JPH01128063A - Photographic sensitive material with improved color retention - Google Patents

Abstract

PURPOSE:To obtain the title material with improved sensitivity and color retention by incorporating a specified photosensitive particle in a photosensitive photographic emulsion, and by composing a sensitizing dye host crystal of a sensitizing dye having cyclodextrin or its derivative as a substituent. CONSTITUTION:The photosensitive photographic emulsion contains a photosensitive particle composed of the sensitizing dye host crystal and a silver salt particle capable of forming a latent image which has a conductive contact, namely a contact capable of transmitting an electron from the host crystal to the conduction band of a silver salt particle. The sensitizing dye host crystal is composed of the sensitizing dye having the cyclodextrin or its derivative as the substituent. The sensitizing dye is exemplified by a cyanine dye, a merocyanine dye, a composite cyanide dye, a composite merocyanine dye, a hollow polar cyanine dye, a hemicyanine dye, a styryl dye and a hemioxanol dye. Thus, the photographic sensitive material with improved sensitivity and color retention is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a photographic light-sensitive material, and more particularly to a photographic light-sensitive material with high sensitivity and improved color retention.

(Prior Art) In recent years, with the development of photographic technology, there has been a strong desire to increase the sensitivity of silver decogenide photographic materials. For example, high-speed camera shutters, rapid processing of color and black and white photographic paper, electronics and simplification in the printing industry, reduction of X-ray exposure dose in the medical field, etc., and higher sensitivity according to the needs of each field. It is.

Amid these trends, various research and developments have been carried out on sensitizing technology for photographic emulsions, and many useful methods have been discovered, one of which is the use of sensitizing dyes. There are techniques for increasing the efficiency of so-called spectral sensitization.

One of the measures to increase the efficiency of spectral sensitization is to increase the amount of light that can be used by increasing the number of dye layers and increasing the light absorption rate. In this case, the light absorption rate can of course be increased by increasing the amount of dye used for spectral sensitization. Unfortunately, however, the efficiency of spectral sensitization does not necessarily increase in proportion to this, and rather begins to decrease after a certain point. This is the 1937
This is a well-known fact since the 2011 report. Therefore, in order to solve this dilemma, dyes are arranged in such a way that the farther from the substrate they are, the shorter the wavelength of light is absorbed, and in order to increase the amount of absorbed light that can be used for spectral sensitization, such an ordering is A method has been proposed that uses spectral sensitizing dyes linked in advance such that
.

However, the conventional methods described above involve devising the arrangement of dyes, and are not necessarily satisfactory in terms of spectral sensitization of only a specific wavelength range.Also, the dyes tend to remain on the photosensitive material after processing. However, it has the disadvantage of poor color retention.

(Object of the Invention) Therefore, an object of the present invention is to provide a photographic emulsion with improved sensitivity from a novel point of view, and a further object of the present invention is to provide a photographic material with improved sensitivity and color retention. That's true.

(Structure of the Invention) An object of the present invention is to provide a photographic material having a light-sensitive photographic emulsion on a support, the light-sensitive photographic emulsion being in conductive contact with a sensitizing dye host crystal (the host crystal). and a silver salt particle capable of forming a latent image, the sensitizing dye host crystal has a cyclodextrin or a derivative thereof as a substituent. This was achieved using a photographic material characterized by being formed from a sensitizing dye having the following properties.

Cyclodextrin is a compound in which many D(+)-glucobylanose units form a ring through α-1,4-bonds, and depending on the number of glucose units that make up one molecule,
α (6 units), β (7 units).

γ (8 units)... are prefixed with a-cyclodextrin, β-cyclodextrin, and γ, respectively.
-It is called cyclodextrin... (general formula (
1)). Among these, α and β.

Three types of γ are well known and commercially available. These are also sometimes called cyclohexamylose, cyclohebutaamylose, cyclooctaamylose, etc. Also known are derivatives in which the hydroxyl group of these cyclodextrins is replaced by an ether, ester, amino group, or the like.

Regarding these cyclodextrins, see Cyclodextrin Chemistry by M.L., Pengu, M., Komyama.
It is described in detail in Springelberg, 1978.

General formula (I) n: an integer of 5 or more The ether derivative of cyclodextrin used in the present invention refers to a compound represented by the above general formula (I) whose hydroxyl group is alkylated to become an ether. . Among various ether derivatives, those etherified at two positions, 2-position and 6-position, are particularly preferred. For example,
heptakis-2゜6-dimethyl-β-cyclodextrin (hereinafter referred to as HDMCD) hexakis-2,6-dimethyl-α-cyclodextrin, octakis-2,6-
Examples include dimethyl-γ-cyclodextrin.

For example, heptakis-2,6-dimethyl-β-cyclodextrin is poorly soluble in water (1,85g/100m
Q) Solubility in water is significantly increased compared to β-cyclodextrin, reaching more than 10 times. Therefore, it becomes possible to prepare a concentrated aqueous solution, which is expected to have many advantages over β-cyclodextrin.

As described above, the dye compound used in the present invention is one in which cyclodextrin or a derivative thereof is linked to a dye component through a suitable linking group. Desirable carbon atoms in the bonding site of the cyclodextrin to the dye component are carbon atoms where the primary or secondary hydroxyl group of the cyclodextrin is originally present, and more preferably the number of carbon atoms where the primary hydroxyl group is present. This is shown by the structural formula: General formula (I[) n: an integer of 5 or more In the above general formula (n), the hydroxyl group is 0-alkylated, (
methylated, ethylated, etc.), 0-acylated (acetylated, tosylated, etc.), or converted into an amino group, an alkylamino group (such as a methylamino group), or an acylamino group (such as an acetylamino group). You can.

Further, in the above general formula (I), the connecting group is represented by the following formula.

+P-1-r+Y+r+Q sorrow (P, Q: >co, >cs, >so.

Y: Substituted or unsubstituted alkylene.

Arylene, aralkylene, divalent heterocycles, aromatic residues, etc. (The methylene group of alkylene and aralkylene may be broken.) t, j, and: o or 1 In addition, R and R' are hydrogen atoms, Represents a substituted or unsubstituted alkyl, aryl, aralkyl, or monovalent heterocyclic group. ) Examples of the dye compounds used in the present invention are shown below, but the scope of the present invention is not limited thereto. In addition, in the following compound examples, cyclodextrin residues are abbreviated as follows according to the number of n.

Next, as sensitizing dyes, for example, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes,
Holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment. Any of the basic basic ring nuclei commonly used for cyanine dyes can be applied to these dyes. That is, a pyridine nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and an alicyclic hydrocarbon ring or an aromatic hydrocarbon ring fused to these nuclei. These include indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, and the like can be applied.

Examples of useful sensitizing dyes used in blue-sensitive silver halide emulsion layers include West German Patent No. 929.080, US Pat. No. 2,231,658, US Pat. No. 2,519,001, No. 2
, No. 912.329, No. 3,656゜959, No. 3,
No. 672,897, No. 3,694,217, No. 4.0
No. 25゜349, No. 4,046,572, British Patent 1
, No. 242.588, Special Publication No. 44-14030, No. 5
Examples include those described in No. 2-24844. Further, useful sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
No. 1, No. 2,072.908, No. 2.739.149
No. 2,945.763, British Patent No. 505.979
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. Furthermore, useful sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat. , No. 629, same 2
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 776.280. Furthermore, cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in U.S. Pat. No. 2,213.995, U.S. Pat. It can be advantageously used in green-sensitive silver halide emulsions or red-sensitive halogen emulsions.

Furthermore, "Heterocyclic Compounds - Cyanine Dyes and Related Compounds" by F., M. Herma, John Wiley and
The dyes listed in the 1964 publication by Sands, New York, London), azo dyes, anthraquinone dyes, etc. can be used, as well as oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, etc. It will be done.

Exemplary compound Br.

lh (lO) ■0 C2H These dye compounds can be produced using a method in which a dye moiety is synthesized and then a cyclodextrin moiety is linked, or conversely, a method in which an intermediate in which a cyclodextrin is linked is synthesized and then used to dye the compound. It is possible to use any of the following.

In preparing this dye compound, cyclodextrin or its derivatives are introduced into the dye by directly reacting with the hydroxy group of cyclodextrin to form an ester bond or ether bond, or by converting the hydroxy group of cyclodextrin into an aryl group. There are methods such as converting the arylsulfonate into a sulfonate and then reacting it with a carboxylard to form an ester bond, further converting the arylsulfonate into an amino group, and roughly forming an amide bond from the amino group.

These methods are described in detail in the documents listed below. R, Preslow and Tori, E, Overman;
Journal of the American Chemical Society (1970), p. 1075; Matsui, Y.

T, Yokoi and Ni, Mochida, Chemistry Letters (
1976) No. 1037 (R, Breslow an
d L, E, Overman J, Am, Chem, So.
c,, 921075 (1979); Y, Mats
ui, T, Yk-oi and K, Mochida
Chem, Lett, 1037 (1976)) In the synthesis of this dye compound, it is preferred to react the cyclodextrin and the dye in a molar ratio of 1:1 to 1:6.

In the present invention, it is preferable to use a dye compound in which both are combined in this molar ratio, but a molar ratio of 1:1 is more preferable.

Synthesis examples of the dye compounds used in the present invention are described below.

Synthesis of Exemplary Compound (1) Dicyclohexylcarbodiimide (DCC) 0.25
9 in pyridine lQmff solution at room temperature with 5 ml of p-toluenesulfonate/acid.
It was synthesized by a method similar to that described in 4th edition.

Add 0.379 g of 3.carboxyethyl-phosphorus-2-ylidene) rhodanine and 1.389 g of β-cyclodextrin and stir for 2 days.

The reaction solution was filtered and the filtrate was concentrated. The resulting residue was subjected to column chromatography using silica gel column chromatography (acetonitrile-methanol-water) and Sephadex LH-20 (trade name, manufactured by Pharmacia Fine Chemicals) (methanol). 163 mg of Exemplary Compound (1) was obtained by purification by graphy.

Yield: 11% Melting point: 300°C Synthesis of Exemplary Compound (2) "Heterocyclic Compounds - Cyanine Dyes and Related Compounds"
3, synthesized by a method similar to that described in
-To a solution of 3.5 g of rpoxymethyl-5-(3-ethylbenzothiazoline.2-ylidene) rhodanine in dimethylformamide 50a+a, at -20°C, isobutyl chloroformate 1.4a+ff and triethylamine 1.
4+mQ was added dropwise and stirred for 1 hour. Next, 6.0 μa of anhydrous ethylenediamine was added to the reaction solution, and the mixture was stirred overnight. The reaction solution was filtered, and the residue was recrystallized from chloroform-methanol to obtain 1.79 of 3-(2-aminoethyl)carbamoylmethyl-5-(3-ethylbenzothiazolin-2-ylidene)rhodanine.

It was synthesized by the method described in Y. Matsui, T. Yokoi, and Ni Mochida, Chemistry Letters Tantan, p. 1037. 0.159 sodium iodide was added to a DMF 1Os4 solution of 1.299 mono(6-〇-tosyl)-β-cyclodextrin, and after stirring at 80°C for 2 hours, 3-(2-aminoethyl) was added to the reaction solution. 3.94 g of carbamoylmethyl 5-(3-ethylbenzothiazoline 2-ylidene) rhodanine are added and the mixture is subsequently stirred at 80'O for 60 hours. The reaction solution was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography (acetonitrile-methanol-water) and Sephadex LH-20.
(Product name, manufactured by Pharmacia Fine Chemicals) (
By purifying by column chromatography using methanol), 150+n of Exemplified Compound (2) was obtained.

Yield: 10% Melting point: 300°C Synthesis of Exemplified Compound (3) In the method for synthesizing Exemplified Compound (1), 3-carboxyethyl-5-(3-ethylbenzothiazolin-2-ylidene) rhodanine was replaced with 3-carboxyethyl-5-(3-ethylbenzothiazolin-2-ylidene) Propyl-5-
(3-ethylbenzothiazolin-2-ylidene) Exemplary compound (3) was prepared in exactly the same manner except that rhodanine was used.
28119 obtained.

Yield: 15% The dye compound host crystal in the present invention can be obtained using a common known crystallization technique.

Moreover, two or more kinds of the dye compounds of the present invention may be used,
Each may be used alone.

It is preferable to control the crystal size of the dye compound, and the size can be controlled by controlling the precipitation rate. Useful crystal sizes can vary widely depending on the photographic application, but are generally comparable to conventional light-sensitive silver halide grains, with average diameters preferably between 0.1 and 5 μm, particularly between 0.2 and 2 μm. 0 um is preferable. However, for high-sensitivity or low-resolution applications, dye crystals with a particle size of 20 μm or more can be used, and dye crystals with extremely small particle sizes such as those found in Lippmann emulsions are also useful. Such fine particles are preferably used in photosensitive materials that do not require extremely high sensitivity, such as printed photosensitive materials and microfilms.

The particle size distribution may be monodisperse or polydisperse; for example, monodisperse crystals can be used to increase contrast and reduce exposure latitude.

Polydisperse crystals widen latitude and reduce contrast.

The effect of particle size distribution on photographic response is discussed in detail in Wey et al., US Pat. No. 4,552,838.

The silver salt particles having conductive contact with the host crystal of the dye compound may have any composition capable of forming a developable latent image. For photography, in addition to silver halides, silver thiosulfate, silver phosphate, silver cyanide and silver carbonate (such as Berriman, U.S. Pat. No. 3,367.77)
No. 8 and Maskasky U.S. Pat. No. 4,471,050. ) are also known.

Preferred silver salt particles capable of forming a latent image are silver halides, specifically silver bromide, silver chloride, silver iodide, silver iodobromide, silver chloroiodide, silver iodobromide, and silver iodobromide. Mention may be made of silver or mixtures thereof.

Particles may be normal or abnormal (e.g. twinned);
Other than silver iodide, it has a rock salt structure and can have seven generally known crystal phases. It is also possible to have more than one of the seven crystal phases at the same time. In the case of silver iodide, alpha, beta, gamma or mixed crystal forms may be used.

Other useful crystalline forms of silver salts are also disclosed in US Pat. No. 4,471.050 to Maskasky.

The particles are in conductive contact with the host dye compound crystals. Although it is possible to interpose a transmission medium that binds the particles and the host dye compound crystals, a simple arrangement allows the particles to contain at least one of the dye compound crystals.
They are directly bonded through two crystal planes. The basic unit of the emulsion of this invention is a host dye compound crystal having conductive contact with at least one grain. One host dye compound crystal requires only one conduction band-bound particle, but many particles can share the same host dye compound crystal, and in some cases the host crystal is effectively shelled by a silver salt. be able to. Of course, minimizing the average conduction bus between the site of 7-oton absorption by the dye compound crystal and the particle site will minimize the chance that the 7-oton in the dyed metal crystal will lose energy. However, closely adjacent particle sites on the same host crystal compete for the energy delivered by the 7 oton, resulting in a split particle that captures some available energy but forms a latent image that can be developed. Not enough to do that. The optimum number and arrangement of particles on the host dye compound crystal determines the conduction loss of the host dye compound crystal.
, the size and shape of the host dye compound crystals, the relative size of the particles, and the relative importance of sensitivity.

The number of moles of dye contained in the host crystal compound relative to the number of moles of silver contained in the silver salt forming the particles can vary within a wide range, but in particular, the number of moles of dye contained in the host crystal compound can range from 0.5 to 500 per mole of silver.
0 mmol, especially 1-500 mmol, especially 5-1
00 mmol is preferably used.

One preferred method of arranging grains in host dye compound crystals for good electron transfer is to arrange them in the presence of host dye compound crystals in the same manner as is used in the preparation of conventional photographic emulsions containing silver salt grains. This is a method of precipitating silver salt particles. However, for direct particle deposition (particularly epitaxial) on the host dye compound crystal planes, it is preferred that no peptitizer be present during particle formation. Once grain nucleation occurs, subsequent grain growth occurs even in the presence of conventional emulsion veptitizers. The method of Mignot (US Pat. No. 4,334,012) is cited as an example of a particularly preferred method for nucleation and initial growth of emulsion grains in the absence of a vebutitizer.

Although a single-jet precipitation method of host dye compound crystals and particles dispersed in a halide salt solution is possible, dispersing the host dye compound crystals in a non-aqueous solvent and using conventional double-jet addition into the solvent is preferable. preferable. Both single and double jet solvent precipitation methods applicable to this invention are described in Research Disclosure Vol.
176, (December 1978 XRD17643). It is also possible to use non-aqueous media in the production of silver halide. This is advantageous if the host dye compound crystals are not water soluble. For example, the dispersion medium can be selected from a number of polar organic solvents, such as ketones, aldehydes and esters, which do not serve as solvents for the sensitizing dyes, and salts of silver and counterions that are soluble in polar organic solvents. can be used for reaction. The addition of tetrabutylammonium chloride and silver trifluoroacetate to ethyl acetate as a dispersing medium can be mentioned as an example of a useful preparation of the emulsion according to the invention.

Once the desired conduction band relationship between the silver halide grains and the host dye compound crystals is established, many common emulsion preparation techniques can be employed to complete the emulsion.

For example, it is possible to add a veptitizer to the dispersion medium containing the host dye compound crystals, to partially grow the grains, and to complete the formation of the silver halide by dry techniques.

Furthermore, washing with water, addition of additives, selection of a support, coating, etc. can be carried out, for example, in accordance with Research Disclosure No. 17643 shown above.

Due to the particular nature of the emulsions used in this invention, variations from the conventional procedure may also be used.

For example, the silver salt initially formed can be different from the silver salt used for grain growth.

1 to form the desired host dye compound crystal interface.
It is particularly preferred to select one silver salt and epitaxially grow a silver salt more suitable for latent image formation thereon.

The particles of this invention can be sensitized by the use of conventional chemical sensitizers, including spectral sensitizing dyes.

It is particularly desirable to improve the light absorption capacity of host dye compound crystals by adsorbing one or more common spectral sensitizing dyes, an attempt that is not possible with a single dye compound crystal. This provides the possibility of dye combinations to achieve supersensitization.

The silver halide emulsion used in the light-sensitive material of the present invention includes:
Any silver halide such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used.

The silver halide grains in the silver halide emulsion may have a regular crystal structure such as a cube, an octahedron, or a dodecahedron, or may have an irregular crystal structure such as a spherical shape or a plate shape. (irregular) crystal forms,
Alternatively, it may have a composite form of these crystal forms.

Furthermore, research disclosure (Research
h Disclosure (hereinafter abbreviated as RD), 22
The tabular grains described in Vol. 5, 22534, pages 20-58 (1983) may also be used. In addition, special public interest public corporation 41-
A combination of internal latent image type silver halide grains and surface latent image type silver halide grains described in No. 2086 can also be used.

The photographic emulsion used in the present invention is P.
(P, Glafkides) "Chimie et P.
hysiquePhotographique)J,
Published by Paul Montel (1)
967), G.F. Duffin (G.

``7 Photographic Emulsion Chemistry'' by F. Duffin)
u)sion Chemistry) J, published by The Focal Press (
(1966), V. L. Zelikman et al.

Zelikn+anet al)r Making and Coating Photographic Emulsion (
Making and Coating Photogr
aphic Emulsion) J, The Bone Focal
It can be prepared using the method described in Press Co., Ltd. (1964). Silver halide emulsions can be prepared using sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. known in the art.
Alternatively, chemical sensitization may be performed using a combination thereof, or spectral sensitization may be performed using a methine dye or the like.

As binders for the photographic constituent layer, proteins such as gelatin and casein; cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose; sugar derivatives such as sodium nialginate and starch derivatives; polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, acrylic acid copolymers, or , synthetic hydrophilic colloids such as their hydrolysates, etc. can be used. Gelatin here refers to so-called lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, and modified gelatin.

Examples of the support used in the photosensitive material of the present invention include polyolefins such as polyethylene, polystyrene,
cellulose derivatives, such as cellulose triacetate,
Polyester film or baryta paper such as polyethylene terephthalate.

Included are supports made of sheets of synthetic paper or paper coated on both sides with these polymer films.

The support used in the present invention can also be provided with an antihalation layer. For this purpose, mention may be made of carbon black or of various dyes, such as oxonol, azo, styryl, anthraquinone, merocyanine and tri(or di)arylmethane.

In addition, chemical sensitizers, spectral sensitizers, antifoggants, stabilizers, hardeners, plasticizers, lubricants, coating aids, brighteners, ultraviolet absorbers, and couplers used in the photosensitive material of the present invention. , color image stabilizers, etc., are not particularly limited; for example, RD,
Volume 176, 17643.22-28 (1978)
You can refer to the description.

The photosensitive material of the present invention includes ordinary black and white photosensitive materials (photosensitive materials for photographing, film, etc.), silver salt diffusion transfer process, gray transfer process, silver dye bleaching method, heat-developable photosensitive materials, etc., but it is particularly effective for photosensitive materials for high-temperature rapid processing and high-sensitivity photosensitive materials. .

Regarding the processing of these photosensitive materials, please refer to L.F.N.
Photographic Grossing Chemistry by Mason (L, F, A, Mason)
graphic processing chemis
try) J, Ther7f-Cal Press (1975) and RD, vol. 176, 17643 (cited above), 28-
You can refer to the description on page 31.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

3.06 g (10 m mo(2)) was dissolved in 5Q methanol at room temperature. After adding 1.0 M potassium nitrate aqueous solution IQ with stirring, it was allowed to stand for 24 hours. The supernatant was discarded, and the precipitated crystals were dissolved in 5Q methanol. redispersed in water. Again 2
After standing still for 4 hours, the supernatant was discarded. This water washing process was repeated once more.

Next, 2.5 mmol of this dye crystal was placed in a container equipped with a stirrer and stirred (finished to 30011 IQ with water).

) At room temperature for 10 minutes, a silver nitrate aqueous solution with a concentration of 0.5M and 0
．． A 5M aqueous potassium chloride solution was added at the same time.

The addition rate was lOm#/win and 0.05 mole of silver was used.

The solution was then heated to 35°C and 18g of gelatin solution was added. The ratio of dye crystals to silver chloride crystals is 50 m o
+o12/Ag moQ. At this time, silver chloride has dye crystals attached, and the particle size is approximately 2.0μ.
It was rich. This emulsion is designated as E-1.

Example 1 The same procedure as in Comparative Example (1) was carried out except that the sensitizing dyes used in Comparative Example (1) were replaced with Exemplary Compounds (3), (4), and (9) of lQm moQ. Emulsions E-2, E-3, and E-4 of the present invention were prepared.

These emulsions E-1 to E-4 were each coated on a triacetyl cellulose film support, and polymethyl methacrylate (average particle size 5.0 μm), gelatin hardening agent (H-1) and (H A gelatin layer containing -2), a surfactant, etc. was applied to prepare samples No. 1-No. 4. (Amount of coated silver 2-597 m"s Amount of gelatin 2.09/I11") C(CHz = CHSOzCHz) scc[(zs
The samples were wedge exposed using white light and developed for 2 minutes at 20° C. using D-19 developer.

The concentration of the sample thus obtained was measured using blue light, and the capri and sensitivity were determined, and the results shown in Table 1 were obtained.

Note that the sensitivity in Table 1 is expressed as a relative value when the value of the comparative sample (NO, 1) is taken as 100. Further, the sensitivity is the reciprocal of the amount of exposure required to obtain a transmitted light blackening density of "fog value + 1.0".

As is clear from Table 1, the samples of the present invention had a remarkable sensitizing effect compared to the comparative samples.

Example 2 Sample No. 6 was prepared in exactly the same manner as in Example I, except that the dye used in Example 1 was changed to Exemplified Compound (14), and the results shown in Table 2 were obtained.

In addition, sample No. with the following dye (B) was used as a comparative dye.
, 5 was used.

As is clear from Table 2, the samples of the present invention had a remarkable sensitizing effect compared to the comparative samples.

Example 3 Monodisperse cubic silver iodobromide containing 2.0 mol% of silver iodide with an average grain size of 0.20 μm was prepared by a double jet method while controlling the temperature at 60°C, pAg-8.0, and pH=2.0. A crystal emulsion was obtained. A portion of this emulsion was used as a core and grown as follows. That is, in a solution containing core particles and gelatin, 4
An ammoniacal silver nitrate solution and a solution containing potassium iodide and potassium bromide were added using a double jet method at 0°O, pAg 9.0, pH 9.0 to form a first coating layer containing 30 mol% silver iodide. . Furthermore, pAg=9.0, pH=9
．． A second coating layer was formed by adding an ammoniacal silver nitrate solution and a potassium bromide solution using a double jet method to prepare a cubic monodisperse silver iodobromide emulsion with an average grain size of 0.50 μm. It was set at 7. The average silver iodide content of this emulsion was 2.2 mol%.

Emulsion E-8 with an average silver iodide content of 2.0 mol% and an average grain size of 1.0 μm was prepared in the same manner as E-7 by changing the addition time and flow rate of the ammoniacal silver nitrate solution and the halide solution. Each was prepared.

Next, desalting was carried out using a conventional flocculation method. That is, the temperature was maintained at 400C, and an aqueous solution of a formalin condensate of sodium naphthalene sulfonate and magnesium sulfate was added to cause coagulation.

After removing the supernatant, add pure water at 40°C, add magnesium sulfate aqueous solution again to coagulate, remove the supernatant,
It was redispersed in an aqueous gelatin solution.

Potassium chloroaurate, sodium thiosulfate, ammonium thiocyanate, and the following sensitizing dyes (C) and (D) were added to E-7 and E-8 for optimal chemical sensitization, and 4-hydroxy -6-methyl-1,3,3a
, 7-titrazaindene 2×·10-” mol/silver halide 1 mol. Sensitizing dye (C) 500+119/silver halide 1 mol Sensitizing dye (D) 20IIIg/silver halide 1 mol Further emulsion As a layer additive, t per mole of silver halide
-Butyl-catechol 4001ng, polyvinylpyrrolidone (molecular weight 10,000) 1.09, styrene/maleic anhydride copolymer 2.59, polyethyl acrylate (molecular weight 250000) 2.59, trimethylolpropane log, diethylene glycol 5g, nitro Phenyl-triphenylphosphonium chloride 50m
g, 4 g of ammonium 1,3-dihydroxybenzene-4-sulfonate, 2-mercaptobenzimidazole-
15 mg of 5-sulfonic acid sorta, 10 mg of 2-mercaptobenzthiazole, 10 mg of -l-bromo-1-nitromethane, (Preparation of coating sample) Polyethylene terephthalate support having subbing layers on both sides to improve adhesion. On one side of the support layer, an emulsion layer prepared in exactly the same manner as in Example 1 by changing the sensitizing dye as shown in Table 3, and then E-7 and E-8.
Three layers were coated at the same time at a coating speed of 120 m/min in order of an emulsion layer in which the emulsions were mixed at a ratio of 8:2, and then a protective layer, and dried in 2 minutes and 30 seconds.

Further, the other side was coated in the same manner to obtain samples No. 7 to No. 12 shown in Table 3.

The amount of gelatin in the protective layer per side is 1.29/I11
”, the amount of silver in the emulsion layer mixed with E-7 and E-8 emulsions was 2.0.
97 m2, gelatin amount 1.8 g 7 m'', silver amount in the emulsion layer according to the present invention 0.2 s/m2, gelatin amount 0.5 g
/m2 Tea Tsuta.

The following compounds were added as protective layer additives.

That is, per gram of gelatin, sodium chloride 10119 formaldehyde 31119 glyoxal 2 mg 2-hydroxy-4,
6-dichloro-1,3,5-triazine sodium salt
3mgCtbCOO(CH2)sCHs Story C, F,, -0i CH2CH2O stone CH, CH*OH2
□C,F+ySO3K
3rag Matting agent 7 consisting of polymethyl methacrylate with an average particle size of 5 μm rtrg, Colloidal silica 7 (htg) with an average particle size of 0.013 μm
etc. were added.

(Method for measuring sensitivity) A sample was sandwiched between X-ray photographic intensifying screens KO-125 (manufactured by Konica Corporation), irradiated with X-rays at a tube voltage of 80 kV at different distances, and then exposed to a roller using the following developer. The film was developed using a transport type automatic developing machine KX-500 (manufactured by Konica Corporation) at 35°C for 130 seconds, fixed, and dried to complete the development process.

Developer solution> Potassium sulfite 70g Hydroxyethylethylenediamine triacetate Trilium acetate
8g 1,4-dihydroxybenzene
289 Boric acid 10
95-Methylbenzotriazole 0.0491
-7enyl-5-mercaptotetrazole 0.01g Sodium metabisulfite 5g Acetic acid (90%
) 1.3g triethylene glycol 15g■-Phenyl-3-pyrazolidone 1.293-nitroindazole
0.2g glutaraldehyde
4.0g ethylenediaminetetraacetic acid disodium 2.0g Potassium bromide 4.0g 5-nitropenzimidazole LOg112 was made into an aqueous solution, and potassium hydroxide was made into a liquid having a pH of 10.50.

Fixer> Sodium thiosulfate pentahydrate 45g Disodium ethylenediaminetetraacetate 0.5g Ammonium thiosulfate 1509 Anhydrous sodium sulfite 8g Potassium acetate
169 Aluminum sulfate lO ~ 18 hydrate 279 Sulfuric acid (50yt%) 6° Citric acid 1g Boric acid
7°glacial acetic acid
This was made into an aqueous solution with a pH of 4.0 by adding glacial acetic acid.

Sensitivity evaluation was performed on the development comparison sample as described above. The sensitivity was expressed as a relative sensitivity, with the reciprocal of the X-ray dose giving a blackening density of sample No. 1 fog + 1.0 being 100.

(Measurement of MTF) The obtained sample was placed on an intensifying screen KO-125 in the same manner as in the measurement of sensitivity.
The square wave chart was photographed using the contrast method, and the aperture size was 300 μ in the parallel direction of the rectangular wave and 25 μ in the perpendicular direction using a Konica Microdensitometer M-5 model (manufactured by Konica Corporation) and magnification magnification. is 20
The MTF was measured in multiples.

Incidentally, the MTF showed a value of 2.0 lines/■ of the indoor frequency.

The higher the MTF value, the higher the sharpness.

(Evaluation of residual color) The obtained sample (20 cm x 30 cm) was treated with the above-mentioned automatic machine and processing agent in an unexposed state, and then the color contamination of the film was visually evaluated. O indicates good quality, Δ indicates fair quality, and × indicates poor quality that cannot be used.

(Results) As understood from the data in Table 3, the samples of the present invention have high sensitivity and high MTF values, and therefore have good sharpness and improved monochromaticity.

Table 3 Below□Lower fortune telling Sensitizing dye E C, H.

Sensitizing dye F Example 4 The sample prepared in Example 3 was exposed in the same manner as in Example 3, and the following treatments were performed.

The treatment follows the following steps, the first one having a total treatment time of 45 seconds.
This was carried out using the roller conveyance type automatic developing machine shown in the figure.

Processing temperature Processing time insertion
1.2 seconds development + transition 35°0 14.6
Arrival + crossing 33°C 8.2 seconds Washer crossing 25°C 7.2 seconds
Dry at 40℃ for 5.7 seconds
Drying 45°C 8.1 seconds total
45.0 seconds still, 1st
The configuration of the automatic developing machine shown in the figure is as described above, but in this example, an apparatus having the following specifications was used.

That is, in this example, a rubber roller is used as the roller, and its material is silicone rubber (hardness 48 degrees) for the transition part, and EPDM, a type of ethylene propylene rubber, for the processing liquid.
(hardness 46 degrees). Surface roughness Dmax of the roller
= 4 μm 1 The number of rollers was 6 in the developing section, making the total number 84. The number of opposing rollers is 51, and the ratio of number of opposing rollers/total number of rollers is 51/84#0.
It is 61. The developer replenishment amount is 20m (2/4 cut, the fixer replenishment amount is 45mff/4 cut, the washing water amount is 1.512/4 cut).
It was set to ff1in. The air volume in the drying section is 11m3/min.

A heater with a capacity of 3 KW (200 V) was used.

The total processing time is 45 seconds as described above.

The developer and fixer used in Example 3 were used. The sample of the present invention showed the same effect as Example 3' even when processed using the above-mentioned automatic developing device.

[Effects of the Invention] The present invention makes it possible to provide a photographic material with improved sensitivity and color retention from a new perspective.

[Brief explanation of the drawing]

FIG. 1 is a block diagram showing an example of an automatic developing apparatus that can be used when processing the photosensitive material according to the present invention, and FIG. 2 is a front view of the operation panel of the apparatus shown in FIG. ■...Film insertion stand, 2...Film basket, 3...Operation panel, 31...Remote control receiver, 3
2...Display, 321...Audio section, 4...
Roller, 5... Conveyance path, 6... Developer tank, 7...
Fixing tank, 8...Washing tank, 9...Drying section, 91...
Squeeze part, 92...Drying means part. Figure 1

Claims (1)

[Claims] A photographic light-sensitive material having a light-sensitive photographic emulsion on a support, the light-sensitive photographic emulsion comprising a sensitizing dye host crystal and silver salt particles capable of forming a latent image and having conductive contact with the crystal. 1. A photographic light-sensitive material comprising particles, and the sensitizing dye host crystal is formed from a sensitizing dye having cyclodextrin or a derivative thereof as a substituent.