JPH06289511A - Silver halide photographic sensitive material using laser beam light source - Google Patents

Abstract

PURPOSE:To enhance scratching and abrasion resistance and antistatic performance by spectrally sensitizing an emulsion layer to a specified value or more and incorporating an F-containing nonionic surfactant and an inorganic nitrate in a hydrophilic colloidal layer for constituting the photosensitive material. CONSTITUTION:A silver halide emulsion layer is spectrally sensitized to the wavelength region of >=600nm with at least one of compounds represented by formulae I and II, and the hydrophilic colloidal layer contains the F- containing nonionic surfactant and at least one of the inorganic nitrates. In formulae I and II, each of R1, R5, R6, R7, R1, and R12 is H, alkyl, alkoxy, halogen, or carboxy; each of R2, R3, R4, R8, R10 is alkyl; each of X1-X4 is an S or selenium atom; each of Y1 and Y2 is counter ion; and each of (m) and (n) is 0 or 1, but when an intramolecular salt is formed, each is 0.

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, and more particularly to a halogenated laser light source having improved antistatic properties, scratch resistance and raw storage stability and suitability for rapid processing. The present invention relates to a silver photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, in a recording system using a laser light source for a silver halide photographic light-sensitive material, image quality has been improved due to the spread of semiconductor lasers and the like, and a 633 nm light source represented by a conventional He-Ne laser. From 680nm to 69 recently
It is exposed by a semiconductor laser of 0 nm.

In the recording system using these laser light sources, since the transportation, exposure and development of the photosensitive material are all automated, a photosensitive material having a strong physical property is required in order to prevent a failure occurring during transportation. For example, there are many occasions such as contact with various rollers and devices or contact friction between photosensitive materials during film loading, photographing, transportation, automatic development processing, etc., including the manufacturing process of photosensitive materials.

The light-sensitive material is generally composed of an electrically insulating support and a photographic emulsion layer. Therefore, during the manufacturing process or use of the photosensitive material, electrostatic charges are easily accumulated due to contact with the surface of the same kind or different kinds of materials and peeling friction, and when electrostatic charges are accumulated before development in this way, the electric charges are discharged. The photosensitive layer is exposed to light and, after development, spot-like spots or dendritic or feather-like spots, so-called static marks are formed. This not only significantly impairs the commercial value of the light-sensitive material, but also involves the risk of misdiagnosis in medical films. In addition, the accumulated electrostatic charge also causes a secondary failure such as adhesion of dust to the photosensitive material.

In addition to the above-mentioned contact friction, the chance of generating static marks is increasing more and more due to the recent high-speed conveyance of photosensitive materials, high-speed automatic processing, and higher sensitivity of photosensitive materials.

A number of proposals have been made in the past as an antistatic method for a light-sensitive material. For example, use of various surfactants or polymers has been disclosed as a method for improving the conductivity of the surface of the light-sensitive material. However, many of these substances adversely affect photographic performance. Further, there is a method of preventing the generation of static electricity due to friction or contact by reducing the power generation property of the surface of the photosensitive material, for example, Japanese Patent Laid-Open No. 51-3
No. 2322 discloses an anionic fluorine-containing surfactant and the like. Photosensitive materials containing these anionic fluorine-containing surfactants are generally negatively charged with respect to various materials with which they come into contact, and the power generation property is adjusted by using a combination of coating agents having positive chargeability. To prevent electrostatic damage. However, if the materials are not uniform, the antistatic performance is often insufficient, and if used in large amounts, there is the drawback that the photographic performance is adversely affected.

With respect to the generation of static electricity due to the above-mentioned contact friction or peeling, it is important to improve the slipperiness of the surface of the photosensitive material. That is, by improving the slipperiness of the photosensitive material,
It is possible to prevent abrasion and film peeling of the film due to friction and scratching, and to reduce contact triboelectric charging.

On the other hand, the recent film processing speed has entered an era of ultra-rapid large-volume processing, and in diagnostic equipment such as CT and MRI for medical use, dedicated processing directly connected to the imaging equipment is performed, and 45 seconds or less. It is desired to further improve the processing performance in the development of a low replenishment amount in the ultra-rapid processing of. As a silver halide photographic light-sensitive material, there has been a demand for a light-sensitive material having excellent storage stability and stable performance, suitability for rapid processing by an automatic processor, and excellent antistatic performance.

[0009]

Therefore, a first object of the present invention is to provide a silver halide photographic light-sensitive material for a laser light source which has excellent scratch resistance and has antistatic performance and which is suitable for ultra-rapid processing. is there. The second object of the present invention is to
The film has a good shelf life and there is no residual color contamination after processing,
Another object of the present invention is to provide a silver halide photographic light-sensitive material for a laser light source having the above performance.

[0010]

The above problems have been solved by the present invention described below. That is, in a silver halide photographic light-sensitive material having at least one silver halide emulsion layer and a non-light-sensitive protective layer on one side of a support, the silver halide emulsion layer has the following general formulas (I) and ( II) is spectrally sensitized to at least 600 nm by at least one selected from the group of compounds represented by II), and the hydrophilic colloid layer constituting the photosensitive material contains a fluorine-containing nonionic surfactant and an inorganic nitrate. It is achieved by a silver halide photographic light-sensitive material for a laser light source, which contains at least one.

[0011]

[Chemical 3]

In the formula (I), R ₁ and R ₅ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a carboxyl group. R ₂
R ₄ and R ₄ may be the same or different and each represents an alkyl group, and R ₃ represents an alkyl group.

X ₁ and X ₂ may be the same or different and each represents a sulfur atom or a selenium atom. Y ₁ ⁻ represents a counter ion, m represents 0 or 1, and m is 0 when an intramolecular salt is formed.

In the formula (II), R ₆ , R ₇ , R ₁₁ and R ₁₂ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group or a carboxyl group. Represent R ₈ and R ₁₀ may be the same or different and each represents an alkyl group or an aralkyl group, and R ₉ represents an alkyl group. X ₃ and X ₄ may be the same or different and each represents a sulfur atom or a selenium atom.
Y ₂ ⁻ represents a counter ion, n represents 0 or 1, and n is 0 when an intramolecular salt is formed.

The present invention will be described in detail below.

First, the sensitizing dyes represented by the general formulas (I) and (II) will be described.

In the general formula (I), the alkyl group represented by R ₁ and R ₅ is preferably a lower alkyl group having 1 to 5 carbon atoms and may be substituted with a hydroxyl group, a carboxyl group or a sulfo group. As the alkoxy group represented by R ₁ and R ₅ , a lower alkoxy group having 1 to 5 carbon atoms is preferable. The halogen atom represented by R ₁ and R ₅ is chlorine,
Examples thereof include fluorine and iodine, but chlorine atom is preferable. R
_The alkyl group represented by ₂ and R ₄ is also preferably a lower alkyl group having 1 to 5 carbon atoms, and may be substituted with a carboxyl group or a sulfo group. The alkyl group represented by R ₃ also has 1 to 1 carbon atoms.
The lower alkyl group of 3 is preferable and may be substituted with an aryl group or a halogen atom. Y ₁ ^- as a counter ion represented by the halogen ion, perchlorate ion, thiocyanate ion, benzenesulfonate ion, p- toluenesulfonate ion, including but methylsulfate ion or the like, R ₁
Alternatively, R ₅ preferably forms an inner salt (m = 0).

In the general formula (II), the alkyl group, the alkoxy group and the halogen atom represented by R ₆ , R ₇ , R ₁₁ and R ₁₂ are as described for R ₁ and R ₅ in the general formula (2). The same group as each group can be mentioned. Examples of the alkyl group represented by R ₈ and R ₁₀ include the same groups as the alkyl groups described for R ₂ and R ₄ in formula (I). R ₈ and R
Examples of the aralkyl group represented by ₁₀ include benzyl and phenethyl groups, which may be substituted with a carboxyl group or a sulfo group. Examples of the counter ion represented by Y ₂ ^— include the same groups as those described for Y ₁ ^— in the general formula (I), but in the general formula (2), R ₈ or R ₁₀ is an intramolecular group. It is preferred to form a salt (m = 0).

Typical specific examples of the sensitizing dyes represented by the general formulas (I) and (II) (referred to as the sensitizing dyes of the present invention) are shown below, but the invention is not limited thereto.

[0020]

[Chemical 4]

[0021]

[Chemical 5]

[0022]

[Chemical 6]

[0023]

[Chemical 7]

[0024]

[Chemical 8]

[0025]

[Chemical 9]

[0026]

[Chemical 10]

[0027]

[Chemical 11]

These sensitizing dyes of the present invention are disclosed in US Pat.
It can be easily synthesized according to the synthetic method described in US Pat. No. 408, US Pat. No. 3,149,105 and the like.

The amount of the sensitizing dye used in the present invention varies depending on the type of silver halide and the amount of silver, but the total amount (I + II or I or a plurality of I or II) per mol of silver halide is 0.005. ~ 1.0 g is preferable, more preferably 0.01
~ 0.6g.

The amount of the fluorine-containing nonionic surfactant used in the present invention is 0.0001 g per 1 m ² of the light-sensitive material.
˜5 g, preferably 0.001 g to 0.5 g. The fluorine-containing nonionic surfactant in the present invention is
It may be used in combination with other known surfactants. Further, another surfactant may be contained in another layer that does not contain the fluorine-containing nonionic surfactant according to the present invention.

The inorganic nitrate used in the present invention may be used in an amount of 0.005 g to 0.5 g, preferably 0.01 g to 0.2 g per 1 m ² of the light-sensitive material.

Next, the fluorine-containing nonionic surfactant used in the present invention will be described.

The preferred fluorine-containing nonionic surfactant used in the present invention has a fluoroalkyl group having 4 or more carbon atoms, or an alkenyl group or an aryl group, and the nonionic group is a substituted or unsubstituted polyoxy group. Examples thereof include compounds having an ethylene group, a polyglyceryl group or a sorbitan residue.

Particularly preferred is a polyoxyethylene group having a perfluoroalkyl group, an alkenyl group or an aryl group having 6 to 14 carbon atoms, which is substituted or unsubstituted as a nonionic group (5 to 50 is preferable as an oxyethylene group). And a fluorine-containing nonionic surfactant having a).

Preferred specific examples are listed below.

[0036]

[Chemical 12]

[0037]

[Chemical 13]

In addition to the above, the fluorine-containing nonionic surfactant used in the present invention includes, for example, JP-A-49-10722, British Patent No. 1,330,356, JP-A-53-84712, and JP-A-54-14224. Same 5
Those described in, for example, 0-113221 can be used.

The above-mentioned fluorine-containing nonionic surfactant according to the present invention may be added to any of the hydrophilic colloid layers constituting the silver halide photographic light-sensitive material. For example, a surface protective layer, an intermediate layer, It is added to a non-photosensitive layer such as an undercoat layer or a backing layer or a silver halide emulsion layer. More preferred are an emulsion layer and its surface protective layer, a backing layer and its surface layer. These may be used not only on one-sided layer but also on both-sided layers simultaneously.

Next, the inorganic nitrate used in the present invention will be described.

Inorganic nitrates useful in the present invention are either water-soluble or water-dispersible salts of nitric acid. Examples of useful salts include ammonium nitrate and metal salts of nitric acid such as aluminum nitrate alkali metal nitrates and alkaline earth metal nitrates. Preferred nitrates are metal nitrates such as lithium nitrate, sodium nitrate, potassium nitrate and alkaline earth metal nitrates such as calcium nitrate and magnesium nitrate. Mixtures of these nitrates can also be used if desired.

The above-mentioned inorganic nitrate according to the present invention may be added to any of the hydrophilic colloid layers constituting the silver halide photographic light-sensitive material. For example, a surface protective layer, an intermediate layer, an undercoat layer or a backing layer. It is added to a non-photosensitive layer such as a layer or a silver halide emulsion layer. More preferred are an emulsion layer and a surface protective layer thereof, a backing layer and a surface layer thereof. These may be used not only on one surface layer but also on both surface layers at the same time.

In a preferred embodiment of the present invention, a silver halide emulsion layer spectrally sensitized with at least one of the dyes represented by formulas (I) and (II) is coated, A constitution in which the above-mentioned fluorine-containing nonionic surfactant and inorganic nitrate are contained in the protective layer on the emulsion layer can be mentioned.

The sensitizing dye may be added at any time between the end of the desalting step and the end of the chemical ripening, but it is preferably the start of chemical ripening.

Next, the silver halide grains used in the silver halide photographic light-sensitive material of the present invention (hereinafter, also simply referred to as "light-sensitive material") will be described.

The light-sensitive material of the present invention is a single-sided light-sensitive material in which a photosensitive silver halide is coated on only one side of the support, and the above-mentioned total amount of silver is 3.5 g / m ² per side.
Or less, more preferably 2.0 to 3.3 g / m ² .

The silver halide composition of the chemically aged silver halide emulsion used in the present invention may be any silver halide such as silver bromide, silver iodobromide and silver chloroiodobromide. Good. 30 mol% as a preferable silver halide composition
The following are silver iodobromide emulsions containing silver iodide.

If the halogenated particles have the constitution of the present invention,
It may be of any crystal type, for example, a single crystal such as a cube, octahedron, or tetrahedron, or multiple twin grains having various shapes.

The emulsion used in the light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No.17643 (December 1978), “Emulsi” on pages 22-23.
on Preparation and Types ”or the same (RD)
No. 18716 (November, 1979), page 648. See also “The Theory of the Ph” by TH James
otographic process ”4th edition, published by Macmillan (1977) 38
~ Method described on page 104, "Photographic Em" by GF Duffin
ulsion Chemistry ”, published by Focal Press (1966), P.Gla
"Chimie et Physique Photographique" by fkides, Pau
l Published by Montel (1967) or VL Zelikman et al. “Making A
nd Coating Photographic Emulsion ", published by Focal Press
It can also be prepared by the method described in (1964) and the like.

That is, the mixing conditions such as the forward mixing method, the reverse mixing method, the double jet method and the control double jet method under the solution conditions such as the acidic method, the ammonia method and the neutral method,
It can be produced using a particle preparation condition such as a conversion method, a core / shell method, or a combination thereof.

The average grain size of silver halide grains is 0.1 to 0.6 μm.
It may be a monodisperse emulsion having a narrow particle size distribution and a polydisperse emulsion having a wide particle size distribution. The monodisperse emulsion referred to herein means a silver halide emulsion having a grain size variation coefficient of 0.20 or less as defined in JP-A-60-162244.

Monodisperse emulsions include those emulsions having an average grain size of greater than 0.1 μm, at least 95 wt% of which are within ± 40% of the average grain diameter. Further, a silver halide emulsion having an average grain size of 0.25 μm to 2 μm and having at least 95% of the silver halide grains by number or weight within the range of the average grain size ± 20% is also included.
The average grain size referred to here is the diameter of a spherical silver halide grain, or the diameter of a cubic image or a spherical grain other than a spherical grain when the projected image is converted into a circular image of the same area. is there.

The method for producing the above-mentioned monodisperse emulsion is known, and for example,
J. Phot. Sci, 12.242 to 251, (1963), JP-A-48-36890,
52-16364, 55-142329, 58-49938, British Patent 1,413,748, US Patents 3,574,628, 3,655,394 and the like. As the emulsion used in the light-sensitive material of the present invention, as a method for obtaining the above monodisperse emulsion, for example, a seed crystal is used, and an emulsion grown by supplying silver ions and halide ions with this seed crystal as a growth nucleus is used. May be. The silver halide composition of the unchemically ripened silver halide emulsion used in the present invention is, for example, silver bromide, silver iodobromide,
Any silver halide such as silver chloroiodobromide may be used. A preferable silver halide composition is a silver iodobromide emulsion containing 30 mol% or less of silver iodide.

The unchemically ripened silver halide grains may have an average grain size of 0.8 μm to 2.0 μm, and may be a monodisperse emulsion having a narrow grain size distribution or a polydisperse emulsion having a wide grain size distribution.

The silver halide grains may be of any crystal type as long as they have the constitution of the present invention, for example, a single crystal such as a cube, an octahedron or a tetrahedron, and various shapes. It may be a multi-twin crystal grain having.

The unchemically-ripened silver halide grains can be prepared by the same method as the above-mentioned chemically-ripened grains according to the present invention. The crystal structures of the chemically ripened silver halide grains and the non-chemically ripened silver halide grains of the emulsion according to the present invention may have different silver halide compositions inside and outside, and have a layered structure. May be. An especially preferred embodiment of the emulsion is a silver halide grain having substantially two distinct layered structures (core / shell structure) consisting of a high iodine core portion and a low iodine shell layer.

The high-iodity core portion is silver iodide, and the silver iodide content is 0 to 20 mol%, preferably 0 to 5 mol%.

The silver halide composition other than silver iodide in the core portion may be either silver bromide or silver chlorobromide, but a composition having a high silver bromide ratio is desirable.

The outermost shell layer is a silver halide containing 5 mol% or less of silver iodide, preferably 2 mol%.
It is a layer containing the following silver iodide. The silver halide other than the silver iodide in the outermost layer may be any of silver chloride, silver bromide and silver chlorobromide, but a composition having a high silver bromide ratio is desirable.

The method for producing the above-mentioned core / shell type emulsion is known, and is described in, for example, J. Photo. Sci, 24.198. (1
976), U.S. Pat. Nos. 2,592,250 and 3,505,06.
No. 8, No. 4,210,450, No. 4,444,877 or JP-A-60-1433.
The method described in No. 31 can be referred to.

In order to remove soluble salts, the emulsion may be subjected to a Nudell water washing method, a flocculation sedimentation method or the like, 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 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 (RD) No. 17643, (RD) No. 18716 and (RD) described above.
Various compounds described in No. 308119 (December 1989) can be used. The types and locations of the compounds described in these three (RD) are listed below.

Additives 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 Photosensitive material of the present invention The water swelling rate of the coating film was compared with that before immersion by immersing the photosensitive material after 3 days at 38 ° C. and 50% relative humidity in distilled water at 21 ° C. for 3 minutes. Expressed as a percentage, the value is 150% or less, preferably 100% or less.

These conditions can be controlled by adjusting the amount of binder such as gelatin, latex and water-soluble polymer and the amount of hardener. The amount of binder is 2.
It is preferably 0 to 3.2 g / m ² , and as the gelatin hardener, aldehyde compounds, triazine compounds, vinyl sulfone compounds and the like are preferably used.

Examples of the support used in the light-sensitive material of the present invention include those described in the above RD. Suitable support is a plastic film or the like, and the support surface has the adhesiveness of the coating layer. An undercoat layer may be provided for improvement, or corona discharge or ultraviolet irradiation may be applied.

The light-sensitive material may be composed of a silver halide emulsion layer, a protective layer, an intermediate layer, a filter layer, an ultraviolet absorbing layer, an antistatic layer, an antihalation layer and a hydrophilic colloid layer such as a backing layer. .

For these hydrophilic colloid layers, various synthetic polymer compounds including gelatin as a binder or protective colloid can be used.

Examples of gelatin include lime-processed gelatin,
Acid-treated gelatin or gelatin derivatives may be used. Examples of synthetic polymers other than gelatin include cellulose derivatives such as hydroxyethyl cellulose, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polyacrylamide, and other single or copolymers. Can be used. Photographic processing of the light-sensitive material of the present invention includes, for example,
RD-17643, XX to XXI, pages 29 to 30 or 308119, XX.
~ XXI, treatments with treatment solutions as described on pages 1011-1012 may be performed. This process may be either a monochrome photographic process for forming a silver image or a color photographic process for forming a dye image. The treatment temperature is usually in the range of 18 ° C to 50 ° C.

Developers for black and white photographic processing include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-P-aminophenol). Etc. can be used alone or in combination. In the developer, well-known preservatives, alkali agents, pH buffers, antifoggants, hardeners, development accelerators, surfactants, defoamers, toning agents, water softeners, dissolution aids, etc. You may use an agent, a viscosity imparting agent, etc. as needed.

A fixing agent such as thiosulfate or thiocyanate is used in the fixing solution, and a water-soluble aluminum salt such as aluminum sulfate or potassium alum may be contained as a hardening agent. In addition, it may contain a preservative, a pH adjuster, a water softener and the like.

[0072]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 Using a silver iodobromide (silver iodide content of 2 mol%) seed emulsion having an average grain size of 0.1 μm, an ammoniacal silver nitrate aqueous solution and a potassium bromide aqueous solution were added by the double jet method, and the average Particle size 0.25μ
A cubic monodisperse emulsion of silver iodobromide (average silver iodide content: 0.1 mol%) of m was grown. The coefficient of variation (σ / r) was 0.17.

The above emulsion was dissolved immediately before chemical ripening, and when the temperature became constant, the dyes represented by the general formulas (1) and (2) according to the present invention shown in Table 1 were added, and ammonium thiocyanate and chloroauric acid were added. Then, sodium thiosulfate was added for chemical sensitization, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added.

Further, this emulsion was mixed with an unchemically ripened emulsion prepared as shown below in a ratio shown in Table 1.

(Preparation of unchemically ripened emulsion) Average grain size 0.3 μm
Silver iodobromide (silver iodide content 2 mol%) seed emulsion of
A monodisperse emulsion having an average grain size of 1.10 μm and a silver iodide content of 3 mol% was grown by the ammonia method. The coefficient of variation was 0.17.

The following additives were added to the emulsion coating solution per mol of silver halide.

Nitrophenyl-triphenylphosphonium chloride 30 mg 1,3-Dihydroxybenzene-4-ammonium sulfonate 1 g 2-Mercaptobenzimidazole-5-sodium sulfonate 10 mg 2-Mercaptobenzothiazole 10 mg Trimethylolpropane 9g 1,1- Dimethylol-1-bromo-1-nitromethane 10mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1g

[0079]

[Chemical 14]

(Emulsion side protective layer liquid) It has the following composition. The added amount is shown as an amount per 1 liter of the coating liquid.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sulfo-succinic acid (i-amyl decyl) ester sodium salt 1 g Polymethylmethacrylate 4 μm particles Silicon dioxide particles (matting agent having an area average particle size of 1.2 μm) 0.5 g Ludox AM ( DuPont colloidal silica) 30g 2-4-dichloro-6-hydroxy-1,3,5-triazine / sodium salt 2% aqueous solution (hardening agent) 10cc 35% formalin (hardening agent) 2cc glyoxal 40% aqueous solution (Hardener) 1.5 cc Further, the fluorine-containing nonionic surfactant according to the present invention and the inorganic nitrate were added to this emulsion surface side protective layer liquid as shown in Table 1.

As a backing layer, a dye emulsion dispersion comprising 400 g of gelatin, 2 g of polymethylmethacrylate having an average particle size of 6 μm, 24 g of potassium nitrate, 6 g of sodium dodecylbenzenesulfonate and 120 g of the following antihalation dye-1 equivalent to 2 g / m ² , And a glyoxal backing layer solution were prepared, and glycidyl methacrylate-methyl acrylate-butyl methacrylate copolymer (50: 1
(0:40 weight ratio) was diluted to a concentration of 10 wt% to obtain an aqueous copolymer dispersion, which was coated as an undercoating solution on one side of a polyethylene terephthalate base. A backed support obtained by coating with a protective layer solution containing glyoxal and sodium dodecylbenzenesulfonate was prepared.

The coating amount for both the backing layer and the protective layer is 2.0 g / m ² as the gelatin coating amount.

[0084]

[Chemical 15]

A sample was obtained by applying the emulsion coating solution and the protective layer to the backed base at the same time in two layers with a slide hopper. Coating amount 3.0 g / m ² of silver amount conversion, gelatin weight emulsion layer 2.5 g / m ^2, the protective layer was 1.2 g / m ^2.

The photographic performance was evaluated using each of the samples thus obtained. The formalization method is as follows.

<Sensitometry> The photographic characteristic is a wavelength of 633n.
A wedge image was printed with a He-Ne laser beam of m and a 670 nm semiconductor laser beam for evaluation on a film of 14 × 17 cm. In addition, the processing is automatic developing machine for X ray SRX-502, developer XD-SR,
A fixing solution XF-SR (both manufactured by Konica Corporation) was used for processing at a developing temperature of 35 ° C. for 45 seconds. Regarding the sensitivity in Table 1, the sensitivity to 633 nm light is 670
The sensitivity to m light is the relative sensitivity expressed as 100 for Comparative Sample 4.

Sensitivity after storage The raw sample was allowed to stand at 40 ° C. and 70% RH for 48 hours, then the sensitivity was determined in the same manner as in the above sensitometry measurement method, and compared with the untreated sample.

<Residual color property> Regarding the residual color property, after the unexposed film (14 × 17 cm) was developed by the above-mentioned processing, the residual color was evaluated visually by the following four stages on a light source for photographic observation.

A: Dye residue is not present B: Dye residue is slightly present, but does not hinder diagnosis C: Dye residue is present in a diagnostically noticeable amount D: Dye residue is apparent and diagnostic There is a problem <Static mark generation test (antistatic performance)> After conditioning the obtained sample for 2 hours in a dark room at a temperature of 23 ° C and a relative humidity of 20%, after rubbing with a sample of neoprene rubber roller After development, the state of generation of static marks was visually evaluated according to the following criteria.

Evaluation Criteria A: No occurrence of static marks B: Very few occurrences C: Somewhat occurrences D: Many occurrences E: Very many occurrences <Scratch resistance (thread-shaped) Desensitization)> Adjust the humidity of the sample for 1 hour in an atmosphere of 70% relative humidity in a dark room, place two samples on a horizontal table, and then load two samples with a load of 1 kg. The upper sample was pulled at a speed of 5 cm / sec to form scratches between the samples. Density 1.0 after 3 minutes
The whole surface was uniformly exposed so as to give the image, and the development processing was performed in the same manner as the sensitometry. The obtained sample was visually evaluated according to the following 5 grades.

Evaluation Criteria A: No desensitization due to threading B: Slight threading desensitization is recognized but hardly noticeable C: Some threading desensitization is recognized, but desensitized area Is blurred in white. D: Thread-like desensitization occurs over about 1/3 of the sample, and white areas are slightly visible. E: Thread-like desensitization occurs over about 2/3 of the sample, resulting in desensitization. The results are as follows.

[0093]

[Table 1]

[0094]

[Table 2]

As is apparent from the table, the sample according to the present invention has more stable sensitivity after storage than the comparative sample, and there is no deterioration in sensitivity. It can also be seen that there are few static marks and scratches, and there is no residual color contamination on the processed film.

[0096]

According to the present invention, a silver halide photographic light-sensitive material for a laser light source, which is excellent in scratch resistance and antistatic property, has a good raw storability of the film, and has no residual color after processing, can be obtained.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer and a non-photosensitive protective layer on one side of a support, wherein the silver halide emulsion layer has the following general formula (I ) And (II), at least one selected from the group of compounds is spectrally sensitized to 600 nm or more, and the hydrophilic colloid layer constituting the photosensitive material contains a fluorine-containing nonionic surfactant. A silver halide photographic light-sensitive material for a laser light source, which contains at least one inorganic nitrate. [Chemical 1] In the formula, R ₁ and R ₅ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a carboxyl group. R ₂ and R ₄ may be the same or different and each represents an alkyl group, and R ₃ represents an alkyl group. X ₁ and X ₂ may be the same or different and each represents a sulfur atom or a selenium atom. Y ₁ ⁻ represents a counter ion, m
Represents 0 or 1, but when forming an intramolecular salt, m is 0. [Chemical 2] In the formula, R ₆ , R ₇ , R ₁₁ and R ₁₂ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group or a carboxyl group. R
₈ and R _{10, which} may be the same or different, each represents an alkyl group or an aralkyl group, and R ₉ represents an alkyl group.
X ₃ and X ₄ may be the same or different and each represents a sulfur atom or a selenium atom. Y ₂ ⁻ represents a counter ion, and n is 0
Alternatively, n is 0 when 1 is represented but an inner salt is formed.