I-9 I -10 1 -11 ■-12 IO 1-13 !-14 !-15 1- 16 ■○ Ic) ■-17 ■-18 I-19 r-zo I C 2 H s ■-21 ■-22 I-23 1-24 1o CH, CH. OH Tech○ IO The sensitizing dye used in the present invention is preferably 1 mg to 2 g, more preferably 5 mg to 1 g per mole of silver halide.
It is contained in the silver halide emulsion within the range of Q.

The sensitizing dye used in the present invention can be directly dispersed into the emulsion. Alternatively, they can be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof, and then added to the emulsion in the form of a solution.

The sensitizing dye used in the present invention may be used alone,
Two or more types may be used in combination. Moreover, sensitizing dyes other than those mentioned above can also be used in combination.

When a sensitizing dye is used in combination, it is preferable that the total amount is the above content.

The sensitizing dye represented by the general formula [Ia] or [Ib] is disclosed in US Pat. No. 2,503,776, British Patent No. 742,112, French Patent No. 2,065,662, It can be easily synthesized with reference to No. 40-2346.

Further, in the present invention, the sensitizing dye may be added at any time, usually during grain formation, before chemical ripening, during chemical ripening, or after chemical ripening.

The silver halide photographic material of the present invention has the general formula [II]
Hardened with at least one hardener represented by:

General formula [II] CH. =CHSO, (CH2)n, ○+L O+Fr
2(CH2)n-SO-CH=
In the C H 2 formula, 1 represents a divalent organic group. n1, n
3 represents a positive integer, and n2 represents O or 1.

The divalent group represented by the general formula [II] is preferably an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a heterocyclic group, -0--S--So-
A divalent group represented by -502--C110 or a divalent group made by combining a plurality of these divalent groups is preferred. 21 indicated by L
Both ends of the 1i group (portions that bond to oxygen atoms) are carbon atoms, and may be substituted.

n1 and n3 are preferably integers of 1 to 6, and 1 is particularly preferable.

Examples of hardeners used in the present invention are listed below, but the present invention is not limited thereto.

Exemplary compound ■-1 CH2=CI-ISO2CH20CH2SO. CH=C
H21I-2 CH. =CHSO. CH. CH. OCH. CH2SO2
CH=CH2? ! -3 CH. =CHSOt1CH. +vO-+CHd7SO.
CH=CH2U-4 CH2=CHSO2CH20
C H 2 C H 2 0 C H z S O
- CH = CH 2■-5 CH. =CHSO,CH20CH. CH, CH. OCH
2SO2CH=CH. ff-6 CH2=CHSO2CH20CHICH20CH2CH
20CH2SO2CH=CH21I-7 CH. =CHSO, CH. CH. OCH2CH. OCH
．． CH2SO. CH=CH2■-8 ■-9 II-10 The synthesis method of these hardening agents is described in Japanese Patent Publication No. 44-29622,
It is described in publications such as No. 47-24259 and No. 47-25373.

The amount of hardening agent used in the present invention can be arbitrarily selected depending on the purpose. Usually it can be used in proportions ranging from 0.01 to 20 weight percent based on dry gelatin. Particular preference is given to using proportions ranging from 0.05 to 15 weight percent.

lii! according to the present invention! The film agent can be used in all black and white photographic materials that use gelatin.

Examples include black-and-white photosensitive materials such as black-and-white photographic film, X-ray film, plate-making film, black-and-white photographic paper, aviation film, microfilm, facsimile film, and graph film.

In this case, there are no particular limitations on the photographic constituent layers in which the hardener is used, including silver halide emulsion layers as well as non-photosensitive layers such as undercoat layers, back layers, filter layers, intermediate layers, overcoat layers, etc. It can be used in any gelatin-containing photographic constituent layer.

The above hardeners may be used alone or in combination of two or more. It may also be used in combination with other hardening agents known so far.

Known hardeners include, for example, formaldehyde,
Aldehyde compounds such as glutaraldehyde, bis(2-chloroethylurea), 2-hydroxy-4.6-
Dichloro1.3.5-triazine, etc. U.S. Patent Nos. 3,288,775M and 2,732,303, British Patent Nos. 974,723 and 1,167,207
Compounds containing reactive halogens, divinyl sulfone, 5-acetyl-1,3-diacryl hexahydride-1,3,5-triazine, and others described in U.S. Patent No. 3,635,718. No. 3, 23
2,763, British Patent No. 994,869, etc., compounds having reactive olefins, N
-Hydroxymethylphthalimide, other U.S. Patent No. 2
, No. 732, 316, l! Examples include N-methylol compounds described in U.S. Pat. No. 2,588,168, sardine acids described in U.S. Pat. Can be done. Alternatively, chromium alum and the like can be used as inorganic compound hardeners. In addition, compounds in the form of precursors instead of the above compounds, such as alkali metal bisulfite aldehyde adducts, methylol derivatives of hydantoin, primary aliphatic ditroalcohols, mesyloxyethylsulfonyl compounds, chloroethyl It may also be used in combination with sulfonyl compounds.

A compound that accelerates the hardening of gelatin can also be used in combination with the above-mentioned hardening agent. For example, a sulfinic acid group-containing polymer described in JP-A No. 56-4141 is used in combination with the hardening agent as a hardening agent.

In the manufacturing process, gelatin to which the above hardening agent is applied is subjected to so-called alkali-treated (lime-treated) gelatin immersed in an alkaline bath, acid-treated gelatin immersed in an acid bath, and both treatments before gelatin oil is extracted. Either double-soaked gelatin or enzyme-treated gelatin may be used. Furthermore, the above-mentioned hardening agent can also be applied to low molecular weight gelatin which has been partially hydrolyzed by heating the gelatin in a water bath or by treating it with a proteolytic enzyme.

(100) of silver halide grains used in the present invention
The plane/(111) plane ratio is 5 or more. Further, the upper limit of the above ratio is 100% for the (100) plane. here,
If the (100) plane/(IN) plane ratio is less than 5, it is not preferable from the viewpoint that photosensitivity in the near-infrared region is significantly lost. On the contrary, it is preferable that the above ratio is 5 or more from the viewpoint that a high level of photosensitivity in the near-infrared region begins to be ensured.

Silver halide grains having a (100) plane/(111) plane ratio of 5 or more used in the present invention can be prepared by various methods. The most common method is I) Ag during particle formation
This is a method in which silver nitrate aqueous solution and alkali halide aqueous solution are simultaneously added by selecting a rate that is faster than the dissolution rate of particles and at which re-nucleation is large, while keeping the value at a constant value of 8.10 or less (
The so-called controlled double jet method). More preferably the pAg value is 7.80 or less, even more preferably l)A(
] value is preferably 7.60 or less. When the silver halide grain shape is divided into two processes: nucleation and its growth, there is no limit to the I)Ag value at the time of nucleation, and 11 at the time of Kaicho.
A! The l value is preferably 8.10 or less, more preferably 7.80 or less, even more preferably 7.60 or less.

Although the soluble silver salt and the soluble halogen salt may be reacted by a one-sided mixing method, a simultaneous mixing method is preferred in order to obtain good monodispersity.

The (100) plane/(111) plane ratio of particles can be determined by Kubelkamunk's dye adsorption method (hereinafter referred to as "Kuberkamunk method"). In this method (10
It adsorbs preferentially to either the 0) plane or the (111) plane, and the association state of the dye on the (100) plane and the (
111) Select dyes whose association states on the surface differ spectrally. Adding such dyes to the emulsion,
The (100) plane/(111) plane ratio can be determined by examining the spectra in detail with respect to the amount of dye added.

The detailed ratio of (ioo) planes on the surface of silver halide grains can be found in Tadaaki Tani, “Identification of crystal phase of silver halide fine grains in photographic emulsions using dye adsorption phenomenon,” Journal of the Chemical Society of Japan, 9.
42-946 (1984).

The particle shape has a (100) plane/(111) plane ratio of 5
As long as the above conditions are met, it may have a regular crystal shape such as a cube, octahedron, or tetradecahedron, or it may have an irregular crystal shape such as a spherical or plate shape.

The silver halide emulsions used in the present invention include conventional silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, and silver chloride. Any silver used in silver chloride can be used, but silver chlorobromide, silver chloroiodobromide, and silver chloride containing 50 mol % or more of silver chloride are particularly preferred. This is because if the silver chloride content is less than 50 mol %, the quality of halftone dots deteriorates rapidly.

The silver halide grains used in the silver halide emulsion may be those obtained by any of the fugitive method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and elongating the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Further, while taking into account the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling the pth and/or pAg in the mixing tank. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. After lengthening, a conversion method may be used to change the halogen composition of the particles.

When producing a silver halide emulsion, a silver halide solvent can be used as necessary to control the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains.

In the process of forming and/or growing the grains, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including IM salts), rhodium salts (including complex salts), and iron salts. By adding metal ions using at least one selected from (including complex salts), these metal elements can be contained inside the particles and/or on the particle surface, and by placing them in an appropriate reducing atmosphere. , reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disclosure (Research Q)
It can be carried out based on the method described in Section 2 of No. 17643 (hereinafter abbreviated as RD).

The silver halide grains may have a uniform silver halide composition or distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the interior and surface layer of the grain.

The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.

The average grain size of the silver halide grains is preferably 2 μm or less, particularly preferably 0.7 μm or less.

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). When divided by the average grain size, the value is 0.20 or less.The grain size here refers to the diameter in the case of spherical silver halide grains, and the diameter in the case of grains with shapes other than spherical. , expressed as the diameter when the projected image is converted into a circular image of the same area) may be used alone or in combination. Further, a polydisperse emulsion and a monofractional emulsion may be mixed and used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

Silver halide emulsions can be prepared using the commonly used chemical sensitization method.
For example, gold sensitization (U.S. Pat. No. 2,540,085, U.S. Pat. No. 2,399,083, etc.), sensitization with Group III metal ions (U.S. Pat. No. 2,448,060, U.S. Pat. No. 2,598, etc.)
, 079, etc.), sulfur sensitization [U.S. Pat. No. 1, 57, etc.]
No. 4,944, No. 2,278,947, No. 3,
021,215@, 3.635, 717, etc.)
, reduction sensitization (U.S. Patent No. 2,518,698, Research Disclosure t-(Research D
isclosure ) Vol. 176 (19
78. 12) R D -17643, item (■), etc.), sensitization with thioether compounds (for example, U.S. Pat. No. 2,521,926, U.S. Pat. No. 3,021,215,
No. 3,048,133, No. 3,165,552, No. 3,625,697, No. 3,635,7
No. 17, No. 4,198,240, etc.), or various combinations of these sensitization methods are applicable.

More specific chemical sensitizers include sodium thiosulfate, allylthiocarb
amide), thiourea, thiosulfate, thioether and cystine;
and reduction sensitizers such as tin chloride, phenylhydrazine, and reductone.

Various additives can be used in the photosensitive material of the present invention depending on the purpose.

These additives are described in detail in RD No. 17643 (1
(December 1978) and No. 18716 (November 1979), and the relevant sections are summarized in the table below.

Furthermore, there are no particular limitations regarding the exposure and development processing conditions for the photosensitive material of the present invention; for example, the above-mentioned RD 1γ643-2
The descriptions on pages 8 to 30 can be referred to.

The photosensitive silver halide emulsion layer containing the silver halide emulsion and other hydrophilic colloid layers contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. be able to.

Examples of the support for the photosensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate,
For example, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate films, polystyrene films, etc. are used depending on the purpose of use.

Further, various inorganic white pigments, inorganic coloring pigments, dispersants, fluorescent whitening agents, antistatic agents, antioxidants, stabilizers, etc. can be added to the support. Further, the surface of the support may be subjected to a surface activation treatment such as a corona discharge treatment or a flame treatment, and an undercoat layer may be provided as necessary.

The silver halide light-sensitive material of the present invention can be constructed by coating a silver halide emulsion layer or other hydrophilic colloid layer on a support or on other layers by various coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used.

[Example 1] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 (Coating solution for emulsion layer manufactured by DI) Solution A Solution B Solution C In the above solution A kept at 40°C, pH 3, oAa 7
．． The above solution B and the above solution C were simultaneously added functionally over 60 minutes while maintaining γ, and after stirring was continued for an additional 10 minutes, the p day was adjusted to 6.0 with an aqueous sodium carbonate solution.
Add 2 Il of 0% aqueous magnesium sulfate solution and 2.55 l of 5% aqueous polynaphthalene sulfonic acid solution to make the emulsion
The mixture was flocculated at 0°C, decanted, and washed with water to remove excess salt from the aqueous solution. Next, 3.12% of water was added to disperse it, and 0.92% of a 20% magnesium sulfate aqueous solution was added again to remove the excess salt in the aqueous solution. Furthermore, 3.71 g of water and 141 g of gelatin were added thereto and dispersed at 50° C. for 30 minutes. As a result, silver bromide 35 mol%, silver chloride 65 mol%, average grain size 0.25μ, monodispersity 9, (100) plane/(111)
Cubic grains with an area ratio of 98/2 were obtained. Similarly, I
) As shown in Table 1, by changing Ag (10
Particles with a ratio of 0) plane/(111) plane were obtained.

Add 1% citric acid aqueous solution to 1201j2 and 5% sodium chloride aqueous solution to pH 5.5, l)Ag7
120 tl2 of a 0.1% aqueous sodium thiosulfate solution and 80 tl2 of a 0.2% aqueous chloroauric acid solution were added to the emulsion prepared in the following manner, and the emulsion was aged at 60°C to obtain the highest sensitivity.

Divide the above emulsion into several parts as necessary, and add 4-hydroxy-6-methyl-1.3.3a as a stabilizer to each part.
．． 180 u of 1% solution of 7-tetrazaindene, 400 u of 10% aqueous solution of gelatin, and sensitizing dye [Ia], [
Ib ] as shown in Table 1, and further added 50 d of 5% potassium bromide aqueous solution, 30 g of Bolimar latex a,
20% aqueous solution of sabonin 17112 as a spreading agent, 4% aqueous solution of styrene-maleic acid copolymer 27 as a thickener
A compound represented by the general formula [II] was added as a hardening agent as shown in Table 11.

Volima latex a2 CI282! Dispersed in the presence of ○(CzH20)-S○pNa (preparation of coating solution for protective 1 film) 100g of amorphous silica with an average particle size of 3.5μ was added to an aqueous solution of 400g of gelatin, and the mixture was separated. A coating solution for a protective film was prepared.

(Preparation of Samples No. 1 to 13) The above-mentioned emulsion layer coating liquid and the above-mentioned Will retaining coating liquid were simultaneously coated on one side of a subbed polyethylene terephthalate support. However, the amount of silver in the emulsion layer is 3.6
The Q/f of gelatin was 1.8 Q/f, and the gelatin of the protective film was applied so that it was 0.7 Q/1'.

In addition, on the opposite side of the support from the emulsion layer, the following dye A
, surfactant and lj! A gelatin solution containing a membrane agent was applied and dried. However, the following dye A was added in an amount that gave an optical density of 1.5 at 780 rv.

Dye A Comparative Sensitizing Dye B Comparative Hardener C Comparative Hardener D 0H (Evaluation of Samples) Sample No. 1 obtained in this manner. 1 to 13 with Ratten filter No. Wedge exposure and halftone exposure were performed at 1/100,000 seconds using a xenon light source equipped with 88A, and at 38°C with a Sakura Automatic Processor GR~26 (manufactured by Konica) using a developer and fixer with the following composition. 13
It was developed for seconds, fixed, washed with water, dried, and the optical density was measured. The results are shown in Table-1.

In Table 1, the relative sensitivity is determined by sample No. It is expressed as a relative value when the sensitivity immediately after coating No. 3 is set as 100.

Fog also includes the base density.

Relative sensitivity processing is immediately after application, relative sensitivity ■ is 40℃, 80%R
．． H. After one day under these conditions, the relative sensitivity ■ is 50% at 23°C.
R. H. It shows the relative sensitivity after 30 days under the conditions. Nao R. H. is the relative humidity. The quality of the halftone dots was evaluated by observing the halftone dots using a microscope with a magnification of 100 times and rating them on a 10-point scale.

10 is the best, 1 to 4 is unusable, and 5 or higher is usable.

Developer formulation> Pure water (ion-exchanged water) Approximately 800 d Potassium sulfite eo g Ethylenediaminetetraacetic acid disodium salt 2 g Potassium hydroxide
10.5 g5-methylbenzotriazole 300mg diethylene glycol
25g 1-phenyl-4,4-dimethyl-3-virazolidinone 300mg 1-phenyl-5-mercaptotetrazole 60mg Potassium bromide 3.5g Hydroquinone 20 Q Potassium carbonate 15 (] Add depleted water (ion-exchanged water) to finish to 1.000112.

of this developer Ku-denfu liquid prescription> (Composition A) pH was 10.8.

Ammonium thiosulfate (72.5% W/V aqueous solution) 24
0 Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid
6g sodium citrate dihydrate 2g acetic acid (90% W/W aqueous solution)
13.6tl2 (11 composition B) Pure water (ion-exchanged water) 17t12 sulfuric acid (50% w/w aqueous solution) 4.7Q aluminum sulfate (Aj!20s equivalent content is 8.1%w/w)
(Aqueous solution of W) 26.5 (When using 1 fixer, the above composition A1 was dissolved in the order of composition B in the order of 1 and used.

The pH of this fixer was about 4.3.

As is clear from Table 1, the samples of the present invention had good halftone dot quality and little fog, and no decrease in sensitivity was observed even after storage.

[Effects of the Invention] As explained in detail above, the present invention has high sensitivity to infrared light and does not cause a decrease in sensitivity during storage.
It was possible to provide a silver halide photographic material with low fog and high contrast.

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, wherein the light-sensitive silver halide emulsion layer has a (100) plane/(111) plane ratio. is 5 or more, and contains silver halide grains spectrally sensitized with at least one sensitizing dye represented by the general formula [Ia] and at least one sensitizing dye represented by the general formula [1b]. , and at least one hardening agent represented by the general formula [II]. General formula [ I a] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [ I b] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Y_1_1, Y_1_2, Y_2_1 and Y
_2_2 each represents a group of nonmetallic atoms necessary to form a 5- or 6-membered nitrogen-containing heterocycle, R_1_1, R_1
_2, R_2_1 and R_2_2 each represent a substituted or unsubstituted alkyl group, aryl group or aralkyl group. R_1_3, R_1_4, R_1_5, R_2_3, R
_2_4, R_2_5 and R_2_6 are each a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group,
Represents phenyl group, benzyl group, ▲numerical formula, chemical formula, table, etc.▼. Here, W_1 and W_2 are each a substituted or unsubstituted alkyl group (the number of carbon atoms in the alkyl part is 1 to
18, preferably 1 to 4), represents an aryl group, W_1
and W_2 can also be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle. Also, R_1_3 and R_1_5 and R_2_3 and R_
2_5 can be linked to each other to form a 5-membered ring or a 6-membered ring. X_1_1 and X_2_1 represent anions. n_1_1, n_1_2, n_2_1 and n
_2_2 represents 0 or 1. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, L represents a divalent organic group. n_3_1, n_
3_3 represents a positive integer, and n_3_2 represents 0 or 1. ]