JPH06301135A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photosensitive material having no humidity dependency at the time of an exposure, no residual color stain, high sensitivity, and red-sensitivity by spectrally sensitizing a silver halide emulsion layer with at least specific two kinds of sensitization pigments. CONSTITUTION:At least one silver halide emulsion layer is spectrally sensitized by a sensitization pigment expressed by the formula I and a sensitization pigment expressed by the formula II. In the formula I, R1, R5 indicate the hydrogen atom and alkyl group, R2-R4 indicate the alkyl group, X1, X2 indicate the sulfur atom and selenium atom, Y indicates the counter ion, and (m) indicates 0 or 1. In the formula II, Y1-Y3 indicate the N(R)- group and oxygen atom, R1 indicates the aliphatic group having the carbon number of 10 or below substituted with the water-soluble group, R, R2, R3 indicate the aliphatic group and allyl group, V1, V2 indicate the hydrogen atom and alkoxy group, L1, L2 indicate methine carbon, M indicates ions required to offset the total charges of the molecule, and (n) indicates the number required to neutralize the charges of the molecule.

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 which has improved spectral sensitivity in the red light wavelength range, has no humidity dependency upon exposure, and has improved residual color contamination.

[0002]

2. Description of the Related Art A means for expanding the photosensitive wavelength range of a silver halide emulsion and increasing the sensitivity is well known as a spectral sensitization technique, and spectral sensitizing dyes used for this purpose include cyanine dyes and merocyanine dyes. The compound of is known.

These spectral sensitizing dyes must not only expand the photosensitive wavelength range of the silver halide emulsion, but must also satisfy the following conditions.

1) Appropriate spectral sensitization range 2) High spectral sensitization efficiency 3) Do not adversely affect the characteristic curve such as fog generation or gamma change 4) Halogen containing sensitizing dye Do not change the photographic performance such as fog when the silver halide photographic light-sensitive material is aged (especially when it is stored under high temperature and high humidity). 5) The added photosensitive dye diffuses to the layer of different light-sensitive wavelength range. 6) It does not cause color turbidity. 6) It does not cause color contamination due to the removal of the photosensitive dye after development, fixing and fixing. However, the spectral sensitizing dye disclosed hitherto is still at a level that satisfies all of these conditions. Has not reached.

Especially, the recent film processing speed has entered an era of ultra-rapid mass processing, for example, medical X-ray CT, MR.
In diagnostic equipment such as I, ultra-rapid processing (45 seconds or less) is performed by dedicated processing directly connected to the imaging equipment. When a low replenishment of the development processing agent is carried out in order to prevent pollution in addition to such rapid processing, residual color contamination is likely to occur on the film, and further improvement in processing property has been desired.

Further, after capturing an image for radiation diagnosis such as X-ray CT, MRI, and digital X-ray diagnosis as a digital or video signal, the image is processed by a laser beam to be drawn on a silver halide photographic light-sensitive material, A means for providing a diagnostic image as a transmission image is becoming popular.

In the recording system using a laser light source, image quality has been improved due to the widespread use of semiconductor lasers and the like, and there has been a demand for a silver halide photographic light-sensitive material for a laser light source which has high sensitivity and is stable over time. He-Ne
From 633 nm light sources such as lasers to 650 in recent years
A silver halide photographic light-sensitive material for a laser light source having stable performance for a semiconductor laser of 680 nm is required.

However, the conventional light-sensitive material has a problem that sensitivity fluctuation occurs if the light-sensitive material is left in a high humidity state during or before exposure.

Most laser imagers using a laser light source these days have a system in which an automatic developing machine is directly connected. Therefore, the inside of the laser imager becomes high in humidity due to moisture evaporated from the automatic developing machine. or,
If the imager is installed in a location that is not air-conditioned, it may be exposed to high humidity during the rainy season. In such a case, there has been a problem that the sensitivity of the film changes due to changes in the weather.

On the other hand, many dyes that have been spectrally sensitized in the red light wavelength region have been reported, for example, the Belgian patent.
541,245, U.S. Patents 2,493,747, 2,743,272, and
3,335,010, French patent 2,113,248, German patent 1,024,80
No. 0, No. 2,153,570, No. 2,300,321, etc. and the complex cyanine dyes and complex merocyanine dyes described in JP-A-3-171135, JP-A-49-111
No. 21, No. 51-33622, No. 51-115821, No. 51-115822,
58-72937, 61-203446, JP-A-2-256045, 3-1
Cyanine dyes described in each publication such as 5042, U.S. Pat.
It is known that the merocyanine dyes described in the respective specifications such as 3,747, 2,493,748, and 2,519,001, and the respective publications of JP-A-51-106422 and 59-214030 are effective.

Although some of these dyes have been attempted to reduce residual color contamination by introducing a water-soluble group into the molecule, they are not sufficient, or the spectral sensitivity decreases and the coating solution ages. Therefore, there is a problem that sensitivity fluctuation easily occurs, and it is not yet satisfactory.

Recently disclosed European Patents 363,104 and 36
The dyes described in No. 3,107 are recognized to have an effect of improving residual color contamination, but have a problem that photographic performance varies when a spectrally sensitized light-sensitive material is stored with time.

[0013]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a highly sensitive red-sensitive silver halide photographic light-sensitive material having no humidity dependency upon exposure and no residual color contamination.

[0014]

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 photosensitive silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has the following general formulas [I] and [II]. A silver halide photographic light-sensitive material, which is spectrally sensitized with at least one sensitizing dye represented by the formula (1) and at least one sensitizing dye represented by the following general formula (III).

[0015]

[Chemical 4]

(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. Well, each represents an alkyl group, 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 and m represents 0 or 1, but m is 0 when an intramolecular salt is formed. )

[0017]

[Chemical 5]

[0018] _{(wherein, R 6, R 7, R} 11 and R ₁₂ may be the same or different, each, .R ₈ represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a hydroxyl group or a carboxyl group And R _{10, which} may be the same or different, each represents an alkyl group or an aralkyl group, 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, although n represents 0 or 1, when forming an intramolecular salt is n is 0).

[0019]

[Chemical 6]

(In the formula, Y ₁ , Y ₂ and Y ₃ are each independently-
It represents an N (R)-group, an oxygen atom, a sulfur atom, or a selenium atom.

R ₁ represents an aliphatic group having 10 or less carbon atoms substituted with a water-solubilizing group, R, R ₂ and R ₃ are each an aliphatic group,
Represents an aryl group or a heterocyclic group, and R, R ₂ and R ₃
At least two of the groups replace the water solubilizing groups.
V ₁ and V ₂ each represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a group which is bonded to V ₁ and V ₂ to form a condensed ring together with an azole ring, and L ₁ and L ₂ are each independently Represents a substituted or unsubstituted methine carbon. M represents an ion necessary for canceling the total charge of the molecule, and n represents a number necessary for neutralizing the charge of the molecule. ) Hereinafter, the present invention will be described in more detail.

R ₁ and R _{5 of the} compound represented by the general formula [I]
The alkyl group is an alkyl group having up to 4 carbon atoms, such as a methyl, ethyl, propyl, or butyl group, the alkoxy group is, for example, a methoxy or ethoxy group, and the halogen atom is, for example, a chlorine atom. R ₂ ,
The alkyl group for R _{4 is} an alkyl group having up to 4 carbon atoms which may have a substituent, and examples thereof include a methyl, ethyl, propyl, sulfoethyl, sulfopropyl, sulfobutyl and sulfobenzyl group.

R ₃ is an alkyl group having up to 4 carbon atoms, such as a methyl or ethyl group. The counter ion of Y ₁ ⁻ has the same meaning as M in formula (III) described later.

R _{6 of} the compound represented by the general formula [II],
The alkyl group of R ₇ , R ₁₁ and R _{12 is} an alkyl group having up to 4 carbon atoms such as methyl, ethyl, propyl and butyl groups, the alkoxy group such as methoxy and ethoxy groups, and the halogen atom such as chlorine. Represents an atom. The alkyl group of R ₈ and R _{10 is} an alkyl group having up to 4 carbon atoms which may have a substituent and has the same meaning as R ₂ and R _{4 in} the general formula [I]. R ₉ is an alkyl group having up to 4 carbon atoms, such as a methyl or ethyl group. Y ₂ ^- formula shown later as counterion (III)
Represents the same meaning as M.

Examples of the water-solubilizing group substituting for R, R ₁ , R ₂ and R ₃ in the compound represented by the general formula [III] include, for example, sulfo group, carboxy group, phosphono group, sulfato group and sulfino. Each acid group such as a group can be mentioned.

The aliphatic group represented by R, R ₁ , R ₂ and R ₃ is, for example, a branched or straight chain alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, n-propyl, n-). Each group such as pentyl and isobutyl), an alkenyl group having 3 to 10 atoms (for example, each group such as 3-butenyl and 2-propenyl) or an aralkyl group having 3 to 10 carbon atoms (for example, benzyl,
Each group such as phenethyl). Examples of the aryl group represented by R, R ₂ and R ₃ include a phenyl group, and examples of the heterocyclic group include a pyridyl group (2-, 4
-), Furyl group (2-), thienyl group (2-), sulforanyl group,
Examples thereof include a tetrahydrofuryl group and a piperidinyl group. Each group of R, R ₁ , R ₂ and R ₃ is a halogen atom (eg fluorine atom, chlorine atom, bromine atom etc.), an alkoxy group (eg methoxy group, ethoxy group etc.), an aryloxy group (eg phenoxy group, p -Tolyloxy group etc.), cyano group, carbamoyl group (eg carbamoyl group, N-methylcarbamoyl group, N, N-tetramethylenecarbamoyl group etc.), sulfamoyl group (eg sulfamoyl group, N,
N-3-oxapentamethyleneaminosulfonyl group etc.), methanesulfonyl group, alkoxycarbonyl group (eg ethoxycarbonyl group, butoxycarbonyl group etc.), aryl group (eg phenyl group, carboxyphenyl group etc.), acyl group (eg acetyl) Group, benzoyl group, etc.) and the like.

Specific examples of the aliphatic group substituted with the water-solubilizing group include carboxymethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, 3-sulfobutyl, 6-sulfo-3-oxahexyl and ω-sulfopropoxy. Carbonylmethyl, ω-sulfopropylaminocarbonylmethyl, 3-sulfinobutyl, 3-phosphonopropyl, 4-sulfo-3-butenyl, 2-carboxy-2-propenyl, O-sulfobenzyl, P-sulfophenethyl, P -Each group such as carboxybenzyl.

Specific examples of the aryl group substituted with the water-solubilizing group include respective groups such as p-sulfophenyl group and p-carboxyphenyl group, and specific examples of the heterocyclic group substituted with the water-solubilizing group. Examples include groups such as 4-sulfothienyl group and 5-carboxypyridyl group. In these, R ₁ is an alkyl group substituted with a sulfo group,
At least two of R, R ₂ and R ₃ are each
A carboxymethyl group is preferred.

The alkyl group represented by V ₁ and V ₂ is a linear or branched group (for example, methyl, ethyl, iso-propyl, t-butyl, iso-butyl, t-pentyl, hexyl and the like). Group). Examples of the alkoxy group represented by V ₁ and V ₂ include groups such as methoxy, ethoxy, and propoxy.

The aryl group represented by V ₁ and V ₂ may have a substituent at any position, and each group such as phenyl, p-tolyl, p-hydroxyphenyl, p-methoxyphenyl and the like. Is mentioned. Examples of the condensed ring formed by combining V ₁ and V ₂ with each other to form an azole ring include benzoxazole, 4,5,6,7-tetrahydrobenzoxazole, naphtho [1,2-d] oxazole and naphtho [2, 3-
d] oxazole, benzothiazole, 4,5,6,7-tetrahydrobenzothiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, benzoselenazole, naphtho
Examples include condensed rings such as [1,2-d] selenazole. The above-mentioned substituents represented by V ₁ and V ₂ and the condensed ring formed may have a substituent at any position, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine). Atom), trifluoromethyl group, alkoxy group (eg, unsubstituted alkyl groups such as methoxy, ethoxy, butoxy, substituted alkoxy groups such as 2-methoxyethoxy, benzyloxy), hydroxy group, cyano group, aryloxy group (Eg, substituted or unsubstituted groups such as phenoxy and tolyloxy), or aryl groups (eg, phenyl, p-
Substituted or unsubstituted groups such as chlorophenyl), styryl groups, heterocyclic groups (eg, groups such as furyl and thienyl), carbamoyl groups (eg, groups such as carbamoyl and N-ethylcarbamoyl), sulfamoyl groups (eg, sulfamoyl) , N, N-dimethylsulfamoyl, etc.), acylamino group (eg, acetylamino, propionylamino, benzoylamino, etc.), acyl group (eg, acetyl, benzoyl, etc.), alkoxycarbonyl group (Eg, groups such as ethoxycarbonyl), sulfonamide groups (eg, groups such as methanesulfonylamide, benzenesulfonamide), sulfonyl groups (eg, groups such as methanesulfonyl, p-toluenesulfonyl), carboxy groups, etc. Is mentioned.

The group substituted on the methine carbon represented by L ₁ and L ₂ includes a lower alkyl group (eg, methyl,
There are groups such as each group such as ethyl), a phenyl group (each group such as phenyl and carboxyphenyl), and an alkoxy group (each group such as methoxy and ethoxy).

M represents a cation or an acid anion, and specific examples of the cation include a proton, an organic ammonium ion (eg, each ion of triethylammonium, triethanolammonium, etc.), and an inorganic cation (eg, each cation of lithium, sodium, calcium, etc.). ), And specific examples of the acid anion include, for example, a halogen ion (eg, chlorine ion, bromine ion, iodine ion, etc.), p-toluenesulfonate ion, perchlorate ion,
4-boron fluoride ion etc. are mentioned. n becomes 0 when an intramolecular salt is formed and the charge is neutralized.

Specific examples of the sensitizing dyes represented by the general formulas [I] and [II] are shown below.

[0034]

[Chemical 7]

[0035]

[Chemical 8]

[0036]

[Chemical 9]

[0037]

[Chemical 10]

The dyes represented by the above general formulas [I] and [II] according to the present invention are described in, for example, US Pat.
It can be easily synthesized by the method described in No. 3,149,105.

Incidentally, in the present invention, a representative example described in Japanese Patent Application No. 4-344178 by the same applicant as the present invention other than the specific sensitizing dye represented by the above general formula [II] is described. Illustrative examples II-1 to II-10, II-16 to II-18, II-20 to II-25
Etc. can be used arbitrarily.

Next, specific examples of the sensitizing dye represented by the general formula [III] according to the present invention will be shown.

[0041]

[Chemical 11]

[0042]

[Chemical 12]

[0043]

[Chemical 13]

[0044]

[Chemical 14]

[0045]

[Chemical 15]

[0046]

[Chemical 16]

[0047]

[Chemical 17]

[0048]

[Chemical 18]

[0049]

[Chemical 19]

The compound of the above-mentioned general formula [III] of the present invention is
For example, F. M. Hama, "Cyanine Soybean and Relayed Compounds" (1964, Inter
(Published by Science Publishers), US Patent 2,454,6
It can be easily synthesized by referring to conventionally known methods described in No. 29, No. 2,493,748 and the like.

As a specific synthetic method, the method described in Japanese Patent Application No. 5-41289 by the same applicant as the present invention can be referred to.

The addition amount of the sensitizing dye according to the present invention is not uniform depending on the conditions used and the type of emulsion, but is preferably one of the formulas [I], [II] and [I] per mol of silver halide.
The total amount of the dye represented by II] may be 0.005 to 1.0 g, preferably 0.01 to 0.6 g.

The ratio of the added amounts of the dyes represented by the general formulas [I], [II] and [III] can be arbitrarily determined according to the purpose.

The spectral sensitizing dye according to the present invention can be added to a silver halide emulsion by a conventionally known method. For example, JP-A-50-80826, a protonated dissolution addition method described in the same 50-80827, U.S. Pat.No. 3,822,135, a method of dispersion addition with a surfactant described in JP-A-50-11419, U.S. Pat.
676,147, 3,469,987, 4,247,627, JP-A-51-
59942, 53-16624, 53-102732, 53-102733
No. 53-137131, a method of dispersing and adding to a hydrophilic substrate, a method of adding as a solid solution of East German Patent 143,324, or Research Disclosure 21,802,
Water-soluble solvents that dissolve the dyes described in JP-B-50-40659 and JP-A-59-148053 (for example, low boiling point solvents such as water, methanol, ethanol, propyl alcohol, acetone, and fluorinated alcohol, dimethyl form). High boiling solvents such as amide, methyl cellosolve, phenyl cellosolve)
Can be used alone or as a method of adding it after dissolving it in a mixed solvent thereof.

The sensitizing dye of the present invention represented by the above general formula may be added at any stage in the emulsion production process from physical ripening to coating after chemical ripening, but from physical ripening to completion of chemical ripening. It is preferable to be added during.

Addition of the sensitizing dye of the present invention during physical ripening or prior to addition of the chemical sensitizer in the chemical ripening step or immediately after addition of the chemical sensitizer gives a higher spectral sensitivity. It has the effect of being used and is preferably used.

The photosensitizing dye used in the present invention can further enhance the spectral sensitivity by using a compound which brings about a supersensitizing effect. Examples of such compounds having a supersensitizing effect include, for example, U.S. Patents 2,933,390 and 3,416,927.
No. 3,51,664, 3,615,613, 3,615,632,
3,635,721, JP-A-3-15042, 3-110545, 4-
Compounds having a pyrimidinylamino group or a triazinylamino group described in 255841 etc., British Patent 1,137,580,
Aromatic organic formaldehyde condensates described in JP-A No. 61-169833, calixarene derivatives described in JP-A No. 4-184332, halogenated benzotriazole derivatives described in US Pat. No. 4,030,927, JP-A-59-142541, and the same. 59-188641
Bispyridinium compounds described in JP-A-59-191032, aromatic heterocyclic quaternary salt compounds described in JP-A-59-191032, electron-donating compounds described in JP-A-60-79348, and aminoallylidene malononitrile described in US Pat. No. 4,307,183. Polymers containing units, hydroxytetrazaindene derivatives described in JP-A-4-149937, 1,3-oxadiazole derivatives described in U.S. Pat.No. 3,615,633, amino-1,2,3, described in U.S. Pat. Four-
Examples thereof include thiatriazole derivatives.

The supersensitizer may be added at any time according to the photosensitive dye addition time. The addition amount is selected in the range of 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver halide, and the addition amount is 1:10 to 10: 1 with the photosensitive dye.

The light-sensitive material to which the present invention is applied may be a single-sided light-sensitive material in which a photosensitive silver halide is coated on only one surface side of a support. The amount of coated silver is 3.
5 g / m ² or less, more preferably 2.0~3.3g / 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. The preferred silver halide composition is 10 mol%
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 silver halide grains 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.

A method for producing the above 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 crystal structure of the silver halide grains obtained by chemically ripening the emulsion according to the present invention may have a different silver halide composition from the inside to the outside, or may have a layered structure.

A method for producing the above core / shell type emulsion is known, and for example, J. Phot. Sci, 24.198. (1976), US Pat.
The methods described in 250, 3,505,068, 4,210,450, 4,444,877 or JP-A-60-143331 can be referred to.

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 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.

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 IV B Dye 25 to 26 VIII 649 to 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006 to 7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004 to 5 X Surfactant Agent 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 As the support used for the material, the above
Examples of suitable supports include plastic films, and the support surface may be provided with an undercoat layer to improve the adhesiveness of the coating layer, corona discharge, ultraviolet irradiation, etc. May be given.

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.

As gelatin, in addition to 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.

[0077]

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 aqueous ammoniacal silver nitrate solution and an aqueous potassium bromide 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 exemplified in Table 1 were added,
After chemical sensitization by adding ammonium thiocyanate, chloroauric acid and sodium thiosulfate, 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene was added.

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-Sodium mercaptobenzimidazole-5-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

[0082]

[Chemical 20]

(Emulsion side protective layer liquid) The addition amount is shown per liter of 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 (hardener) 10ml 35% formalin (hardener) 2ml glyoxal 40% aqueous solution (Hardener) 1.5 ml As a backing layer, 2 g of a dye emulsion dispersion consisting of 400 g of gelatin, 2 g of polymethyl methacrylate 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-1O2. m
^A backing layer solution consisting of ² equivalents and glyoxal was prepared, and glycidyl methacrylate-methyl acrylate-butyl methacrylate copolymer (50:10:40 weight ratio) was diluted to a concentration of 10 wt% to obtain A backing obtained by coating with a protective layer liquid consisting of gelatin, a matting agent, glyoxal, and sodium dodecylbenzenesulfonate on one surface of a polyethylene terephthalate base coated with an aqueous copolymer dispersion as an undercoating liquid. A support 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.

[0086]

[Chemical 21]

A sample was obtained by simultaneously coating the emulsion coating solution and the protective layer on the backed base with a slide hopper in two layers. 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.

<Evaluation Method of Sensitometry and Humidity Dependence during Exposure> The photographic characteristics were that a wedge image was printed with He-Ne laser light with a wavelength of 633 nm and 670 nm semiconductor laser light.
Evaluation was made with a film of 17 cm. The processing was performed for 45 seconds at a developing temperature of 35 ° C. using an automatic processor for X-ray SRX-502, developing solution XD-SR, and fixing solution XF-SR (all manufactured by Konica Corporation). When exposing each sample, 1
From the time before to the exposure, exposure was performed in the atmosphere of the humidity shown in Table 1, and the sensitizing performance at that time was evaluated. Regarding the sensitivities in Table 1, the sensitivity to 633 nm light is 100 relative to the comparative sample 7, and the sensitivity to 670 nm light is relative sensitivity to 100 for the comparative sample 7.

<Residual color property> Regarding the residual color property, the unexposed film (14 × 17 cm) was developed by the above-mentioned treatment, and then visually evaluated with a light source for photographic observation to evaluate the residual color according to the following four stages.

A: No dye residue at all B: Dye residue is slightly present, but does not hinder diagnosis C: Dye residue is present in a diagnostically appreciable amount D: Dye residue is apparently present in diagnosis Have trouble

[0092]

[Table 1]

As is apparent from the table, the sample of the present invention exhibits excellent red light sensitivity as compared with the comparative sample, and the sensitivity variation due to humidity during exposure is small. Further, the sample of the present invention had less residual color on the processed film.

[0094]

According to the present invention, a high-sensitivity red-sensitive silver halide photographic light-sensitive material having less humidity dependency upon exposure of the light-sensitive material and improved residual color contamination can be obtained.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has the following general formula [I] and A silver halide photographic light-sensitive material characterized by being spectrally sensitized with at least one sensitizing dye represented by [II] and at least one sensitizing dye represented by the following general formula [III] . [Chemical 1] (In the formula, R ₁ and R ₅ may be the same or different, and
It 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 and m represents 0 or 1, but m is 0 when an intramolecular salt is formed. ) [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 or a hydroxyl group or a carboxyl group. R ₈ and R ₁₀ May be the same or different, each represents an alkyl group or an aralkyl group, 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, but n is 0 when forming an intramolecular salt.
Is. ) [Chemical 3] (In the formula, Y ₁ , Y ₂ and Y ₃ are each independently a —N (R) -group,
Represents an oxygen atom, a sulfur atom, and a selenium atom. R ₁ represents an aliphatic group having 10 or less carbon atoms substituted with a water-solubilizing group, and R, R
₂ and R ₃ each represent an aliphatic group, an aryl group or a heterocyclic group, and at least two groups out of R, R ₂ and R ₃ replace the water-solubilizing group. V ₁ and V ₂ are each a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or V ₁
Represents a group which forms a fused ring together with V ₂ by an azole ring, and L ₁ and L ₂ each independently represent a substituted or unsubstituted methine carbon. M represents an ion necessary for canceling the total charge of the molecule, and n represents a number necessary for neutralizing the charge of the molecule. )