JPH05289223A - Silver halide photographic sensitive material for laser light source - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material for laser light source having high sensitivity without fog and showing no decrease in sensitivity or gamma after storage, by spectrally sensitizing it with a specified spectral sensitizing dye. CONSTITUTION:This silver halide photographic sensitive material has at least one silver halide emulsion layer which is spectrally sensitized with at least one kind of sepctral sensitizing dye expressed by formula I-III in >600nm wavelength range. The silver halide photographic sensitive material has a protective surfactant expressed by (Cf)-(Y)n, and at least one kind of fluorinated cation surfactant expressed by Rf'-L-X<+>Z<->. In the formulae, Z1 and Z2 are nonmetal atoms necessary to form azole rings having substituents, Z3 and Z5 are nonmetal atoms necessary to form benzothiazol or naphthothiazol rings which may have substituents, and Z4 is a five- or six-member carbon atom rings which may have substituents.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material for a laser light source. More specifically, the silver halide photographic light-sensitive material has good storability over time and the color tone of a silver image after development is good, and it is The present invention relates to a silver halide photographic light-sensitive material for a laser light source, which has a property of preventing the film surface from being contaminated.

[0002]

BACKGROUND OF THE INVENTION In recent years, images for radiation diagnosis such as MRI (Magnetic Resonance Imaging), X-ray CT (Computed Tomography), CR (Computed Radiography), and Computer Aided Diagnosis are available. It is common to use it as a digital or analog (video) signal that is processed by a processing device such as a computer, scanned with a laser beam, and then visualized on a silver halide photographic light-sensitive material for diagnostic use as a transmission photographic image. ..

In these scanning type laser exposure apparatuses, coherent light such as helium-neon or a semiconductor laser is used as a laser light source. Therefore, the photosensitive material needs to be spectrally sensitized in the laser light region from red light to near infrared, which is the oscillation wavelength of these laser lights.

As a means for spectrally sensitizing a silver halide photographic emulsion to a wavelength of 600 nm or more, there is a technique in which a certain cyanine dye is added to the silver halide photographic emulsion to extend its photosensitive wavelength range to the long wavelength side. Applied.

In order to spectrally sensitize a silver halide photographic light-sensitive material to the infrared region, a sensitizing dye having an absorptivity for infrared light is used, and these are described, for example, in "Theory of t" by Mees.
he Photographic Process "3rd edition Macmillan Co., 1966. Described on pages 198 to 201. Many sensitizing dyes have been proposed for the spectral sensitization method to the infrared region or near infrared region. For example, U.S. Patents 2,095,854 and 2,095,8
56, 2,955,939, 3,482,978, 3,552,974
Nos. 3,573,921 and 3,582,344 are disclosed.

However, a silver halide emulsion which has been spectrally sensitized to the infrared region has a poor stability of the dye because of poor storage stability of the light-sensitive material, resulting in a decrease in sensitivity and an increase in fog. The above technologies are no exception.

Further, in the silver halide photographic light-sensitive material for laser light source, since fine silver halide grains are used, the blue light component is scattered depending on the grain size of developed silver to form an image with a strong yellow tint. easy.

In the case of a medical light-sensitive material for diagnosing a silver image directly with the naked eye, it is desired that the silver image has no yellowish tint and a pure black tone because the image diagnosis is easy and the eyes are not tired. is there.

Toning agents are generally used to adjust the tone of developed silver. For example certain mercapto compounds
(For example, 1-phenyl-5-mercaptotetrazole, etc.)
Is known to be used as an emulsion or a developing solution, but it has a drawback that the sensitivity is remarkably reduced.

In addition to the above-mentioned photographic performance, when a raw film is handled with bare hands before development, fingerprint marks often occur in the form of unevenness or white spots. Since such a phenomenon leads to misdiagnosis for medical light-sensitive materials, its improvement has been desired.

[0011]

SUMMARY OF THE INVENTION Therefore, a first object of the present invention is to provide a high-sensitivity silver halide photographic light-sensitive material for a laser light source, which is free from deterioration of sensitivity and gamma upon storage of the light-sensitive material with time and does not cause fog. Is. A second object of the present invention is to provide a silver halide photographic light-sensitive material for a laser light source, in which the image silver has a pure black tone and is less likely to cause fingerprint marks when handling a raw film. .. Other objects will be apparent from the following specification.

[0012]

The above objects of the present invention have been accomplished by the following finding. That is, a silver halide photograph having at least one silver halide emulsion layer spectrally sensitized to 600 nm or more by at least one of the spectral sensitizing dyes represented by the following general formula [1], [2] or [3] In the light-sensitive material, in the protective layer of the silver halide photographic light-sensitive material, at least one fluorine-based anionic surfactant represented by the following general formula [4] and fluorine represented by the following general formula [5] are used. This is achieved by a silver halide photographic light-sensitive material for a laser light source, which contains at least one cationic cationic surfactant.

[0013]

[Chemical 4]

In the formula, Z ₁ and Z ₂ represent a non-metal atom group necessary for forming an azole ring which may have a substituent,
R ₁ and R ₂ each represent an alkyl group or a substituted alkyl group.

X ⁻ represents a counter ion, and n is 1 or 2, and n is 1 when forming an intramolecular salt. Z ₁ and Z ₂ in the formula
The non-metal atom group may be the same or different as long as it can complete an azole ring, for example, benzothiazole ring as benzothiazole, 5-chlorobenzothiazole, 5-methylbenzothiazole, 5-methoxybenzothiazole, 5-hydroxybenzothiazole, 5-hydroxy-6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5-ethoxy-6-methylbenzothiazole, 5-
Examples thereof include phenylbenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5,6-dimethylaminobenzothiazole and 5-acetylaminobenzothiazole.

Examples of the benzoselenazole ring include benzoselenazole, 5-chlorobenzoselenazole, 5-methylbenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole and 5,6-dimethylbenzoselena. Examples thereof include sol, 5,6-dimethoxybenzoselenazole, 5-ethoxy-6-methylbenzoselenazole, 5-hydroxy-6-methylbenzoselenazole, 5-phenylbenzoselenazole and the like. Further, as the naphthothiazole ring, for example, β-naphthothiazole, β, β '
-Naphthothiazole and the like. Further, examples of the naphthoselenazole ring include β-naphthoselenazole. Specific examples of R ₁ and R ₂ include, for example, alkyl groups such as methyl group, ethyl group, n-propyl group, β-carboxyethyl group, γ-carboxypropyl group, γ-sulfopropyl group, γ-sulfobutyl group. And substituted alkyl groups such as δ-sulfobutyl group and sulfoethoxyethyl group.

Specific examples of the counter ion represented by X ⁻ include halogen ion, perchlorate ion, thiocyanate ion, benzenesulfonate ion, p-toluenesulfonate ion, methylsulfate ion and the like. Can be done.

[0018]

[Chemical 5]

In the formula, Z ₃ and Z ₅ represent a group of non-metal atoms necessary for forming a benzothiazole, naphthothiazole, benzoxazole and naphthoxazole ring which may have a substituent. Z ₄ represents a 5- to 6-membered carbon atom ring which may have a substituent, and R ₃ and R ₄ each represent an alkyl group or a substituted alkyl group. X ⁻ represents a counter ion, n is 1 or 2, and n is 1 when forming an intramolecular salt.

In the formula [2], a benzothiazole ring and a naphthothiazole ring represented by Z ₃ and Z ₅ (for example, [1,2
d), [2,1d] and [2,3d] naphthothiazole ring), etc., benzoxazole ring, naphthoxazole ring (for example, [1,2d], [2,1d] and [2,3d] naphthothiazole ring) The ring) may have a substituent, for example, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group or a halogen atom (for example, a chloro atom,
Brom atom) and the like.

R ₃ and R ₄ are alkyl groups having 1 to ₄ carbon atoms which may have a substituent, for example, methyl group, ethyl group, 2-
Hydroxyethyl group, 2-methoxyethyl group, 2-acetoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group,
2-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, vinylmethyl group, benzyl group, phenethyl group, P-
Sulfophenethyl group, n-propyl group, isopropyl group,
For example, n-butyl group.

When Z ₄ of the above general formula [2] of the present invention is a 5-membered carbon atom ring, it can be represented by the following general formula [2-a].

[0023]

[Chemical 6]

In the formula, R ₈ and R ₉ are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms,
Represents a halogen atom (eg, chlor, bromine atom, etc.), R ₁₀ and R ₁₁ are each an alkyl group having 1 to 12 carbon atoms,
A phenyl group which may have a substituent (for example, a phenyl group, m
-Tolyl group, p-tolyl group, m-chlorophenyl group, p-chlorophenyl group, for example, p-methoxyphenyl group substituted with an alkoxy group having 1 to 4 carbon atoms), alkoxycarbonylalkyl group having 1 to 4 carbon atoms ( For example, ethoxycarbonylmethyl group) can be mentioned. R ₁₂ is an alkyl group having 1 to ₁₂ carbon atoms, an alkoxy group having 1 to 4 carbon atoms,
It represents an alkoxycarbonyl group having 1 to 4 carbon atoms or a phenyl group. Z ₃ , Z ₅ , R ₃ , R ₄ and X, n have the same meanings as in the general formula [2].

When Z ₄ of the above general formula [2] of the present invention is a 6-membered carbon atom ring, it can be represented by the following general formula [2-b].

[0026]

[Chemical 7]

In the formula, R ₁₃ and R ₁₄ each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group. Z ₃ ,
Z ₅ , R ₃ , R ₄ and X ⁻ , n have the same meanings as in the general formula [2].

Next, the compound of the general formula [3] according to the present invention will be described in more detail.

[0029]

[Chemical 8]

In the formula, R ₅ and R ₆ represent an alkyl group or a substituted alkyl group, preferably an alkyl group having 1 to 8 carbon atoms. Examples of the substituent which may be substituted on these alkyl groups include a carboxyl group, a sulfone group, a cyano group, a halogen atom (for example, a chlor atom, a bromine atom, a fluorine atom, etc.), a hydroxyl group, an alkoxycarbonyl group.
(Preferably having 8 or less carbon atoms), alkoxy group (preferably having 7 or less carbon atoms), aryloxy group, acyloxy group (preferably having 3 or less carbon atoms), acyl group (preferably having 8 carbon atoms)
The following), carbamoyl group, sulfamoyl group, aryl group and the like can be mentioned.

R ₇ is a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group or a benzyl group, preferably an alkyl group having 1 to 4 carbon atoms or a benzyl group.

Y is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, or a halogen atom, and the alkyl group may have a substituent, and examples of the substituent include a carboxymethyl group and trifluoro. Examples thereof include a methyl group and an alkoxy group. Examples of the 5- or 6-membered nitrogen-containing heterocycle represented by Z ₆ include a thiazole ring, a selenazole ring, an oxazole ring, a 3,3-alkylindolenine ring and an imidazole ring. Of these, a thiazole ring and an oxazole ring are preferable, and a benzothiazole ring, a naphthothiazole ring, a benzoxazole ring, and a naphthoxazole ring are more preferable. X ⁻ represents a counter ion, m, n and
p represents 1 or 2. Next, specific examples of the compounds represented by the general formulas [1], [2] and [3] are shown, but the present invention is not limited thereto.

[0033]

[Chemical 9]

[0034]

[Chemical 10]

[0035]

[Chemical 11]

As the dye of the general formula [1], the dyes of the specific examples (1) to (32) of the dye described in Japanese Patent Application No. 1-223473 filed by the same applicant as the present invention including the above dyes Can be used.

Further, as the dye of the general formula [2], 1-1 to 1-16 of the general formula [1] described in Japanese Patent Application No. 3-8620 filed by the same applicant as the present invention including the above are included. The above dyes can be used.

Also, as the dye of the general formula [3], as in the above, 2-1 to 2-1 of the general formula [2] described in Japanese Patent Application No. 3-8620.
0 dyes can be used.

The dyes represented by the general formulas [1], [2] and [3] according to the present invention are, for example, "The Che" by FM Hamer.
It can be synthesized according to the method described in “Mistry of Heterocyclic Compound” Vol. 18, or according to it.

The amount of these compounds used is preferably in the range of 0.003 g to 0.3 g, and more preferably 0.005 g to 0.15 g, per mol of silver halide. These dyes may be added directly to the emulsion, or may be added by dissolving in a suitable hydrophilic solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water or a mixed solution thereof. An ultrasonic method may be used as the dissolution method.

The method of addition to the emulsion is, for example, US Pat. Nos. 3,469,987 and 3,822,135, and Japanese Patent Publication No. 46-24185.
The methods described in JP-A Nos. 50-80826 and 51-74624 may be used.

Next, the fluorine compound according to the present invention will be described in detail. The surfactant will be simply referred to as "active agent" hereinafter.

General formula [4] (Cf)-(Y) _{n In the} formula, Cf is an n-valent group containing at least 3 fluorine atoms and at least 2 carbon atoms, and Y is -COOM, -SO. ₃
M, -OSO ₃ M or -P (= O) (OM) ₂ is represented. M represents a hydrogen atom or a cation such as an alkali metal or a quaternary ammonium salt, and n is 1 or 2.

In the present invention, the fluorine-based anionic activator represented by the general formula [4] is particularly preferably the one represented by the following general formula [4a].

General formula [4a] Rf- (D) _t -Y In the formula, Rf represents a fluorine-substituted alkyl group or aryl group having 3 to 30 carbon atoms, and D represents -O-, -COO-, -CON. (R ₁ )-or —SO ₂ N (R ₁ ) — represents a divalent group having 1 to 12 carbon atoms and containing at least one bond. R ₁ represents an alkyl group having 1 to 5 carbon atoms, t is 1 or 2, Y is —COOM—, —S
Represents O ₃ M, —OSO ₃ M or —P (═O) (OM) ₂ , and M represents a hydrogen atom or an alkali metal or a cation such as a quaternary ammonium salt.

Specific examples of the anionic activator represented by the general formula [4] and the general formula [4a] are shown below, but the invention is not limited thereto.

[0047]

[Chemical 12]

[0048]

[Chemical 13]

[0049]

[Chemical 14]

[0050]

[Chemical 15]

[0051]

[Chemical 16]

Next, the fluorine-based cationic activator used in the present invention will be described.

General formula [5] Rf'-L-X ⁺ Z ^{-In the} formula, Rf 'represents a hydrocarbon group having 1 to 20 carbon atoms,
At least one hydrogen atom is replaced by a fluorine atom. L represents a chemical bond or a divalent group.

X ⁺ represents a cation and Z ⁻ represents a counter anion.

In the general formula [5], Rf 'in the formula represents a hydrocarbon group having 1 to 20 carbon atoms, and at least one hydrogen atom is preferably substituted with a fluorine atom.

Rf 'is, for example, -C _k F _{k + 1} (k = 1 to 20,
3-12 is particularly preferable), -C _m F _2m , -C _m F _2m-1 (m = 2-2
0, particularly preferably 3 to 12).

Examples of L include -SO ₂ N (R ¹ ) (CH ₂ ) _p- , -CON (R
¹ ) (CH ₂ ) _p- , -OASO ₂ N (R ¹ ) (CH ₂ ) _p- , -OACON (R ¹ ) (CH ₂ ) _p- ,
_{-OAO (CH 2) p -,} - OA (CH 2) p -, - O (CH 2 CH 2 O) q (CH 2) p -, - O (C
H ₂ ) p-, -N (R ¹ ) (CH ₂ ) _p- , -SO ₂ N (R ¹ ) (CH ₂ ) _p O (CH ₂ ) _r- , -CO
N (R ¹ ) (CH ₂ ) _p O (CH ₂ ) _r- , -OASO ₂ N (R ¹ ) (CHR ¹ ) _p OA-,-(CH ₂ )
_p (CHOH) _s (CH ₂ ) _r- and the like can be mentioned. A represents alkyl or arylene.

Examples of X ⁺ are -N ⁺ (R ¹ ) ₃ , -N ⁺ (CH ₂ CH ₂ OCH
₃ ) ₃ , -N ⁺ C ₄ H ₈ O (R ¹ ) ₃ , -N ⁺ (R ¹ ) (R ² ) (CH ₂ CH ₂ OCH ₃ ), -N ⁺ C _{5
^{H 5, -N + (R 1}} ) (R 2) (CH 2) p C 6 H 5, -N + (R 1) (R 2) (R 2) , and the like. Here, R ¹ and R ² each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (which may have a substituent), p, r and s are each 0 to 6 and q is 1 to Twenty.

Examples of Y ⁻ include I ⁻ , Cl ⁻ , Br ⁻ , CH ₃ S
_{^{O 3 -, CH 3 -C 6}} H 4 -SO 3 - , and the like.

Specific examples of the fluorine-based cationic activator preferably used in the present invention are shown below, but the present invention is not limited thereto.

[0061]

[Chemical 17]

[0062]

[Chemical 18]

In the present invention, it is more preferable to use a fluorinated cationic activator containing at least one bond of —SO ₂ N (R ¹ ) — which is hardly soluble. Here, the term “poorly soluble” means that 2.0 g of the activator was added to 100 cc of pure water at 23 ° C. and the mixture was stirred for 1 hour.
It becomes insoluble when a precipitate is formed or a floating substance is observed after standing for 24 hours.

For example, 5-1, 5-8, 5-15, 5-16 and the like correspond, but the present invention is not limited to these and can be divided by the above test.

The fluorinated anionic activator or fluorinated cationic activator according to the present invention is described in, for example, US Pat.
No. 751, No. 2,567,011, No. 2,732,398, No. 2,764,602
No. 2, No. 2,806,866, No. 2,809,998, No. 2,915,376,
2,915,528, 2,918,501, 2,934,450, 2,9
37,098, 2,957,031, 3,472,894, British Patent 1,
No. 143,927, No. 1,130,822, Japanese Patent Publication No. 45-37304, Japanese Patent Laid-Open No.
47-9613, 49-134614, 50-117705, 50-1177
No. 27, No. 50-121243, No. 52-41182, No. 51-12392,
Journal of the British Chemical Society (J. Chem. Soc.), 1950, 2789, 1957, 257.
4 and 2640, Journal of American Chemical Society (J. Amer. Chem. Soc.) Vol. 79 2
549 (1957), Oil Chemistry (J. Japan Oil Chemists Soc.) 12
Vol. 653, Journal of Organic Chemistry (J. Org. Chem.), Vol. 30, 3524 (1965)
, Etc.) and the like. Some of these fluorine-based activators are trade names of Megafac F from Dainippon Ink and Chemicals, Inc., and Fluorad from MN Mining and Manufacturing Company.
ad) FC under the trade name, Imperial Chemical Industry under the name Monflor, Ei DuPont Nemeras & Company under the name Zonyls, and Farbeberke Hoechst. They are each sold under the trade name of Licowet VPF by the company.

The total amount of the fluorine-based cationic activator and the fluorine-based anionic activator used in the present invention is preferably 0.1 to 1000 mg, preferably 0.5 to 300 mg, and more preferably 1.0 to 150 mg per 1 m ² .

When used in combination, two or more kinds may be used in combination. Further, other fluorine-based nonionic activators, fluorine-based betaine activators, and hydrocarbon-based activators may be used in combination.

The addition ratio of the fluorine-based anionic activator and the fluorine-based cationic activator of the present invention is 1:10 to a molar ratio.
The ratio is preferably 10: 1, more preferably 3: 7 to 7: 3.

The place where the fluorine-based anionic activator and the fluorine-based cationic activator of the present invention are added is preferably the emulsion layer surface protective layer of the light-sensitive material. The surface of the emulsion protective layer may be overcoated with the fluorine-containing activator according to the present invention as a solution containing no binder.

The emulsion used in the silver halide photographic light-sensitive material of the present invention may be silver bromide, silver iodobromide, or a silver iodochlorobromide emulsion containing a small amount of silver chloride, but particularly high sensitivity. A silver iodobromide emulsion is preferred from the standpoint of obtaining the above.

These emulsions are used at the stage of physical ripening or grain preparation, for example, using cadmium salt, lead salt, zinc salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or its complex salt and the like. May be.

The size of silver halide grains used in the emulsion is not limited, but those having a size of 0.05 to 2 μm are preferable.
It is preferable that at least 40% of the silver halide grains of the present invention are substantially cubic or tetradecahedral grains by weight or the number of grains and the apex of the crystal surface is round.

The silver halide grains used in this emulsion are 0.7
It is preferable to contain 80% or more of particles having a size of μm or less. The size distribution of the silver halide grains used in the present invention may be monodisperse or polydisperse, but monodisperse is preferred. Here, the monodisperse is a dispersion system in which 95% of particles fall within a size of ± 40% of the number average particle diameter. The number average particle diameter is the number average diameter of the projected area diameters of the particles.

The internal structure of the silver halide grain used in the present invention is arbitrary, but a core-shell structure having a different silver halide composition is preferred.

The emulsion may be subjected to a Nudel water washing method, a flocculation sedimentation method or the like in order to remove soluble salts, and a preferable water washing method is, for example, an aromatic hydrocarbon containing a sulfo group described in JP-B-35-16086. Examples thereof include a method using a system aldehyde resin, and a desalting method using a polymer flocculant such as Exemplified G-3 and G-8 described in JP-A-63-158644.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. Examples of the compound used in such a step include Research Disclosure (RD) No. 17643, (RD) No. 18716 and (RD) No.
Various compounds described in 308119 (December 1989) can be used.

The types and locations of the compounds described in these three Research Disclosures (RD) are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 B Dye 25 ~ 26 VIII 649 ~ 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant 26-27 XI 650 Right 1005-6 XI Plasticizer 27 XII 650 Right 1006 XII Sliding Agent 27 XII Matting Agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII Halogenation of the Invention Examples of the support used in the silver photographic light-sensitive material include those described in the above RD,
A suitable support is a plastic film or the like, and the surface of the support may be provided with an undercoat layer to improve the adhesiveness of the coating layer, or may be subjected to corona discharge or ultraviolet irradiation.

[0079]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the following examples.

Example 1 A monodispersed cubic crystal emulsion of silver iodobromide containing 2 mol% of silver iodide having an average grain size of 0.1 μm by the double jet method while controlling at 60 ° C., pH = 8, and pH = 2.0 ( A) was obtained. This emulsion is
From the electron micrograph, the generation rate of twins was 1% or less in number. This emulsion (A) was used as a seed crystal and grown as follows.

That is, the seed crystal (A) was dispersed in 8.5 l of a solution containing protected gelatin and ammonia as needed kept at 40 ° C., and the pH was adjusted with acetic acid. Using this solution as a mother liquor, an aqueous solution of 3.1N ammoniacal silver nitrate and an aqueous solution of potassium bromide and potassium iodide were added by the double jet method. In other words, control pAg to 7.3 and pH to 9.7,
A layer having a silver iodide content of 35 mol% was formed. Next, the pH was changed from 9.0 to 8.0, the pH was kept at 9.0, and a 3.2 N aqueous ammoniacal silver nitrate solution and an aqueous potassium bromide solution were added by the double jet method to grow. Then add the potassium bromide solution through the nozzle over 8 minutes, reduce the pAg to 11.0,
Mixing was terminated 3 minutes after the addition of the potassium bromide.

This emulsion was a 14-sided monodisperse emulsion having an average grain size of 0.3 μm and rounded vertices, and the average silver iodide content of all grains was 1.5 mol%. Next, desalting was carried out in order to remove excess soluble salt of this reaction solution. That is, the reaction solution was kept at 40 ° C., a formaldehyde condensate of sodium naphthalenesulfonate and magnesium sulfate were added, and the mixture was allowed to stand with stirring, excess salts were removed by decantation, and a gelatin solution was further added and dispersed.

Next, the emulsion after desalting was brought to 55 ° C., and ammonium thiocyanate, chloroauric acid and sodium thiosulfate were added for chemical sensitization, and then the general formula [1] according to the present invention,
The dyes exemplified in [2] and [3] were spectrally sensitized by adding 35 mg per mol of silver halide as shown in Table 1.

When the maximum sensitivity was reached, 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene was added and stabilized at 1.2 g per mol of silver halide. Then, the following additives were added per mol of silver halide as follows.

Trimethylolpropane 9 g, nitrophenyl-triphenylphosphonium chloride 30 mg, 1,3-
Ammonium dihydroxybenzene-4-sulfonate 1g, 2
-Mercaptobenzimidazole-5-sodium sulfonate 10
mg, 2-mercaptobenzothiazole 10 mg, nC ₄ H ₉ OCH ₂ CH
(OH) CH ₂ N (CH ₂ COOH) ₂ 100 mg, trimethylolpropane 9
g, 1,1-dimethylol-1-bromo-1-nitromethane (10 mg) and the following were added to give an emulsion coating solution.

[0086]

[Chemical 19]

Further, as a protective layer for the emulsion layer, the following was added per 1 g of gelatin to prepare a coating solution.

70 m of colloidal silica having an average particle size of 0.013 μm
g, i-amyl-n-decyl-sodium sulfosuccinate 7 mg,
1.5 ml of 40% glyoxal aqueous solution, 2 ml of 35% formalin aqueous solution, the following preservatives and the general formulas [4] and [4] of the present invention.
Fluorine-based activators represented by a] and [5] were added as shown in the table to prepare a coating solution for the protective layer on the emulsion layer.

[0089]

[Chemical 20]

Next, 400 g of gelatin, 2 g of polymethylmethacrylate, 6 g of sodium dodecylbenzenesulfonate, 20 g of the following antihalation dye and glyoxal were prepared as a backing layer liquid, and a backing layer liquid of 50 wt% glycidyl methacrylate and 10 wt% of methyl acrylate was prepared. %, Butyl methacrylate 40 wt% of a copolymer of three kinds of monomers was diluted to a concentration of 10 wt%, and an aqueous dispersion of the copolymer was applied as an undercoating liquid. One side was coated with a protective layer liquid consisting of gelatin, a matting agent, sodium dodecylbenzenesulfonate and glyoxal to prepare a backed support.

[0091] The coating amount backing layer, 2.5 g / m ² of the same protective layer as each amount with gelatin was coated so as to be 2.0 g / m ^2.

[0092]

[Chemical 21]

A sample was obtained by simultaneously coating two layers of the emulsion layer coating solution and the protective layer coating solution on one surface of the backing layer-provided support with a slide hopper.

The coating amount was 3 g of silver per 1 m ^{2, the} coating amount of gelatin was 3 g of the emulsion layer and 1.2 g of the protective layer.

The following evaluations were performed on the obtained samples.

Using an automatic processor SRX-501 (manufactured by Konica Corporation), processing was carried out in a mode in which development, fixing, washing with water and drying were completed in 45 seconds, and the following evaluations were carried out. Evaluation of raw storability of the film The obtained sample was conditioned for 2 hours at a temperature of 23 ° C and a relative humidity of 47%, placed in a light-proof moisture-proof bag and sealed. It was left for 6 months and 6 months.

An optical wedge image was printed on a 354 mm × 430 mm size film of the obtained preserved sample with a He-Ne laser (A) having a wavelength of 633 nm and a semiconductor laser beam (B) having a wavelength of 820 nm, and a treatment agent replenishing mechanism was provided. Automatic processor SRX-502,
The sensitivity, fog and gamma were measured by using the developing solution XD-SR and the fixing solution XF-SR (both (manufactured by Konica Corporation) in the following processing step (developing temperature 35 ° C., 45 seconds).

The sensitivities shown in the table are those when the sample sensitized with the dye represented by the general formula [1] is exposed to an optical wedge image in (A) and the sensitivity of sample No. 1 is set to 100. It was expressed as a relative value. The samples sensitized with the dyes represented by the general formulas [2] and [3] were exposed to an optical wedge image in (B), and the relative values are shown when the sensitivity of Sample No. 2 is 100. ..

Further, in the table, gamma is indicated by the straight line gamma on the characteristic curve, and fog is the density of the unexposed area after subtracting the density of the support.

(Treatment process) Process Treatment temperature (° C) Treatment time (sec) Replenishment amount Insertion-1.2 Development + crossover 35 14.6 33 ml / four cut Fixing / crossover 33 8.2 63 ml / four cut Water washing + crossover 18 7.2 3.5 l / Min Squeeze 40 5.7 Dry 45 8.1 Total-45.0 Evaluation of silver tone Using the same sample, a wedge pattern having a density value of 2.0 or less was visually evaluated for silver tone according to the following three grades of A, B and C. A: Good yellowish color with no yellowishness in low density area B: Yellowishness in slightly low density area C: Yellowish color in obviously low density area Evaluation of fingerprint mark adhesion temperature 23 ° C, relative In a room kept at a humidity of 50%, a concentration of 1.0-
The palm was placed for 3 seconds on a sample film having a size of 354 mm × 430 mm exposed to 1.3, and the film subjected to the same processing as the above developing conditions was visually evaluated on a photographic observation table by the following three-stage method. In the table, black means a sample that has been exposed to light, and white means an unexposed sample.

A: Almost no fingerprint is visible B: Slight fingerprint is attached C: Fingerprint is clearly attached The above results are shown in Tables 1 and 2 below.

[0102]

[Table 1]

[0103]

[Table 2]

As is apparent from the above table, the dyes represented by the general formulas [1], [2] and [3] of the present invention are 600 nm.
The samples of the present invention which have been spectrally sensitized as described above and which contain the fluorine-based activators represented by the general formulas [4], [4a] and [5] have little deterioration in photographic performance even after storage for a long time and have a silver image color tone. It can be seen that the occurrence of fingerprint marks is suppressed.

[0105]

According to the present invention, a high-sensitivity silver halide photographic light-sensitive material for a laser light source can be obtained, which is free from deterioration of sensitivity and gamma even after storage of the light-sensitive material with time and does not cause fog.

Further, according to the present invention, a silver halide photographic light-sensitive material for a laser light source can be obtained in which the image silver has a tone of pure black tone and is less likely to cause fingerprint marks when handling the raw film.

Claims (1)

[Claims] 1. At least one silver halide emulsion layer spectrally sensitized to 600 nm or more with at least one spectral sensitizing dye represented by the following general formula [1], [2] or [3].
In a silver halide photographic light-sensitive material having a layer, in the protective layer of the silver halide photographic light-sensitive material, at least one fluorine-based anionic surfactant represented by the following general formula [4] and the following general formula [5 ] A silver halide photographic light-sensitive material for a laser light source, comprising at least one kind of a fluorine-based cationic surfactant represented by [Chemical 1] In the formula, Z ₁ and Z ₂ each represent a non-metal atom group necessary for forming an azole ring which may have a substituent, and R ₁ and R ₂ each represent an alkyl group or a substituted alkyl group. X ⁻ represents a counter ion, n is 1 or 2, and n is 1 when forming an intramolecular salt. [Chemical 2] In the formula, Z ₃ and Z ₅ represent a non-metal atom group necessary for forming a benzothiazole, naphthothiazole, benzoxazole and naphthoxazole ring which may have a substituent. Z ₄ represents a 5- to 6-membered carbon atom ring which may have a substituent, and R ₃ and R ₄ each represent an alkyl group or a substituted alkyl group. X ⁻ represents a counter ion, and n is 1 or 2
N is 1 when forming an intramolecular salt with. [Chemical 3] In the formula, Z ₆ represents a nonmetallic atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. Y represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxy group or a halogen atom. R ₅ and R ₆ each represent an alkyl group or a substituted alkyl group, and R ₇ represents a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group or a benzyl group. X ⁻ represents a counter ion, m and p represent 1 or 2, n is 1 or 2, and n is 1 when forming an intramolecular salt. In formula (4) (Cf)-(Y) _n , Cf is an n-valent group containing at least 3 fluorine atoms and at least 2 carbon atoms, and Y is -COOM, -SO ₃
M, -OSO ₃ M or -P (= O) (OM) ₂ . M represents a hydrogen atom or a cation such as an alkali metal or a quaternary ammonium salt, and n is 1 or 2. General formula [5] Rf'-L-X ⁺ Z ^{-In the} formula, Rf 'represents a hydrocarbon group having 1 to 20 carbon atoms,
At least one hydrogen atom is replaced by a fluorine atom. L represents a chemical bond or a divalent group. X ⁺ represents a cation and Z ⁻ represents a counter anion.