JPH0580451A - Silver halide photographic sensitive material for laser exposure and its processing method - Google Patents

Abstract

PURPOSE:To obtain a high-sensitivity photographic sensitive material capable of being rapidly processed, excellent in development progress and free of remaining colors by incorporating a specified amt. of an iridium compd. into an emulsion and spectral-sensitizing the emulsion by a sensitizing pigment. CONSTITUTION:A photosensitive silver halide emulsion layer is formed on a transparent substrate, and the emulsion contains >=10<-8> mols of an iridium compd. per mol of silver halide and is spectral-sensitized by the sensitizing pigment shown by formula. In the formula, V1...V8 are a hydrogen atom or a univalent substituent, and the following conditions are fulfilled. Namely, when the f value (distribution coefficient by fragmentation method) of V. (K=1 to 8) is denoted by VKf, A1=V1f+V2f+V3f+V4f and A2=V5f+V6f+V7f+V8f, A1<1.63. R1 and R2 are an alkyl, L1...L3 are a methine group, M1 is a counter ion for charge neutralization, and m1 is a number of >=0 necessary for neutralizing the charge in 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 for laser exposure, and more particularly to a silver halide photographic light-sensitive material for laser exposure excellent in ultra-rapid processability and a processing method thereof.

[0002]

2. Description of the Related Art In recent years, high-temperature rapid processing has rapidly spread in the development process of photographic light-sensitive materials (hereinafter abbreviated as "light-sensitive materials"), and the processing time is greatly shortened even when processing various kinds of light-sensitive materials in an automatic developing machine. Came. In order to achieve rapid processing, a developer for achieving sufficient sensitivity in a short time, a photosensitive material that is excellent in development progress and gives a sufficient degree of blackening in a short time, and dried in a short time after washing with water. The characteristics to do are necessary.
As a method commonly used for improving the drying property of a light-sensitive material, a sufficient amount of a hardening agent (gelatin cross-linking agent) is added in advance in the coating step of the light-sensitive material, and the development-fixing-water washing step is carried out. There is a method in which the water content in the light-sensitive material before the start of drying is reduced by reducing the swelling amount of the emulsion layer or the hydrophilic colloid layer. In this method, if a large amount of a hardener is used, the drying time can be shortened by that much, but the development amount will be delayed due to the smaller swelling amount, and the desensitization and softening will be caused, and the covering power will be lowered. Further, even if the development progress can be improved, the fixing speed of the hard film causes problems such as residual silver and residual hypo, and residual color of the sensitizing dye, which is an obstacle to shortening the processing time. on the other hand,
A method for increasing the activity of a processing solution is also known, and a method of increasing the amount of the main agent or auxiliary developing agent in the developing solution, increasing the pH of the developing solution, or raising the processing temperature is effective. However, all of these methods have drawbacks such as impairing the stability of the treating solution over time, softening the tone, and increasing fog. Also in this case, if the processing time of each step of development-fixation-washing is shortened, not only the photographic sensitivity decreases but also the residual silver and the amount of residual hypo increase due to the deterioration of the fixing property. In addition, the problem of residual color comes to the surface in a light-sensitive material that has been spectrally sensitized with a sensitizing dye.

On the other hand, in the medical field, X-ray CT, MRI
As a recording system of an output image of a diagnostic device such as a (nuclear magnetic resonance absorber), a laser imager for scanning a laser beam to record on a photographic light-sensitive material and a photographic light-sensitive material for laser exposure have been widely used. As a recording laser of a laser imager, there are a He-Ne laser and a semiconductor laser, and as an exposure wavelength, a He-Ne laser,
600-700n such as AlGaP (semiconductor) laser
m region and infrared region of semiconductor laser. Among them, the laser imager having an exposure wavelength of 600 to 700 nm is in the visible range, and thus has become popular in recent years due to the ease of adjusting the optical system. However, a photographic light-sensitive material corresponding to this must use a sensitizing dye in the visible region, and it has been desired to improve the residual color at the time of rapid processing, as compared with the sensitizing dye in the infrared region. To improve the residual color, it suffices to reduce the amount of dye added, but with this method the sensitivity was lowered. Further, the method of improving the residual color by using an adsorbent is substantially improved by substituting the dye and the adsorbent on the surface of the silver halide, so that it is unavoidable that the sensitivity is lowered. Further, in addition to the improvement of residual color, the photographic light-sensitive material for laser exposure is exposed for a short time of 10 ^-3 to 10 ^-7 seconds, so that high sensitivity is an essential condition even under such conditions. .. In addition, the laser output image for medical use has a part where the density difference is clearly adjacent in the image, and that part becomes uneven in processing when it is rapidly processed by an automatic processor, which is recently required. It has been known. Since this can be improved by accelerating the development progress of the light-sensitive material, it is necessary that the sensitivity of the light-sensitive material varies little with the development time.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to provide a silver halide photograph for laser exposure which has a high sensitivity and an excellent development progress even when a rapid processing is carried out, and is improved to a level in which residual color is not hindered. To provide a light-sensitive material.

[0005]

The object of the present invention is to have a photosensitive silver halide emulsion layer on at least one side of a transparent support, wherein the silver halide emulsion comprises 1 mol of silver halide (1 mol of silver). ) containing per 10 ^-8 mole or more of iridium compounds, and are achieved by a sensitizing dye represented by the general formula (I) by a silver halide photographic light-sensitive material for laser exposure, characterized in that it is spectrally sensitized I found that.

[0006]

[Chemical 2]

In the formula (I), V ₁ , V ₂ , V ₃ , V ₄ , V
₅ , V ₆ , V ₇ and V ₈ are hydrogen atoms or monovalent substituents and satisfy the following conditions. Vk
Let the f value of (k = 1 to 8) be Vkf, and let A ₁ = V ₁ f + V ₂ f + V ₃ f + V ₄ f A ₂ = V ₅ f + V ₆ f + V ₇ f + V ₈ f. At this time, A ₁ <1.63 or A ₂ <1.63.
R ₁ and R ₂ represent an alkyl group. L ₁ , L ₂ and L ₃ represent a methine group. M ₁ represents a charge-neutralizing counterion, and m ₁ is a number of 0 or more necessary for neutralizing the charge in the molecule. The general formula (I) will be described in more detail below.

R ₁ and R ₂ are preferably unsubstituted alkyl groups having 18 or less carbon atoms (eg, methyl, ethyl,
(Purupyl, butyl, pentyl, octyl, decyl, dodecyl, octadecyl), or a substituted alkyl group (as a substituent, for example, a carboxy group, a sulfo group, a cyano group, a halogen atom (eg, fluorine, chlorine, bromine), a hydroxy group. , An alkoxycarbonyl group having 8 or less carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl), an alkoxy group having 8 or less carbon atoms (eg, methoxy, ethoxy, benzyloxy, phenethyloxy), 10 carbon atoms
The following monocyclic aryloxy groups (eg phenoxy,
p-tolyloxy), an acyloxy group having 3 or less carbon atoms (for example, acetyloxy, propionyloxy), an acyl group having 8 or less carbon atoms (for example, acetyl, propionyl,
Benzoyl, mesyl), carbamoyl group (eg carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), sulfamoyl group (eg sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl). , An aryl group having 10 or less carbon atoms (eg, phenyl,
4-chlorophenyl, 4-methylphenyl, α-naphthyl) -substituted alkyl groups having 18 or less carbon atoms}. Preferably, an unsubstituted alkyl group (eg, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group), carboxyalkyl group (eg, 2-carboxyethyl group, carboxymethyl group) ), A sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-
Sulfobutyl group).

L ₁ , L ₂ and L ₃ are methine groups or substituted methine groups (eg, substituted or unsubstituted alkyl groups (eg, methyl group, ethyl group, propyl group, 2-carboxyethyl group), substituted or unsubstituted). Aryl group (eg, phenyl group, o-carboxyphenyl group), heterocyclic group (eg, barbituric acid), halogen atom (eg, chlorine atom, bromine atom), alkoxy group (eg, methoxy group, ethoxy group), amino group (For example, N, N-diphenylamino group, N-methyl-N-phenylamino group, N
-Methylpiperazino group), an alkylthio group (eg, a methylthio group, an ethylthio group), and the like}, and may form a ring with another methine group or form a ring with an auxochrome group. You can also do it. L ₁
And L ₃ is preferably an unsubstituted methine group. L
Preferred as ₂ are an unsubstituted methine group and a substituted methine group {those substituted with an unsubstituted alkyl group (for example, a methyl group, an ethyl group, a propyl group)}, and an ethyl group-substituted methine group is more preferred.

(M ₁ ) m ₁ is included in the formula to indicate the presence or absence of a cation or anion, as required to neutralize the ionic charge of the dye. Whether a dye is a cation, an anion, or has a net ionic charge depends on its auxochrome and substituents. Typical cations are inorganic or organic ammonium ions (eg triethylammonium ion, pyridinium ion) and alkali metal ions (eg sodium ion, potassium ion, calcium ion), while anions are specifically inorganic anions or It may be any of organic anions such as a halogen anion (eg, fluorine ion, chlorine ion, bromine ion, iodine ion), a substituted aryl sulfonate ion (eg, p-toluene sulfonate ion, p
-Chlorobenzene sulfonate ion), aryl disulfonate ion (for example, 1,3-benzenedisulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6
-Naphthalenedisulfonate ion), alkylsulfate ion (eg methylsulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate salt, acetate ion, trifluoromethanesulfonate ion. .. Preferred are triethylammonium ion, pyridinium ion, iodine ion, p-toluenesulfonate ion, and alkali metal ion (sodium ion, potassium ion).

V ₁ , V ₂ , V ₃ , V ₄ , V ₅ , V ₆ , V
₇ and V ₈ are hydrogen atoms or monovalent substituents and satisfy the following conditions. Vk (k = 1 to 8)
And the f value of Vkf is set to A ₁ = V ₁ f + V ₂ f + V ₃ f + V ₄ f A ₂ = V ₅ f + V ₆ f + V ₇ f + V ₈ f. At this time, A ₁ <1.63 or A ₂ <1.63,
The case where A ₁ and A ₂ <1.63 is more preferable. More preferably A ₁ <1.33 or A ₂ <1.33,
It is more preferable that A ₁ and A ₂ <1.33. Particularly preferably, A ₁ ≦ 1.06 or A ₂ ≦ 1.06,
It is more preferable that A ₁ and A ₂ ≦ 1.06.

The f value will be described. The Vkf value means a calculated value of the partition coefficient of the substituents V _{1 to} V ₈ by the fragment method described in the literature. The partial structure for which the f value is not described can be obtained by actual measurement by the method described in the literature. Literature: C. Hansch, A.J.
AJ Leo, `` Substituent Constants for Correlation Analysis in Chemistry and Biology (Substituent C
onstants for Correlation Analysis in Chemistry and
Biology) ”John Wiley, New York, 1979.

Examples of the monovalent substituents of V _{1 to} V ₈ include a halogen atom (eg, chlorine atom, fluorine atom, bromine atom),
Preferably an unsubstituted alkyl group having 6 or less carbon atoms (eg, methyl group, ethyl group, etc.), preferably a substituted alkyl group having 10 or less carbon atoms (eg, benzyl group, α-naphthylmethyl group, 2-phenylethyl group, trialkyl group) A fluoromethyl group), preferably an acyl group having 10 or less carbon atoms (eg, acetyl group, benzoyl group, mesyl group), preferably an acyloxy group having 10 or less carbon atoms (eg, acetoxy group),
Preferably, an alkoxycarbonyl group having 10 or less carbon atoms (eg, methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group), preferably a carbamoyl group having 10 or less carbon atoms (eg, carbamoyl group,
N, N-dimethylcarbamoyl group, N-butylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group), preferably sulfamoyl group having 10 or less carbon atoms (eg sulfamoyl group, N, N-dimethylsulfamoyl group, morpholino Sulfonyl group, piperidinosulfonyl group), carboxy group, cyano group, hydroxy group, amino group, preferably an acylamino group having 8 or less carbon atoms (eg, acetylamino group), preferably an alkoxy group having 10 or less carbon atoms (eg, methoxy group). Group, ethoxy group, benzyloxy group), aryl group (eg phenyl group, tolyl group), preferably ureido group having 10 or less carbon atoms (eg N-methylureido group), heterocyclic group (eg 2-pyridyl group, 2 -Thiazolyl group), preferably an alkylthio group having 10 or less carbon atoms Such as methylthio group, ethylthio group), a thiocyanato group. Further, these monovalent substituents may be further substituted. Particularly preferably, V _{1 to} V ₈ are a hydrogen atom, an unsubstituted alkyl group having 3 or less carbon atoms (eg, methyl group, ethyl group), an alkoxy group having 3 or less carbon atoms (eg, methoxy group, ethoxy group),
Halogen atom (eg fluorine atom), hydroxy group, carboxy group, acyl group having 3 or less carbon atoms (eg acetyl group) acyloxy group having 3 or less carbon atoms (eg acetoxy group), alkoxycarbonyl group having 3 or less carbon atoms (eg methoxy) Carbonyl group), carbamoyl group having 5 or less carbon atoms (for example, N, N-dimethylcarbamoyl group, N-butylcarbamoyl group), sulfamoyl group having 3 or less carbon atoms (for example, N, N-dimethylsulfamoyl group), carbon number 3 The following acylamino group (for example, acetylamino group),
An ureido group having 3 or less carbon atoms (for example, N-methylureido group), an alkylthio group having 3 or less carbon atoms (for example, methylthio group), and a thiocyanato group. More preferably, V
₁ , V ₂ , V ₄ , V ₅ , V ₆ , V ₈ are hydrogen atoms, V ₃ ,
V ₇ is a fluorine atom.

Specific examples of the compound represented by formula (I) of the present invention are shown below. However, it is not limited to these.

[0015]

[Chemical 3]

[0016]

[Chemical 4]

[0017]

[Chemical 5]

[0018]

[Chemical 6]

[0019]

[Chemical 7]

[0020]

[Chemical 8]

[0021]

[Chemical 9]

[0022]

[Chemical 10]

The compound represented by the general formula (I) of the present invention is described in "Heterocyclic Compounds-Cyanine Die and." By FM Harmer.
Heterocyclic Compounds-
Cyanine dyes and related Compounds) (John Wiley & Sons, Inc.-New York, London, 1964).

The sensitizing dyes of the present invention may be used alone, or may be used in combination, or in combination with sensitizing dyes other than the present invention. Combinations of sensitizing dyes are often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. Research Disclosure is a useful sensitizing dye, a combination of dyes exhibiting supersensitization and a substance exhibiting supersensitization.
Volume 176, 17643 (issued in December 1978) Page 23
Item J of IV, or Japanese Patent Publication Nos. 49-25500, 43-4933, and JP-A-59-19032, 59-1.
92242 and the like. The content of the sensitizing dye of the present invention depends on the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the silver halide emulsion, the kind of the antifoggant compound, etc. It is desirable to select the optimum amount accordingly, and the test method for the selection is well known to those skilled in the art. Usually, preferably 10 ^-7 to 1 × 1 mol per mol of silver halide.
It is used in an amount of 0 ^-2 mol, particularly 10 ^{-6 to} 5 × 10 ^-3 mol. The spectral sensitizing dye of the present invention can be directly dispersed in the emulsion. Further, these may be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. The dye is usually added after chemical sensitization in many cases, but it may be added during grain formation or before chemical sensitization. Ultrasonic waves can also be used for dissolution.

The photosensitive silver halide used in the present invention is, for example, silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, or the like, and a halogen containing chlorine, bromine and / or iodide. In the case of silver iodide and silver iodobromide or silver chloroiodobromide, silver iodide is 0 to 3 mol%, preferably 0 to 1 mol%, and silver chloride is 0 to 50 mol%, preferably It is 0 to 30 mol%.
Further, in the case of silver chlorobromide, silver chloride is 0 to 98 mol%,
It is preferably 0 to 70 mol%. Further, the ratio of (100) plane / (111) plane of the silver halide grain used in the present invention is preferably 3 or more, particularly preferably 4 or more, and further preferably 5 or more. The above ratio may be 100% on the (100) plane. 5 silver halide grains having a (100) face / (111) face ratio of 3 or more, preferably 5 or more are used.
It is preferable to contain 0 wt% or more, especially 80 wt%
It is preferable to contain the above. (100) plane of the present invention /
The silver halide grains having a (111) face ratio of 3 or more can be prepared by various methods. The most common method is to maintain the pAg value during grain formation at a constant value of 8.1 or less, and simultaneously add the silver nitrate aqueous solution and the alkali halide aqueous solution at a rate higher than the dissolution rate of the particles and at a rate at which re-nucleation does not occur. There is (so-called control double jet method). More preferably, the pAg value is 7.8 or less, and further preferably 7.6.
The following is good. PAg during nucleation of silver halide
There is no particular limitation on the value, but the pAg value during grain growth is 8.1.
Hereafter, it is preferably 7.8 or less, more preferably 7.6 or less. The method of reacting the aqueous solution of silver nitrate and the aqueous solution of alkali halide may be a one-sided mixing method, but the simultaneous mixing method is preferable to obtain good monodispersity. These emulsions may be coarse grains, fine grains, or mixed grains thereof, but preferably have an average grain size (measured by projection photography, number average) of about 0.0.
Desirably, the emulsion particles are composed of 4 μ to 1.0 μ, preferably 0.2 μ to 0.7 μ.

The particle shape is preferably cubic, but spherical, potato-like, plate-like, and tabular particles having an aspect ratio of 5 or more (see Research Disclosure Item No. 2253
4 p. 20-p. 58)) and an irregular crystal form. These light-sensitive silver halide emulsions may be mixed with a substantially light-sensitive silver halide emulsion (for example, an internally fogged fine grain emulsion). Of course, emulsions having different grain sizes, halogen compositions, etc. may be separately coated in different layers to increase the exposure latitude. As the particle size distribution, narrow so-called monodisperse particles are preferably used. More specifically, as the monodisperse emulsion, an emulsion having 90% or more of all grains within ± 40% of the average grain size, and preferably 90% or more of all grains within ± 20% is preferable. Further, even if the crystal structure of the silver halide grains is uniform to the inside, it has a layered structure in which the inside and the outside are different, and British Patent No. 635,841 and US Pat. No. 3,622. Three
A so-called conversion type as described in No. 18 may be used, or a latent image mainly formed on the surface or an internal latent image type formed inside the grain may be used. The photosensitive material of the present invention contains 10 ^-8 mol or more per mol of iridium ion silver halide (per mol of silver). To contain iridium ions,
A common method is to add a water-soluble iridium compound (eg, hexachloroiridium (IV) salt) in the form of an aqueous solution when preparing a silver halide emulsion. It may be added in the form of the same aqueous solution as the halide for grain formation,
It may be added before grain formation, during grain formation, or after grain formation until chemical sensitization, but particularly preferable is grain formation addition. The iridium ion is preferably used in an amount of 10 ^-8 to 10 ^-5 mol, and more preferably 10 ^-7 to 10 ^-6 mol, per 1 mol of silver halide (silver 1 mol). When forming the silver halide grains, as a silver halide solvent for controlling the growth of the grains, for example, ammonia, rhodan potassium, rhodan ammon, and a thioether compound (for example, US Pat. No. 3,271,156).
Nos. 3,574,628 and 3,704,13
0, 4,297,439, 4,276,3
74) and thione compounds (for example, JP-A-53-14).
No. 4,319, No. 53-82, No. 408, No. 55-
77,737, etc.), amine compounds (for example, Japanese Patent Laid-Open No.
4-100,717, etc.) and the like can be used.
In addition to the silver halide solvent, a compound that adsorbs on the grain surface to control the crystal habit, such as a cyanine sensitizing dye, a tetrazaindene compound, or a mercapto compound, can be used during grain formation.

The emulsion used in the present invention is a chemical sensitization method which is usually used, for example, sulfur sensitization (US Pat. Nos. 1,574,944, 2,278,947, and 3,3). 021,215, 3,635,717, etc.), reduction sensitization (US Pat. No. 2,518,698, Research Disclosure Vo).
l. 176 (1978.12) 17643, Item 3, etc., and sensitization with thioether compounds (for example, US Pat. Nos. 2,521,926 and 3,021,215,
No. 3,046,133, No. 3,165,552
Issue No. 3,625,697, No. 3,635,71
No. 7, No. 4,198,240, etc.), or various sensitizing methods combined therewith are applied. More specific chemical sensitizers include sodium thiosulfate, Allyl thiocarbamide, thiourea, thiosulfate, sulfur sensitizers such as thioether and cystine; reduction sensitizers such as tin chloride, phenylhydrazine and reductone. Sensitizers and the like can be mentioned.

Further, the emulsion used in the present invention is preferably gold sensitized (for example, US Pat. Nos. 2,540,085 and 2,399,083). As a specific gold sensitizer, potassium chloroaurate,
There are aura thiosulfate and potassium chloroparadate. These gold compounds may be added before or after the sulfur sensitizer. It can also be added at the same time as the sulfur sensitizer. The amount of the gold sensitizer used in the present invention is 10 ^-7 to 10 ^-3 per mol of silver halide.
It is preferably used in a molar ratio, further 10 ⁻⁶ to 10
^It is particularly preferable to use it at a ratio of ^-4 mol.

The photographic light-sensitive material of the present invention has a manufacturing process,
Various compounds can be added in order to prevent sensitivity deterioration and fog generation during storage or processing. These compounds include nitrobenzene imidazole, ammonium chloroplatinate, 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene, 1-phenyl-
An extremely large number of compounds such as 5-mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercapto compounds and metal salts have long been known. An example of a compound that can be used is "The Thoery of t" by CEK Mees.
he Photographi Process "(3rd edition, 1966) 34
The original documents are listed on pages 4 to 349. For example,
U.S. Pat. Nos. 2,131,038 and 2,649,7
Thiazolium salts described in US Pat. No. 16, etc .; Azaindenes described in US Pat. Nos. 2,886,437 and 2,444,605; US Pat.
Urazols described in US Pat. No. 7,135; Sulfocatechols described in US Pat. No. 3,236,652; Oximes described in UK Patent No. 623,448; US Patents Second 2,403,9
No. 27, No. 3,266,897, No. 3,397,
987, etc., mercaptotetrazoles, nitrones, nitroindazoles; US Pat.
839,405 and other polyvalent metal salts (Po
lyvalent metalsalts); US Pat. No. 3,220,83
Thiuronium salts (Thiuroniu
m salts); U.S. Pat. Nos. 2,566,263;
597,915 and the like, salts of palladium, platinum and gold.

Particularly, a polyhydroxybenzene compound is preferable in terms of reducing fog and improving pressure resistance without impairing sensitivity. The polyhydroxybenzene compound is preferably a compound having any one of the structures below.

[0031]

[Chemical 11]

X and Y are --H, --OH, a halogen atom --OM (M is an alkali metal ion), --alkyl group, phenyl group, amino group, carbonyl group, sulfone group, sulfonated phenyl group, sulfonated alkyl, respectively. Group, sulfonated amino group, sulfonated carbonyl group, carboxyphenyl group, carboxyalkyl group, carboxyamino group, hydroxyphenyl group, hydroxyalkyl group,
It is an alkyl ether group, an alkylphenyl group, an alkylthioether group, or a phenylthioether group. More preferably, -H, -OH, -Cl, -Br, -C.
_{OOH, -CH 2 CH 2 COOH,} -CH 3, -CH 2
_{CH 3, -CH (CH 3)} 2, -C (CH 3) 3, -O
_{CH 3, -CHO, -SO 3 K} , -SO 3 H, -SCH
₃ ,

[0033]

[Chemical formula 12]

And so on. X and Y may be the same or different. Particularly preferable representative compound examples are shown below.

[0035]

[Chemical 13]

[0036]

[Chemical 14]

[0037]

[Chemical 15]

[0038]

[Chemical 16]

The polyhydroxybenzene compound may be added to the emulsion layer in the light-sensitive material or to a layer other than the emulsion layer. The addition amount is effective in the range of 10 ^-5 to 1 mol, and particularly effective in the range of 10 ^-3 to 10 ^-1 mol, per 1 mol.

The light-sensitive material produced by using the present invention may contain a water-soluble dye as a filter dye in the hydrophilic colloid layer or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced by using the present invention may include a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example, development acceleration). , High contrast, sensitization) and various other surfactants may be included. As the antistatic agent, especially US Pat. No. 4,201,586, JP-A-60
-80,849, 59-74,554, Japanese Patent Application No. 6
0-249,021 and 61-32,462, the fluorine-containing surfactants or polymers described in JP-A-60-7.
No. 6,742, No. 60-80846, No. 60-808
No. 48, No. 60-80, 839, No. 60-76, 74
No. 1, 60-58-208,743, Japanese Patent Application No. 61-
No. 13,398, No. 61-16,056, No. 61-3
No. 2,462, and the like, or nonionic surfactants described in JP-A-57-204,540.
A conductive polymer or latex (nonionic, anionic, cationic, amphoteric) described in Japanese Patent Application No. 61-32,462 can be preferably used. As the inorganic antistatic agent, conductive tin oxide, zinc oxide described in JP-A-57-118242 or the like, or a complex oxide doped with antimony or the like described in these metal oxides can be preferably used.

As the hardener used in the present invention, mucochloric acid, mucobromic acid, mucophenoxycycloric acid, mucophenoxybromic acid, formaldehyde, dimethylolurea, trimethylolmelamine, glyoxal, monomethylglyoxal, 2,3-dihydroxy- 1,
4-dioxane, 2,3-dihydroxy-5-methyl-
Aldehyde compounds such as 1,4-dioxane, succinaldehyde, 2,5-dimethoxytetrahydrofuran and glutaraldehyde; divinyl sulfone, methylene bismaleimide, 5-acetyl-1,3-diacryloyl-hexahydro-s-triazine, 1, 3,5-triacryloyl-hexahydro-s-triazine, 1,
3,5-trivinylsulfonyl-hexahydro-s-
Active vinyl compounds such as triazine bis (vinylsulfonylmethyl) ether and 1,3-bis (vinylsulfonylmethyl) propanol-2-bis (α-vinylsulfonylacetamido) ethane; 2,4-dichloro-6-hydroxy-s -Triazine sodium salt,
2,4-dichloro-6-methoxy-s-triazine,
2,4-dichloro-6- (4-sulfolinino) -s-
Triazine sodium salt, 2,4-dichloro-6-
(2-Sulfoethylamino) -s-triazine, N,
Active halogen compounds such as N'-bis (2-chloroethylcarbamyl) piperazine; bis (2,3-epoxypropyl) methylpropylammonium p-toluenesulfonate, 1,4-bis (2 ', 3) ′ -Epoxypropyloxy) butane, 1,3,5-triglycidyl isocyanurate, 1,3-diglycidyl-5- (γ-
Epoxy compounds such as acetoxy-β-oxypropyl) isocyanate; 2,4,6-triethyleneimino-s-triazine, 1,6-hexamethylene-N,
Ethyleneimine compounds such as N'-bisethyleneurea and bis-β-ethyleneiminoethylthioether; 1,
Methanesulfonic acid ester compounds such as 2-di (methanesulfonoxy) ethane, 1,4-di (methanesulfonoxy) butane, and 1,5-di (methanesulfonoxy) pentane; carbodiimide compounds; isoxazole Inorganic compounds such as system compounds; and chrome alum.

In the present invention, as a matting agent, US Pat. Nos. 2,992,101 and 2,701,245,
Homopolymers of polymethylmethacrylate or polymers of methylmethacrylate and methacrylic acid, organic compounds such as starch, silica, titanium dioxide, and strontium sulfate as described in U.S. Pat. Nos. 4,142,894 and 4,396,706. Fine particles of an inorganic compound such as barium or barium can be used. Particle size is 1-10μ
m, and particularly preferably 2 to 5 μm.

The surface layer of the photographic light-sensitive material of the present invention is used as a slip agent in US Pat. Nos. 3,489,576 and 4,04.
Silicone compounds described in 7,958, etc., Japanese Examined Patent Publication No. 56
In addition to the colloidal silica described in No. 23,139, paraffin wax, higher fatty acid ester, starch derivative and the like can be used.

Polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be used as plasticizers in the hydrophilic colloid layer of the photographic light-sensitive material of the present invention. The hydrophilic colloid layer of the photographic light-sensitive material of the present invention may contain a polymer latex for the purpose of improving pressure resistance. Examples of the polymer include a homopolymer of an acrylic acid alkyl ester, a copolymer with acrylic acid, a styrene-butadiene copolymer, and a polymer or copolymer including a monomer having an active methylene group.

The silver halide photographic light-sensitive material of the present invention may have a non-light-sensitive layer such as a surface protective layer, an intermediate layer, an antihalation layer and a back layer in addition to the light-sensitive silver halide emulsion layer. The number of silver halide emulsion layers may be two or more, and the sensitivity and gradation of the two or more silver halide emulsion layers may be different. Further, it may have one or more silver halide emulsion layers or a non-photosensitive layer on both sides of the support.

The support is preferably a polyethylene terephthalate film or a cellulose triacetate film, and particularly preferably colored blue. In order to improve the adhesion of the support to the hydrophilic colloid layer,
It is preferable that the surface is subjected to corona discharge treatment, glow discharge treatment or ultraviolet irradiation treatment. Alternatively,
An undercoat layer made of styrene-butadiene-based latex, vinylidene chloride-based latex or the like may be provided, or a gelatin layer may be provided thereon. An undercoat layer using an organic solvent containing a polyethylene swelling agent and gelatin may be provided. By applying a surface treatment to these undercoat layers, the adhesion with the hydrophilic colloid layer can be further improved. In the silver halide emulsion layer, intermediate layer, protective layer, antihalation layer, back layer, etc. used in the present invention, acylated gelatin such as phthalated gelatin or malonated gelatin in addition to gelatin as a binder; hydroxyethyl cellulose, Cellulose compounds such as carboxymethyl cellulose; soluble starch such as textulin; hydrophilic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide and polystyrene sulfonic acid can be added. Of these, it is preferable to use dextran and polyacrylamide together with gelatin.

The total coating amount of gelatin on the silver halide emulsion layer side of the support of the present invention is preferably 3.5 g / m ² or less, more preferably 3.3 g / m ² or less,
Further, 3.0 g / m ² is preferable. The coated Ag amount per one side of the silver halide emulsion of the present invention is 2.8 g / m ^2.
Or less, preferably 2.6 g / m ² or less, and more preferably 2.5 g / m ² or less. Further, the weight ratio of silver to gelatin in the silver halide emulsion layer is also an important factor from the viewpoint of suitability for rapid processing. Increasing the ratio of silver and gelatin in the silver halide emulsion layer, when processed by an automatic processor,
The so-called emulsion pick-off occurs in which the silver halide photographic light-sensitive material is peeled off by the projections of the roller and the image becomes difficult to see. From this viewpoint, the weight ratio of silver to gelatin in the silver halide emulsion layer is preferably 1.4 or less, more preferably 1.2 or less, and further preferably 1.1 or less.

The developing solution used in the present invention may contain a known developing agent. Examples of developing agents include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p-).
Aminophenol and the like can be used alone or in combination. The developer generally contains other known preservatives, alkali agents, pH buffers, antifoggants, and the like, and if necessary, a dissolution aid, a color tone agent, a development accelerator (for example,
A quaternary salt, hydrazine, benzyl alcohol), a surfactant, an antifoaming agent, a water softener, a hardener (eg, glutaraldehyde), a viscosity imparting agent and the like may be contained. As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as a fixing agent can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent. The development processing method by the automatic processor in the present invention is described in US Pat.
No. 779, No. 3515556, No. 3573914
No. 3,647,459 and British Patent No. 1269268.
It is preferable to use the roller-conveying type automatic developing machine described in Japanese Patent No. The development temperature is 18 ° C to 50
C., preferably 30.degree. C. to 45.degree. C., and the developing time is preferably 6 seconds to 40 seconds, particularly 6 seconds to 25 seconds. The total processing steps from the start of development to the fixing, washing with water, and completion of drying are preferably 25 seconds to 200 seconds, and particularly preferably 25 seconds to 100 seconds, but the silver halide photographic light-sensitive material of the present invention is preferably used. If used, the treatment for 25 to 60 seconds becomes possible, which is more preferable. Regarding the development processing method, JP-A-2-103037, page 16, upper right column, line 7 to page 19, left lower column, line 15 and JP-A-2-115837, page 3, lower right column 5, 6th from line
The description on the 10th line in the upper right column of the page can be referred to. Next, the present invention will be described more specifically by way of examples.

[0050]

【Example】

Example 1 1. Preparation of silver halide emulsion 32 g of gelatin was dissolved in 1 liter of H ₂ O, and the temperature was adjusted to 53 ° C.
0.3 g of potassium bromide, 5 g of sodium chloride and compound (I) in a container heated to

[0051]

[Chemical 17]

After adding 46 mg, 444 ml of an aqueous solution containing 80 g of silver nitrate, 45 g of potassium bromide, 5.5 g of sodium chloride and 1.7 × 10 ^-7 mol of potassium hexachloroiridium (III) in a molar ratio to silver. Aqueous solution containing 45
2 ml was added by the double jet method over about 20 minutes to form a core portion of 20 mol% silver chloride, and then 80 g
452 ml of an aqueous solution containing 8.2 g of silver nitrate was added by the double jet method over about 20 minutes, and then 400 ml of an aqueous solution containing 80 g of silver nitrate and 46.4 g of potassium bromide,
5.7 g of sodium chloride and 1.7 × 10 in molar ratio to silver
^-7 ml of an aqueous solution containing ⁷ mol of potassium hexachloroiridium (III) ate was added by the double jet method over about 25 minutes to form a shell part of 17 mol% silver chloride, and the average particle size (projected area diameter) 0.35 μm cubic monodisperse silver chlorobromide grains (variation coefficient of projected area diameter 1
0%) was prepared.

After this emulsion was desalted, 62 g of gelatin,
1.75 g of phenoxyethanol was added to adjust the pH to 6.5,
Matched to pAg 8.5. After that, the temperature was raised to 65 ° C., 2 mg of sodium thiosulfate was added, and 2 minutes later, 5 mg of chloroauric acid was added.
Was added and after 80 minutes 4-hydroxy-6-methyl-
Emulsion A was prepared by adding 512 mg of 1,3,3a, 7-tetrazaindene and then rapidly cooling to solidify. 2. Preparation of Emulsion Layer Coating Solution The following chemicals were added to Emulsion A per mol of silver halide to prepare an emulsion layer coating solution.

B. Spectral sensitizing dye (I) Comparative dyes D, E, F, G

[0055]

[Chemical 18]

Alternatively, exemplary compounds A-3, A-6, A-3
0 is shown in Table-1 b. Spectral sensitizing dye (II) Amount shown in Table-1

[0057]

[Chemical 19]

C. Polyacrylamide (molecular weight 40,000) 8.54 g d. Trimethylolpropane 1.2 g e. Sodium polystyrene sulfonate (average molecular weight 600,000) 0.46 g f. Latex of poly (ethyl acrylate / methacrylic acid) 32.8 g. 1,2-bis (vinylsulfonylacetamide) ethane 2 g h. Hydroquinone potassium monosulfonate 3.9mg

3. Preparation of Coating Solution for Surface Protective Layer of Emulsion Layer The container was heated to 40 ° C., and the following chemicals were added to prepare a coating solution. I. Gelatin 100 g b. Polyacrylamide (molecular weight 40,000) 12.3 g c. Sodium polystyrene sulfonate (molecular weight 600,000) 0.6 g d. Polymethylmethacrylate fine particles (average particle size 2.5 μm) 2.7 g e. Sodium polyacrylate 3.7 g f. t-octylphenoxyethoxyethanesulfonic acid sodium salt 1.5 g. _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 3.3g Ji. C ₈ F ₁₇ SO ₃ K 84 mg li. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 84mg j. NaOH 0.2 g. Methanol 78cc. 1,2-bis (vinylsulfonylacetamide) ethane 2. Based on the total amount of gelatin in the emulsion layer and the surface protective layer, 2. Adjust to 3% by weight. Wa. Compound (II) 52mg

[0060]

[Chemical 20]

4. Preparation of Back Layer Coating Liquid The container was heated to 40 ° C. and the chemicals shown below were added to prepare a back layer coating liquid. I. Gelatin amount 100 g b. Dye I 2.39g

[0062]

[Chemical 21]

C. Sodium polystyrene sulfonate (molecular weight 600,000) 1.1 g d. Phosphoric acid 0.55 g E. Poly (ethyl acrylate / methacrylic acid) latex 2.9 g f. Compound (II) 46 mg g. Oil dispersion of dye II described in JP-A-61-285445 246 mg as dye itself Dye II

[0064]

[Chemical formula 22]

Chi. Dye III Oligomer described in JP-A-62-276539 Surfactant dispersion Dye itself 46 mg Dye III

[0066]

[Chemical formula 23]

5. Preparation of coating liquid for surface protective layer of back layer

The container was heated to 40 ° C., and the chemicals shown below were added to prepare a coating solution.

B. Gelatin 100 g b. Sodium polystyrene sulfonate (molecular weight 600,000) 0.3 g c. Polymethylmethacrylate fine particles (average particle size 3.5 μm) 4.3 g d. Sodium t-octylphenoxyethoxyethane sulfonate 1.8 g e. Sodium polyacrylate 1.7 g f. _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 3.6g bets. C ₈ F ₁₇ SO ₃ K 268 mg h. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 45mg Li. NaOH 0.3 g Nu. 131 ml of methanol 1,2-Bis (vinylsulfonylacetamide) ethane Adjusted to 2.2% by weight based on the total amount of gelatin in the back layer and surface protective layer. Wo. 45 mg of the compound (II)

6. Preparation of Photographic Material The back layer coating solution and the surface protective layer coating solution of the back layer were coated on one side of a polyethylene terephthalate support colored in blue, and the gelatin coating amount of the back layer was 2.6.
The coating amount was 9 g / m ² , and the coating amount of gelatin in the surface protective layer of the back layer was 1.13 g / m ² . Following this,
On the opposite side of the support, the above-mentioned emulsion layer coating solution and surface protective layer coating solution were used. The emulsion layer coating solution had a coating Ag amount of 2.4 g / m ² , a gelatin amount of 1.85 g / m ² and a surface protective layer. The photographic materials 1 to 1 were coated so that the amount of gelatin of 1.2 g / m ² was applied.
5 was produced.

7. Sensitometric Method The photographic material thus prepared was subjected to sensitometry by the following method to measure the photographic sensitivity. 25 ° C for photographic material,
It is kept at 60% temperature and humidity and left for 7 days after coating, and AC-1 633 nm He-Ne manufactured by Fuji Photo Film Co., Ltd.
It exposed using the laser exposure part. The development process is CEPROS-M manufactured by Fuji Photo Film Co., Ltd., and the processing solution is CE.
-D1 · F1 The temperature was set to 35 ° C. and the treatment was performed for 45 seconds in Dry-to-Dry. As the sensitivity, the reciprocal of the exposure amount indicating D = 1.5 was taken, the sensitivity of the photographic material 1 was set to 100, and the other values were shown in relative sensitivity.

8. Evaluation of residual color The photographic materials 1 to 15 were processed without being exposed to light. FPM9000 manufactured by Fuji Photo Film Co., Ltd.
Then, the development was RD-7, 35 ° C., the fixing was Fuji F, and the processing speed was changed to an electric circuit to adjust the rotation speed of the roller, followed by dry-to-dry processing for 30 seconds. The residual color was evaluated by measuring the absorbance of the photographic material after the above treatment with a Hitachi spectrophotometer (type U-3410), and measuring the absorbance at the maximum peak wavelength (λmax) of the sensitizing dye remaining after the treatment. It was evaluated by. The larger the absorbance, the worse the residual color. The results are summarized in Table-1.

[0073]

[Table 1]

From the results shown in Table 1, it is understood that by using the sensitizing dye of the present invention, it is possible to provide a photographic material having high sensitivity and less residual color. Further, when the sensitizing dye of the present invention is used in combination with a sensitizing dye (II) other than the present invention (used as a supersensitizer), the sensitivity can be further increased, and in this case as well, residual color It can be seen that it has been reduced. From the above, it is clear that the present invention is excellent.

Example 2 1. Preparation of silver halide emulsion 1) Preparation of silver halide emulsions B to C 32 g of gelatin was dissolved in 1 liter of H ₂ O, and the mixture was heated to 70 ° C.
After putting 1.2 g of potassium bromide and 92 mg of the compound (I) in a container heated to 1, 444 ml of an aqueous solution containing 80 g of silver nitrate and an aqueous solution containing 56.3 g of potassium bromide 4
52 ml was added by the double jet method over about 20 minutes to form a silver bromide core portion, and then 400 ml of an aqueous solution containing 80 g of silver nitrate and 56.2 g of potassium bromide, the molar ratio of which is shown in Table-2. Amount of hexachloroiridium (II
I) An aqueous solution containing potassium acid (415 ml) was added by the double jet method over about 25 minutes to give a slightly rounded cubic monodispersed silver bromide grain (projected area diameter) of 0.36 μm in average particle size. Coefficient of variation of 11%) was produced.

After desalting this emulsion, 62 g of gelatin,
1.75 g of phenoxyethanol was added to adjust the pH to 6.5,
Matched to pAg 8.6. After that, the temperature was raised to 65 ° C., 2 mg of sodium thiosulfate was added, and 2 minutes later, 5 mg of chloroauric acid was added.
Was added and after 80 minutes 4-hydroxy-6-methyl-
Emulsions B to C were obtained by adding 512 mg of 1,3,3a, 7-tetrazaindene and then rapidly cooling to solidify.

2) Preparation of Silver Halide Emulsions D to G Prepared in exactly the same manner as Emulsion A except that the amount of potassium hexachloroiridium (III) in Emulsion A of Example 1 was changed as shown in Table 2. Emulsions D to G were prepared. 2. Preparation of Photographic Material The emulsion layer coating solution, emulsion layer surface protective layer coating solution, back layer coating solution, back layer surface protective layer coating solution and photographic material were prepared in the same manner as in Example 1. However, the sensitizing dyes (I) and (II) used in the emulsion layer coating solution were the same types and amounts as in the photographic material 15 of Example 1. In this way, photographic materials 16 to 21 were produced.

3. Sensitometric Method The photographic material thus prepared was subjected to sensitometry by the following method to measure the photographic sensitivity. 25 photographic materials
The temperature is kept at 60 ° C and humidity of 60% and left for 7 days after coating, and AC-633 He- of AC-1 manufactured by Fuji Photo Film Co., Ltd.
It exposed using the Ne laser exposure part. The development processing is RD using FPM-9000 manufactured by Fuji Photo Film Co., Ltd.
-7, 35 ℃, Fuji F fixing, processing speed,
Adjust the rotation speed of the roller by modifying the electric circuit,
Dry-to-Dry was processed under two conditions of 30 seconds and 90 seconds. As the sensitivity, the logarithm of the reciprocal of the exposure amount showing D = 1.5 was taken, and the sensitivity in the processing of the photographic material 15 for 30 seconds was set to 100, and the other was shown in relative sensitivity. The results are summarized in Table-2.

[0079]

[Table 2]

From the results shown in Table-2, if the iridium compound was not contained in the silver halide emulsion, Dry-to-Dry 9
It can be seen that the sensitivity difference between 0 seconds and 30 seconds is large, and the processing unevenness described in the section of the prior art is likely to occur, which is not suitable for rapid processing. From the above, it is understood that the present invention using a silver halide emulsion containing an iridium compound in an amount of 10 ⁻⁸ mol or more per 1 mol of silver is excellent.

Claims (2)

[Claims] 1. A transparent support having a photosensitive silver halide emulsion layer on at least one side thereof, wherein the silver halide emulsion contains 10 ^-8 mol or more of iridium compound per mol of silver halide (1 mol of silver). A silver halide photographic light-sensitive material for laser exposure, which is spectrally sensitized with a sensitizing dye represented by formula (I). [Chemical 1] In the formula (I), V ₁ , V ₂ , V ₃ , V ₄ , V ₅ , V ₆ , V
₇ and V ₈ are hydrogen atoms or monovalent substituents and satisfy the following conditions. Vk (k = 1 to 8)
And the f value of Vkf is set to A ₁ = V ₁ f + V ₂ f + V ₃ f + V ₄ f A ₂ = V ₅ f + V ₆ f + V ₇ f + V ₈ f. At this time, A ₁ <1.63 or A ₂ <1.63.
R ₁ and R ₂ represent an alkyl group. L ₁ , L ₂ and L ₃ represent a methine group. M ₁ represents a charge-neutralizing counterion, and m ₁ is a number of 0 or more necessary for neutralizing the charge in the molecule. 2. A method of processing the silver halide photographic light-sensitive material according to claim 1 in an automatic processor having a total processing time of 25 to 60 seconds.