JPH03213844A - Method for packing and preserving silver halide photographic sensitibe material - Google Patents

Abstract

PURPOSE:To prevent changes of the photographic characteristics of a silver halide photographic sensitive material with the lapse of time by preserving the sensitive material having a layer spectrally sensitized with at least one of specified sensitizing dyes in a deoxidized state. CONSTITUTION:A silver halide photographic sensitive material having at least one layer spectrally sensitized with at least one kind of sensitizing dye rendering a peak of spectral sensitivity at >=720 nm wavelength on the substrate is preserved in a deoxidized state. The sensitizing dye is selected among tricarbocyanine, hexamethine merocyanine, pentamethine rhodanecyanine and heptamethine rhodanecyanine. Changes of the photographic characteristics of the silver halide photographic sensitive material spectrally sensitized in the wavelength region of IR with the lapse of time can be prevented and the sensitive material can always maintain constant high sensitivity.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for packaging or preserving silver halide photographic materials, and more specifically, silver halide photographic materials spectrally sensitized in the infrared wavelength region. The present invention relates to a packaging method or a preservation method that prevents changes in the photographic properties of material r1 over time. In particular, the present invention relates to a packaging method or a storage method for preventing changes in photographic properties over time of a silver halide color photographic material having sensitivity spectrally sensitized in the infrared wavelength region for laser scanning exposure.

(Prior Art) In recent years, information storage and output, especially in the case of information including images, has been developed to store processed information, or to process stored information and output it on a display or hard copy. This is becoming widely practiced.

Conventionally, methods for obtaining hard copies from soft information include methods using electric or magnetic signals, methods using non-photosensitive recording materials such as inkjet methods, and photosensitive recording materials such as silver halide photosensitive materials and electrophotographic materials. There is a method using.

The latter method is a means of recording using an optical system that emits light controlled by image information, and the optical system itself, resolution,
Not only multi-level recording but also multi-gradation recording is possible, which is advantageous in obtaining high image quality. In particular, compared to systems using electrophotographic materials, silver halide photosensitive materials form images chemically, so higher image quality can be obtained and a larger amount of information can be recorded.

On the other hand, image formation using this silver halide photosensitive material is
Since it involves wet development processing, it is inferior to methods using electrophotographic recording materials in terms of processing time, and has not been widely used in fields where image quality requirements are not very high.

However, recent advances have been made in photographic image forming systems that use silver halide color photographic materials and compact, simple, rapid development methods, making it possible to supply extremely high-quality photographic prints relatively easily and at low cost. It is becoming. If images are obtained from software information using this method, high-quality hard copies can be easily provided at low cost.

Special efforts are required to quickly and easily develop such silver halide color photographic materials. Color photographic materials must have sufficient performance in terms of sensitivity wavelength, optimum sensitivity, color separation, and sensitivity stability that are compatible with the optical system and application used.

Conventional color copying technologies include copying machines using electrophotography, laser printers, and those that combine LEDs, silver halide heat development, and dye diffusion methods, but
No. 1-137149 discloses that at least three silver halide emulsion layers using ordinary color couplers are provided on a support, and at least two of the layers are spectrally resistant to laser light in the infrared wavelength region. A silver halide color photographic light-sensitive material containing a sensitizing dye is disclosed.

JP-A No. 63-197947 discloses a support having at least three photosensitive layers containing color couplers, at least one of which has a maximum spectral sensitivity wavelength of longer than about 670 nm. full-color recording materials that are made to be sensitive to LEDs or semiconductor lasers and that produce color images by scanning exposure and subsequent development, particularly the use of highly sensitive and stable spectral sensitization techniques and dyes; Discloses the law.

JP-A-55-13505 discloses an image recording method for color photographic materials by controlling the development of yellow, magenta, and cyan colors using three types of light beams each having a different wavelength, such as green, red, and infrared light beams. is disclosed.

4th non-invacuum I by S, H, Baek et al.
Printing International Conference Li (SPSE) Proceedings 245~
On page 247, a continuous scanning printer having a semiconductor laser output control mechanism is described.

(Problems to be Solved by the Invention) The means of using silver halide color photosensitive materials to make hard copies of soft information provides higher image quality than the means of using non-photosensitive recording means or electrophotographic materials. The use of a semiconductor laser for scanning exposure is advantageous because the exposure apparatus becomes compact and inexpensive.

However, even today, the wavelength of semiconductor lasers that can be used cannot be selected arbitrarily, and recently 67
Although wavelengths near 0 nm have reached a practical level,
Most of them are in practical use in the infrared wavelength range.

In the subtractive color photography system of the present invention, at least three photosensitive layers having spectral sensitivities in different wavelength ranges are required, and at least one or two of them, and in some cases three or more layers are required. This means that the photosensitive layer must have spectral sensitivity in the infrared wavelength range.

Furthermore, semiconductor lasers not only cannot output as large an output as those with shorter wavelengths in the visible region or infrared region close to the visible region, but also have difficulty in stably obtaining the output itself.

Therefore, the characteristics required of a photosensitive material using such a semiconductor laser are high sensitivity, stable performance even against wavelength and other fluctuations of the semiconductor laser, and all of these characteristics in the red. What is achieved in the outer range of optical wavelengths is very important.

It is difficult to satisfy such requirements in the infrared region even with silver iodobromide, which is advantageous in obtaining high sensitivity.

On the other hand, if a color image is to be rapidly obtained from a light-sensitive material exposed by such a method, it is well known that silver iodobromide lacks the speed and that silver chlorobromide is preferable.

It is also well known that so-called high silver chloride emulsions containing a high silver chloride content are particularly preferred.

However, it has been found that it is more difficult to satisfy the above requirements in the infrared region with such a high silver chloride emulsion. Silver chloride emulsions are very disadvantageous for sensitization with infrared spectral sensitizing dyes, and not only is it difficult to efficiently spectral sensitize to obtain high sensitivity, but the resulting sensitivity is also difficult to preserve the photosensitive material. It was found that there was a significant decline over time.

Generally, in such spectral sensitization, if a sensitive material using a sensitizing dye with insufficient adsorption power for silver halide is stored, or even if the adsorption power is not so sufficient, it may be stored under high humidity conditions. It is known that when a light-sensitive material is stored in the 2000s, the sensitizing dye is desorbed and the spectral exacerbation sensitivity decreases over time.

However, when this infrared spectral sensitizing dye is used, the desensitization due to storage of the photosensitive material is different from such desensitization, and is due to the sensitivity of the silver halide emulsion itself to which the infrared spectral sensitizing dye is adsorbed. This was due to a significant decline in

Conventionally, it has been known to lower the temperature at which silver halide photographic materials are stored, such as by storing them under refrigeration or freezing, as a method to prevent changes in photographic performance when storing silver halide photographic materials. In particular, silver halide photographic materials having spectral sensitivity in the infrared region are even commercially available which require such storage conditions even after they are delivered to the user. However, it is difficult in practice to carry out such preservation, and in some applications, it may even be impossible.

JP-A-53-144727 discloses a photographic product in which a photosensitive material containing a sensitizing dye is sealed with a packaging material having a low oxygen permeability under a low oxygen partial pressure. However, there is no specific description herein that it is effective for sensitizing dyes that give a spectral sensitization peak in the long wavelength infrared light region like the present invention.

The present inventor further conducted research on desensitization during storage of silver halide photographic materials containing long-wavelength infrared spectral sensitizing dyes. In the case of silver halide photographic materials using a spectral sensitizing dye selected from compounds included in thimmerocyanine sensitizing dyes, pentamethine rhodacyanine sensitizing dyes, or hebutamethine rhodacyanine sensitizing dyes, the It was found that the desensitization was remarkable.

It has also been found that when the above long wavelength infrared spectral sensitizing dye is used in a high silver chloride emulsion containing 90 mol % or more of silver chloride, desensitization during storage is more likely to become a problem.

Therefore, the technical problem to be solved here is how to maintain stable sensitivity in emulsions using long-wavelength infrared spectral sensitizing dyes, especially in high-silver chloride emulsions. The purpose is to provide a method.

(Means for Solving the Problems) The objects of the present invention have been achieved by the following silver halide color photographic material and color image forming method.

(1) In a method for packaging or storing a silver halide photographic material, at least one photosensitive layer of the silver halide photographic material is sensitized by a tricarbocyanine sensitizing dye or hexamethine merocyanine that provides a spectral sensitivity peak at 720 nm or more. The silver halide photographic light-sensitive material is spectral sensitized with at least one sensitizing dye derived from a pentamethine rhodacyanine sensitizing dye or a heptamethine rhodacyanine sensitizing dye, and the silver halide photographic light-sensitive material is in a deoxidized state. A method for packaging or storing a silver halide photographic material, characterized in that the material is packaged or stored in a.

(2) The method for packaging or storing a silver halide photographic material according to item (1), wherein the deoxidized state is an oxygen volume fraction of 2% or less.

(3) The method for packaging or storing a silver halide photographic material according to item (1) or item (2), wherein the deoxidized state is created by an oxygen scavenger.

(4) The method for packaging or storing a silver halide photographic material according to item (1) or item (2), wherein the deoxidized state is created by a solid oxygen pump.

(5) A method for packaging or storing a silver halide photographic material as described in the halogenation section of paragraph (1) or (2), characterized in that the deoxidized state is created by vacuum degassing. Method.

(6) Item (1) characterized in that the deoxidized state is created by an air replacement operation with an inert gas other than oxygen.
2. A method for packaging or storing a silver halide photographic material as described in the halogenation section or item (2).

(7) The silver halide according to items (1) to (6), wherein the deoxidized state is an oxygen volume fraction of 2% or less, and at the same time, the equilibrium relative humidity is 20% or less. Methods of packaging or storing photographic materials.

(8) The silver halide photographic light-sensitive material has at least two photosensitive layers having a spectral sensitivity peak at 720 nm or more, and each photosensitive layer contains at least one of a cyan coupler, a magenta coupler, or a yellow coupler. The method for packaging or storing a silver halide photographic material according to items (1) to (7), which is a silver halide color photographic material.

(9) The silver halide photographic light-sensitive material consists of at least three photosensitive layers containing silver chlorobromide or a silver chloride emulsion with an average silver chloride content of 10 mol% or more, and each photosensitive layer contains a cyan coupler and a magenta coupler. or yellow coupler, and the three photosensitive layers each have three light wavelength regions of 650 to 690 nm, 72 nm,
Packaging of the silver halide photographic material according to items (1) to (8), which is a silver halide color photographic material having different spectral sensitivity peaks in the wavelength ranges of 0 to 790 nm and 770 to 850 nm. method or storage method.

(10) Item (1), wherein the silver halide photographic light-sensitive material comprises at least one photosensitive layer containing silver chlorobromide or a silver chloride emulsion with an average silver chloride content of 96 mol % or more. A method for packaging or storing a silver halide photographic material according to item (9).

In the present invention, at least one photosensitive layer of the silver halide photographic light-sensitive material is a tricarbocyanine sensitizing dye, a hexamethine merocyanine sensitizing dye, a pentamethine rhodacyanine sensitizing dye, or a heptamethine sensitizing dye that has a spectral sensitivity peak at 720 nm or above. Spectral sensitization is performed using a rhodacyanine sensitizing dye, and the effects of the present invention are fully expressed at this time.

Sensitizing dyes that can be used in combination with the light-sensitive materials defined in the present invention include ordinary cyanine dyes, merocyanine dyes, composite merocyanine dyes, and the like. In addition, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes are also used. As cyanine dyes, simple cyanine dyes, carbocyanine dyes, dicarbocyanine dyes, etc. are used. Similarly, the merocyanine dye can be selected from among zeromethine merocyanine dye, dimethine merocyanine dye, tetramethine merocyanine dye, and the like.

In the present invention, even when the light-sensitive material is a color light-sensitive material, at least one light-sensitive layer has a spectral sensitivity peak at 720 nm or more, such as a tricarbocyanine sensitizing dye, a hexamethine merocyanine sensitizing dye, or a pentamethine rhodacyanine sensitizing dye. Alternatively, it is sufficient that the layer is spectrally sensitized with at least one sensitizing dye selected from heptamethine rhodacyanine sensitizing dyes, and the other photosensitive layers may be layers having a spectral sensitivity peak of 720 nm or less.

That is, the photosensitive layer of a normal color photosensitive material is composed of a plurality of photosensitive layers each containing at least one of cyan, magenta, and yellow couplers. It must be spectrally sensitized with a tricarbocyanine sensitizing dye, a hexamethine merocyanine sensitizing dye, a pentamethine rhodacyanine sensitizing dye, or a heptamethine rhodacyanine sensitizing dye, which has a spectral sensitivity peak at a wavelength of 720 nm or more, Preferably, the two different color-producing photosensitive layers are spectrally sensitized to have a spectral sensitivity peak at 720 nm or more.

In the present invention, when all three or more different color-producing photosensitive layers are spectrally sensitized to have a spectral sensitization peak at 720 nm or more, the effects of the invention are more likely to be exhibited in all of the layers.

In all of these cases, spectral sensitization was performed with a tricarbocyanine sensitizing dye, a hexamethine merocyanine sensitizing dye, a pentamethine rhodacyanine sensitizing dye, or a heptamethine rhodacyanine sensitizing dye, which gives a spectral sensitivity peak at 720 nm or higher. It is sufficient that there is at least one layer.

If a photosensitive material can also incorporate a photosensitive layer with a spectral sensitization peak at 720 nm or less, it is of course necessary to spectral sensitize all the photosensitive layers so that they have a spectral sensitization peak at 720 nm or more. That is, when exposing a photosensitive material using a laser diode, exposure can be performed using a wavelength of 720 nm or less, specifically, for example, a wavelength around 670 nm.

Therefore, in color photosensitive materials for laser diode exposure, for example, 650 to 690 nm, 720 to 790 nm,
It is only necessary to selectively spectral sensitize each coloring layer in accordance with a laser diode having an emission wavelength somewhere within each wavelength range of different wavelengths such as m, 770-850 nm, etc. Here, selective spectral sensitization This means that when a photosensitive material is exposed to light at the dominant wavelength of one laser diode, the sensitivities between different color-forming layers are separated to such an extent that they do not cause color mixing in terms of spectral sensitivity and result in undesirable color reproduction. It refers to being present.

In the present invention, the spectral sensitizing dyes preferably used, that is, the spectral sensitizing dyes used for visible sensitization or infrared sensitization, are compounds represented by the following - maximum CI), [■] and (1). You can choose from among them.

In the color photosensitive material of the present invention, at least one photosensitive layer contains a tricarbocyanine sensitizing dye represented by a compound in which m11=3 at -maximum (I); -maximum (I);
In n), pentamethine rhodacyanine sensitizing dyes or heptamethine rhodacyanine sensitizing dyes represented by compounds in which m210m22 = 3 to 4, or - maximum (I
In n), it is necessary to be spectral sensitized with at least one sensitizing dye selected from the group of hexamethine merocyanine sensitizing dyes represented by compounds with m31=3 so as to have a spectral sensitivity peak at 720 nm or more.

In addition, a sensitizing dye represented by a compound in which m11 = 3 at -maximum CI) is referred to as a tricarbocyanine sensitizing dye, and - a compound represented by a compound in which m31 = 3 at maximum (I [I)] The sensitizing dye is called a hexamethine merocyanine sensitizing dye in accordance with the common and customary nomenclature among those skilled in the art. However, calling a methine rhodacyanine sensitizing dye and calling a sensitizing dye represented by a compound where m21 + m22 = 4 a heptamethine rhodacyanine sensitizing dye do not follow the general and conventional nomenclature.
In the present invention, it will be referred to as such for the sake of simplicity.

In the present invention, spectral sensitization is more preferably performed using a specific sensitizing dye as described above so as to give a spectral sensitivity peak at 735 nm or more, and still more preferably spectral sensitization is performed so as to give a spectral sensitivity peak at 750 nm or more. , most preferably spectrally sensitized to give a spectral sensitivity peak at 770 nm or higher.

Another preferred embodiment is that the two or more photosensitive layers with different color development are composed of a sensitizing dye selected from the compounds of -8 formula (I), (If) and [■] and have a spectral sensitivity peak at 720 nm or more. This is the case when the light is spectrally sensitized to have the following properties.

The compounds represented by the general formulas CI), (II) and CDI) include compounds that adsorb to silver halide emulsion grains and spectral sensitize them so that they have a spectral sensitivity peak at 720 nm or more. Of course, as mentioned above,
Also included are compounds that spectral sensitize to have a spectral sensitization peak at 720 nm or less.

Therefore, as long as at least one photosensitive layer is spectrally sensitized with the above-mentioned sensitizing dye to have a spectral sensitization peak at 720 nm or more, other photosensitive layers that should have a spectral sensitization peak at 720 nm or less But these −maximum CI
), [11) and [■], or may be spectrally sensitized with a compound not included in these.

The present invention relates to a technique for maintaining the storage performance after coating of a silver halide photographic light-sensitive material that has been sensitized using a specific sensitizing dye on silver halide emulsion grains to give a spectral sensitivity peak of 720 nm or more. Therefore, the spectral sensitizing dyes that can be used in the present invention are not limited to the compounds represented by these maximum CI), [■] and ([1)].

The sensitizing dyes represented by general formulas CI), (II) and (III) are detailed below.

-Both formulas [1] (χ1.)9 In the formula, Zll and Zl! each represents an atomic group necessary to form a heterocyclic nucleus.

The heterocyclic nucleus includes a 5- to 6-membered ring nucleus containing a nitrogen atom and optionally a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom as a heteroatom (a fused ring is further bonded to these rings). Moyo (and may further have a substituent bonded thereto) is preferred.

Specific examples of the heterocyclic nucleus include thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, imidazole nucleus, and pen. Zimigzole nucleus, naphthimidazole nucleus, 4-quinoline nucleus, pyridine nucleus, pyridine nucleus, tetrazole nucleus, indolenine nucleus, benzindolenine nucleus, indole nucleus, tellurazole nucleus, penzotelllazole nucleus, naphthotellazole nucleus, etc. can be mentioned.

R11 and! ? +t each represents an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group.

These groups and the groups described below are used to include each of the 119 forms.For example, taking alkyl groups as an example, they include unsubstituted and yllA alkyl groups, and these groups may be linear or branched. Alternatively, the alkyl group, which may be cyclic, preferably has 1 to B carbon atoms.

Specific examples of substituents for substituted alkyl groups include halogen atoms (chlorine, bromine, fluorine, etc.), cyano groups, alkoxy groups, substituted or unsubstituted amino groups, carboxylic acid groups, sulfonic acid groups, hydroxyl groups, etc. One or more of them may be used in combination.

A specific example of the alkenyl group is a vinylmethyl group.

Specific examples of the aralkyl group include benzyl group and phenethyl group.

m represents a positive number of 1.2 or 3.

R12 represents a hydrogen atom, and Rla represents a hydrogen atom, a lower alkyl group, or an aralkyl group, and can be linked to ll+x to form a 5- to 6-membered ring.

In addition, when R14 represents a hydrogen atom, R13 represents another R1
may be linked with ゜ to form a hydrocarbon ring or a heterocycle, these rings are preferably 5- to 6-membered rings, j, 1, kll
represents 0 or 1, X represents an acid anion,
i represents 0 or 1.

-Both formulas (I[) (X!+)-,.

During the ceremony, 2, 1, Z! z has the same meaning as Z+ or Lx described above. Itt+, Fht are synonymous with I+++ or R11, and l1tz represents an alkyl, alkenyl, alkynyl, or aryol group (for example, a substituted or unsubstituted phenyl group), It! 1. Ill! represents l, 2 or 3.

R14 and Rts represent a hydrogen atom, a lower alkyl group, or an aryl group, and R14 and another R14 or Rxs and another Ls may be linked to form a hydrocarbon ring or a heterocycle. A 5- or 6-membered ring is preferred.

at+ is a sulfur atom, oxygen atom, selenium atom or N
-Rts, and Ls is synonymous with R13.

Jt+, kll %χ□ and ntt are respectively III
, kll sχ1. and n.

General formula (I[I) In the formula, Z31 represents an atomic group necessary to form a heterocycle. Examples of this heterocycle include those described in connection with 211 and zti, and other specific examples thereof such as thiazolidine, thiazoline, and benzodidine. Nuclei such as thiazoline, naphthothiazoline, selenazolidine, selenazoline, benzoselenazoline, naphthoselenazoline, benzoxazoline, naphthoxazoline, dihydropyridine, dihydroquinoline, benzimidacilline, and naphthymidacillin may be mentioned.

Q! l is Q! It is synonymous with I. R□ is Ro or Rlf
and R31 have the same meaning as Ro. h represents 2 or 3; R33 has the same meaning as Rta; Ls and another Ro may be linked to form a hydrocarbon ring or a heterocycle; j□ has the same meaning as jll;

- at maximum (1), 2. and/or zl.

Especially preferred are sensitizing dyes in which the heterocyclic nucleus of is a naphthothiazole nucleus, a naphthoselenazole nucleus, a naphthoxazole nucleus, a naphthoimidazole nucleus, a 4-quinoline nucleus. The same applies to III).

Furthermore, aggravating dyes in which the methine chain forms a hydrocarbon ring or a heterocycle are preferred.

Since infrared exacerbation uses exacerbation due to the M band of a sensitizing dye, the spectral sensitivity distribution is generally broader than exacerbation due to J band. For this reason, it is preferable to correct the spectral sensitivity distribution by providing a colored layer containing a dye in the colloid layer on the side of the bright light side of the predetermined photosensitive layer.This colored layer prevents color mixing due to its filter effect. It is effective for

As the sensitizing dye for red sensitivity or infrared sensitization, compounds having a reduction potential of -1.00 (VvsSCE) or less than that are particularly preferred, and in particular compounds with a reduction potential of -1.
.

The reduction potential can be measured using phase-discriminative second harmonic AC polarography using a mercury dropping electrode as the working electrode, a saturated calomel electrode as the reference electrode, and platinum as the counter electrode.

Also action [1! Measurement of reduction potential by phase-discriminative second harmonic AC polkunmetry using platinum for i was published in ``Journal of Imaging Science'' (Jourr+
al or Ia+aging 5science
), 309, pp. 27-35 (1986).

Furthermore, compounds selected from the group of compounds represented by general formulas (IV), (V), (Vl) and (■) shown in Japanese Patent Application No. 1983-310211, or -
It is preferable to use the compound in combination with formaldehyde condensates of the compounds represented by [■-a], [■-b], (■-C] and the like.

- Specific examples of exacerbating pigments of (II) and (I[I) are shown.

(V-3) (V-4) (V-5) (V-6) (V-7) (V-8) (V-9) (V-10) (V-11) (V-12) (V-13) (V-14) C, 8% (V-15) (V-16) (V-17) 2%% UL, II engineering (V-18) (V-19) (V- 20) し211S ■ し ziS (v-21) (V-22) (V-23) し、H％ しχ11s (V-24) (V-25) (V-26) (V-27) (■ 30) (V-31) (V-32) EtO5Off- (V-33) (V-34) (V-35) (V-36) (V-37) (V-38) Cz H4011 (V-40 ) (V-41) (V-42) tH% - tl'ls (V-43) (V-46) (V-47) (V-48) (V-49) (V-50) ( V-51) - The sensitizing dye used in the present invention is 5X per mole of silver halide.
10-'mol to 5X10-comole, preferably IX
It is contained in the silver halide photographic emulsion in a proportion of 10-''mol-lXl0-' x 104 mol to 5 X]O-' mol.

The sensitizing dye used in the present invention can be directly dispersed into the emulsion. These can also be prepared using a suitable solvent, such as methyl alcohol, ethyl alcohol, methyl cellosolve,
It can also be dissolved in acetone, water, lysine, or a mixed solvent of these, and added to the emulsion in the form of a solution. Ultrasonic waves can also be used for dissolution. In addition, as a method of adding this infrared aggravating dye, US Patent Box 3,
No. 469.987, etc., the pigment is a volatile organic! 8 medium, dispersing the solution in a hydrophilic colloid, and adding this dispersion to an emulsion, Japanese Patent Publication No. 4
No. 6-24185, etc., a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it and adding this dispersion to an emulsion, as described in US Pat. No. 3,822. 13
Surfactant Permit No. 3.822.1 as described in Specification No. 5
A method of dissolving a dye in a surfactant and adding an acid solution to an emulsion as described in JP-A-51-746
A method of dissolving a red-shifting compound as described in No. 24, and adding the solution into an emulsion, JP-A-1989-1999.
A method such as that described in Japanese Patent No. 80826, in which a dye is dissolved in an acid substantially free of water and the solution is added to an emulsion, is used. Other additions to emulsions include U.S. Patent Nos. 2 and 9
12.343, 3,342,605, 2,99
The methods described in No. 6,287 and No. 3,429,835 can also be used. The infrared enhancing dye may also be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, or may be added prior to chemical sensitization and may be added prior to the formation of silver halide grains. It is best to add it in the latter half of the season.

In the silver halide color light-sensitive material according to the present invention, in order to be compatible with rapid color development processing, it is preferable to use a coupler having a high molar ratio of the color-forming coupler to the developed silver halide. The amount of silver oxide used can be reduced. In particular, so-called 2-equivalent couplers are preferably used. Furthermore, we have proposed a method for using so-called 1-equivalent couplers in which a quinone diimine form of an aromatic amine in a color developing agent is coupled with a color coupler, and the color development process is then preformed using an oxidizing agent other than silver halide. May be used together.

Usually, color photosensitive materials use a color coupler so that the maximum color density is 3 or more in transmission density and 2 or more in reflection density. Since color gradation conversion processing is performed in conjunction with color correction processing, the maximum colored reflection density is approximately 1.2,
An excellent color image can be obtained preferably at a ratio of about 1.6 to 2.0. Therefore, the amount of color coupler and photosensitive silver halide used can be reduced.

The amount of each yellow coupler, magenta coupler and cyan coupler used in the color photosensitive material used in the present invention, especially the reflective color photosensitive material, is 2.5 to 10×10−
', 1.5-8X10-' and 1.5-7XIO-'
It is mole/po.

A coupler suitable for the color photosensitive material according to the present invention will be explained.

The cyan coupler, magenta coupler, and yellow coupler preferably used in the present invention are as follows: (C-1), (C-11), (M-1), (M-11)
and (Y).

General formula (C-1) H Y.

General formula (c-n) Oi+ General formula (M-1) General formula (M-It) General formula (Y) In general formulas (C-1) and (C-n), R5, R? and R4 represents a substituted or unsubstituted aliphatic, aromatic, or heterocyclic IF group; R1, R1, and R6 represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, or an acylamino group; R1 represents R1 May also represent a group of nonmetallic atoms forming a nitrogen-containing 5- or 6-membered ring with
Yl and Y represent a hydrogen atom or a group that can be separated during a coupling reaction with an oxidized form of a developing agent, and n represents 0 or 1.

R1 in the general formula (C-n) is preferably an aliphatic group, such as a methyl group, ethyl group, propyl group, butyl group, pentadecyl group, Ler t-butyl group, cyclohexyl group, cyclohexylmethyl group, Examples include phenylthiomethyl group, dodecyloxyphenylthiomethyl group, pukunamidomethyl group, and methoxymethyl group.

Preferred examples of the cyan coupler represented by (C-1) or (C-It) are as follows.

In general formula (C-1), preferable R1 is an aryl group,
A heterocyclic group, such as a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group,
More preferably, it is an aryl group substituted with a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group.

- In the binding margin (C-1), Ry (!: When Rz does not form a ring, R1 is preferably a substituted IA or an unsubstituted alkyl group or aryl group, particularly preferably a substituted!).
^Aryloxy is an alkyl group of flA, and R1 is preferably a hydrogen atom.

In the general formula (cn), R1 is preferably IIA or an unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

- In formula (C-It), preferable RS has 2 to 2 carbon atoms.
It is a methyl group having 15 alkyl groups and a substituent IA group having one or more carbon atoms, and the substituent IA group is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In the general formula (C-n), R2 is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

- Preferred R& in the binding margin (C-11) is a hydrogen atom,
A halogen atom, and chlorine and fluorine atoms are particularly preferred. Yl and Yt, which are preferred in (C-1) and (C-It), are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, respectively. group, a sulfonamide group.

In general formula (M-1), R1 and R9 represent an aryl group, R1 represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group,
Y represents a hydrogen atom or a radical group.

Aryl group (preferably phenyl group) of R1 and R1
Is this acceptable? The A group is the same as the zlAi allowed for the substituent R6, and may be the same or different when there are two or more B tA'L, R1 is preferably a hydrogen atom, an aliphatic acyl group or sulfonyl group, and particularly preferably a hydrogen atom.

Preferred Y is of the type that leaves off with either sulfur, oxygen or nitrogen atoms, such as those disclosed in U.S. Pat.
351, No. 897 and International Publication W 088104795
Particularly preferred is the sulfur atom hoof demolding as described in the above issue.

In general formula (M-11), R11 represents a hydrogen atom or a substituted 1A group, Y4 represents a hydrogen atom or a pulmonary radical,
Particularly preferred are halogen atoms and arylthio groups, Za,
Zb and Zc are methine, i? A represents methine, 3N- or -NH-, one of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond.

When the Zb-Zc bond is a carbon-carbon double bond, including when it is part of an aromatic ring, eFlys or Y
When forming a dimer or more multimer with 4, also Za, Z
When b or Zc is a substituted methine, this includes the case where the substituted methine forms a dimer or more multimer.

Among the pyrazoloazole couplers represented by the general formula (M-n), imidazo (1,2 -b) Virazoles are preferred, pyrazolo (1,
5-b)(1,2,4)) riazoles are particularly preferred.

In addition, a branched alkyl group as described in JP-A No. 61-65245 is directly connected to the 2.3 or 6-position of the pyrazolotriazole ring to create a pyrazolotriazole coupler, which is described in JP-A No. 61-65246. pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, European Patent Publication No. 226, It is preferred to use pyrazolotriazole couplers having an alkoxy or aryloxy group in the 6-position, such as those described in No. 849 and No. 294.785.

-m In formula (Y), R1+ represents a halogen atom, an alkoxy group, a trifluoromethyl group, or an aryl group, R11 represents a hydrogen atom, a halogen atom, or an alkoxy group, A represents -NHCOR+ 3, -NH5Ox-R
+i, -5OJHR+2, -COOR+3, -5OtN
-R+ffI4, where R12 and R14 each represent an alkyl group, an aryl group, or an acyl group, and Ys represents a leaving group.
The leaving group Ys is the same as the allowed IA group for R1, and the leaving group Ys is preferably of the type leaving off at either an oxygen atom or a nitrogen atom, with the leaving type leaving a nitrogen atom being particularly preferred.

General formula (C-1), (C-n), (M-1), (M-I
Specific examples of couplers represented by t) and (Y) are listed below.

(C-1) (C-2) tHs (C-3) ctH (C-4) 11 (C-5) Shi! (C-6) tHs (C-7) (C-8) C! H5 (C-9) (C-10) (C-12) 0■ (C-13) (C-14) (C-15) (C-16) (C-17) (C-18) (C -19) ■ Shi! (C-20) (C-21) (C-22) (M ■) (M-2) (M-3) 9 (M-4) (M-6) (M-7) (M-8) ShiL (Y-1) (Y-2) (Y-3) fl (Y-4) (Y-5) (Y-6) (Y-7) (y-a) (Y-9) (Y -10) (Y-11) The couplers represented by the above formulas (C-1) to (Y) are:
The silver halide emulsion layer constituting the photosensitive layer usually contains 0.1 to 1.0 mol per mol of silver halide, preferably 0.
．． It is contained in an amount of 1 to 0.5 mol.

In the present invention, in order to add the coupler to the photosensitive layer, various known techniques can be applied.6 Usually, it can be added by an oil-in-water dispersion method known as an oil protection method, and it can be added to a solvent. After dissolving, it is emulsified and dispersed in an aqueous gelatin solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water droplet dispersion with phase inversion.

Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method. From the coupler dispersion,
The low-boiling organic solvent may be removed by distillation, noodle washing, ultrafiltration, or the like, and then mixed with the photographic emulsion.

As a dispersion medium for such couplers, the dielectric constant (25°C
) 2 to 20 and a high boiling point RTQ medium having a refractive index (25° C.) of 1.5 to 1.7 and/or a water-insoluble polymer compound.

High boiling point 8! ! As a solvent, preferably the following general formula (A
) to (E) are used.

General formula (B) W+-COOL General formula (E) W, -0-W.

In formula C, 1, d, and d each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group,
represents an aryl group or a heterocyclic group, i is 1, OW,
or S-W, where n is an integer from 1 to 5, and when n is 2 or more, , and may be the same or different from each other, and in the general formula (E), Hl and 6 are condensed. (may form a ring).

The high boiling point organic solvent that can be used in the present invention also has a melting point of 100°C or less and a boiling point of 140°C or less, even if it is not the general formula (A) or E).
It can be used as long as it is a compound that is immiscible with water at temperatures above °C and is a good solvent for the coupler. The melting point of the high boiling point organic solvent is preferably 80'C or less. The boiling point of the high boiling point organic solvent is preferably 160°C or higher, more preferably 170°C.
That's all.

For details on these high boiling point organic solvents, please refer to JP-A-62
-215272 Publication Mei[i! It is written on the lower right side of page 137 to the upper right side of page 144 of @.

These couplers can also be impregnated into Rhodapul latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling 8!1 solvents mentioned above, or water-insoluble and 81 can be dissolved in a solvent-soluble polymer and emulsified and dispersed in an aqueous hydrophilic colloid solution.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. W08B100723 are used, and the use of acrylamide-based polymers is particularly preferred from the viewpoint of color image stabilization.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

Various anti-fading agents can be used in the photosensitive material of the present invention. That is, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, P-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and silylation and alkylation of the phenolic hydroxyl groups of these compounds. Typical examples include ether or ester IWi forms. Further, gold i-complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

Specific examples of organic antifade agents are described in the following patent specifications:

Hydroquinones are U.S. Patent No. 2.360.290,
Same No. 2.418.613, Same No. 2.700.453, Same No. 2,701.197, Same No. 2.728,659
No. 2,732,300, No. 2,735.76
No. 5, No. 3,982,944, No. 4.430.4
25, British Patent No. 1,363.921, U.S. Patent No. 2.710.801, U.S. Patent No. 2.816,028, etc., 6-hydroxychromans, 5-hydroxycoumarans, spirochromans U.S. Patent No. 3.432.30
No. 0, No. 3,573,050, No. 3,574,6
No. 27, No. 3.698゜909, No. 3,764,
No. 337, JP-A-52-152225, etc., and spiroindanes are described in U.S. Pat. No. 4,360,589, p-
Alkoxyphenols are U.S. Patent No. 2,735,76
No. 5, British Patent No. 2.066.975, Japanese Unexamined Patent Publication No. 1983-
No. 10539, Japanese Patent Publication No. 57-19765, etc., and hindered phenol necks are disclosed in U.S. Pat.
No. 35 and Japanese Patent Publication No. 52-6623, gallic acid derivatives, methylenedioxybenzene, and aminophenols are disclosed in US Pat. No. 3,457,079 and US Pat. No. 4, respectively.
332.886, Special Publication No. 56-21144, etc.
Hindered amine necks include U.S. Patent No. 3.336.135, U.S. Patent No. 4.268.593, British Patent No. 1.326,
No. 889, No. 1.354.313, No. 1.410
, No. 846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. 58-1
No. 14036, No. 59-53846, No. 59-7
No. 8344, metal complexes are disclosed in U.S. Patent No. 4.050,
No. 938, No. 4.241°155, British Patent No. 2.
027.731(A), etc., respectively. The purpose of these compounds can be achieved by co-emulsifying them with Kabu-5, usually in an amount of 5 to 100% by weight based on the corresponding color coupler, and adding them to the light-emitting layer. Cyan color! In order to prevent the deterioration of AI due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to it.

As ultraviolet absorbers, benzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533,7
94), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3,314,794, U.S. Pat. No. 3,352.
681), benzophenone compounds (e.g., those described in JP-A No. 46-2784), cinnamic acid ester compounds (e.g., U.S. Pat. No. 3,705-805),
No. 3,707,395), bucdiene compounds (as described in U.S. Pat. No. 4,045,229), or benzoxazole compounds (e.g., U.S. Pat. No. 3,406,070). Same No. 3,677.76
No. 2, No. 4, No. 271, No. 307) can be used. Ultraviolet absorbing couplers (for example, α-naphthol cyan dye-forming couplers), ultraviolet absorbing polymers, and the like may be used, and these ultraviolet absorbers may be mordanted in specific layers.

Among these, benzotriazole compounds substituted with the aforementioned aryl group are preferred.

In addition, it is particularly preferable to use the following compounds together with the couplers described above, particularly in combination with pyrazoloazole couplers.

That is, a compound (CF) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aromatic compound remaining after color development processing. For example, the use of a compound (G) that chemically bonds with the oxidized form of an amine-based color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly, for example, for film storage after processing. This is preferable in order to prevent staining and other side effects caused by the formation of coloring dyes due to the reaction between the remaining color developing agent or its oxidized product and the coupler.

A preferred compound (F) has a second-order reaction rate constant kl (in trioctyl phosphate at 80°C) with P-anisidine of 1. Oj! /+ol-sec ~I
X1O−%I! , /# Ao1·sec.

Incidentally, the second-order reaction rate constant can be measured by the method described in JP-A-63-158545.

When R2 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, k! If it is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, it may not be possible to prevent side effects of the remaining aromatic amine developing agent.

A more preferable compound (F) can be represented by the following formula (Fl) or (Fn).

General formula (FriR+-(A)ax General formula (FIG) R, -CmaroY In the formula, R1 and R1 each represent an aliphatic group, an aromatic group, or a heterocyclic group, and n is Represents 1 or 0.

A represents a group that reacts with an aromatic amine developer to form a chemical bond, and X represents a group that reacts with an aromatic amine developer.
B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group; represents a group that promotes addition to R
1 and X, Y and R2 or B may be bonded to each other to form a cyclic structure.

What is the typical method of chemically bonding with residual aromatic amine developing agents? 1ftA reaction and addition reaction.

-e For specific examples of compounds represented by formula (Fri, (FII)), see JP-A-63-158545 and JP-A No. 62-2.
83338, European Patent Publication No. 298321, European Patent Publication No. 277
Those described in specifications such as No. 589 are preferred.

On the other hand, more preferred compounds (G) that chemically bond with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inert and colorless compound are as follows - both formulas ( Gl).

General formula (Gl) -Z In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group, and Z is a nucleophilic group or a nucleophilic group that is decomposed in the photosensitive material to form a monophilic group. Representing a releasing group, -compounds of formula (G1) in which Z is Pearson's nucleophilic I'ICHs
l(i (R, G, Pearson, eL at,
, J., Am.

Chew, Soc., 90.319 (1968)
) is preferably 5 or more, or a group derived therefrom.

- Both formulas (for specific examples of compounds represented by G
No. 8, No. 62-229145, patent application No. 63-1367
No. 24, No. 62-214681, European Patent Publication No. 298
Those described in No. 321, No. 277589, etc. are preferred.

Further, details of the combination of the above-mentioned compound (G) and compound CF) are described in European Patent Publication No. 277589.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer.For example, an aryl group may be added. benzotriazole compounds (e.g., those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (e.g., those described in U.S. Pat. No. 3,314,794),
No. 3,352.681), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., those described in U.S. Pat. No. 3,352,681),
, 705,805 and 3,707,375), butadiene compounds (e.g., U.S. Pat. No. 4.04)
5.229) or benzoxidol compounds (eg, those described in US Pat. No. 3.700.455). An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used, and these ultraviolet absorbers may be mordanted in a specific layer.

In the photosensitive material prepared for the present invention, colloidal dyes and dyes are used to prevent irradiation and halation, particularly to separate the spectral intensity distribution of each photosensitive layer and to ensure safety against safelight in the visible wavelength range. Such dyes include oxonol dyes i4, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol DH and merocyanine dyes are useful. Indolenine dyes are particularly useful.

Especially for dyes for red end or infrared, for example, JP-A-62-32
No. 50, No. 62-181381, No. 62-12345
4, No. 63-197947, etc., as well as dyes for back layers and JP-A-62-39682, JP-A-62-123192, JP-A-62-158779, JP-A-62-174741, etc. The dye described above or the same dye can be used by introducing a water-soluble group that can flow out during processing.The infrared dye of the present invention is colorless and has no substantial light absorption in the visible wavelength range. You can.

In the present invention, when an infrared dye is mixed with a silver halide emulsion that has been spectrally sensitized in the end-red to infrared wavelength range, it causes desensitization, generation of capri, and in some cases, the dye itself adsorbs to silver halide grains and becomes weak. Broad spectral sensitization may occur. Preferably, it is preferable to substantially contain the dye only in the colloid layer other than the photosensitive layer.For this purpose, it is preferable to contain the dye in a predetermined colored layer in a diffusion-resistant state.
The first step is to add a ballast group to the dye to make it resistant to diffusion. However, the second problem is that the anionic dye of the present invention is mordanted with a polymer or polymer latex that provides cation sites. The third method is to use a dye that is insoluble in water with a pH of 1 or less and is decolored and eluted during the treatment process in fine particle dispersion.

For this purpose, it is used by dissolving it in a low-boiling organic solvent or solubilizing it in a surfactant and dispersing it in an aqueous solution of a hydrophilic protective colloid such as gelatin. Preferably, the solid dye is kneaded with an aqueous surfactant solution and mechanically turned into fine particles using a mill, which is then dispersed in an aqueous solution of a hydrophilic colloid such as gelatin.

As the binder or protective colloid that can be used in the photosensitive layer of the photosensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the gelatin manufacturing method can be found in "The Macromolecular Chemistry of Gelatin" by Arthur Weiss ( Published by Academic Press, 1964).

The color photosensitive material according to the present invention includes known photographic additives,
In particular, materials used in commercially available color papers using high silver chloride (particle average silver chloride content of 96 mol % or more) can be selected and used. You can select and use the additives and materials listed in Research Disclosure below.

Additive type 1 Chemical sensitizer 2 Sensitivity enhancer RD17643 Page 23 Same as above RO18716 Page 648 Right column Same as above 4 Super sensitizer 5 Brightener Same as above 24 Same as above 7 Coupler 8 Organic solvent Page 25 Same as above Same as above Ultraviolet absorption agent stain inhibitor dye image stabilizer hardener binder desensitizer, lubricant Same as above 25 pages right page 25 pages 26 pages 26 pages 27 pages same as above 650 pages left to right side Same as above 651 pages left ladle Same as above 650 pages right column Present invention The halogen composition of the silver halide emulsion used in the photosensitive layer of the silver halide photographic light-sensitive material may be any of silver chloride, silver bromide, silver chlorobromide, silver chloroiodobromide, silver iodochloride, etc. Or a silver chlorobromide emulsion containing silver chloride such as silver chloride is preferable for rapid processing and for greatly obtaining the storage stability effect of the present invention, and contains silver chloride in an amount of 96 mol% or more. or a silver chloride emulsion, and if silver bromide is contained, it is preferably present locally within or on the surface of the grains;
Having a localized partial structure with a different silver bromide content inside or on at least one of the surface of a silver halide grain is called having a localized structure, and in pure silver chloride, metal ions different from silver ions are used. In the present invention, having a localized partial structure having different contents of iridium, rhodium, iron, etc. is also referred to as having a localized structure in the present invention.

In the present invention, when the silver halide grains are made of silver chlorobromide, the silver halide grains are silver chlorobromide having an average silver chloride content of 96 mol% or more and having a localized silver bromide content of more than 15 mol%. It is preferable that there be.

The localization of such a high silver bromide content can be arbitrarily determined depending on the performance to be obtained from the emulsion, and may be located inside the silver halide grains, or on or near the grain surface. , and may exist in two or more places simultaneously.For localization, a layered tR structure surrounding the grain may be present inside the silver halide grain, on the grain surface, or near the grain surface. Even if it has a very isolated structure or a discontinuously isolated structure, it can also have a mesh-like structure,
It may have such a composite structure.

An example of a preferred arrangement for localization is one in which silver chlorobromide with a silver bromide content of at least more than 15 mol % is localized on the surface of the silver halide grain. Preferably, the silver content exceeds 15 mol%, but 7
It is undesirable to exceed 0 mol%; if the silver bromide content is too high, so-called pressure desensitization may increase when a photosensitive material using the emulsion is exposed after applying mechanical pressure, or processing Fluctuations in the composition of the liquid may result in unfavorable performance, such as large fluctuations in photographic properties.

Therefore, the silver bromide content for localization is preferably in the range of 15 to 70 mol%, more preferably in the range of 20 to 60 mol%, and even more preferably in the range of 30 to 50 mol%.

The localization layer preferably consists of 0.01 to 20 mol% of silver, more preferably 0.02 to 7 mol% of silver, based on the total amount of silver constituting the silver halide grains of the present invention. It is preferable that

The interface between such a local phase with a high silver bromide content and other phases may have a sharp boundary, or may have a boundary region where the halogen composition gradually and continuously changes. Good too.

The silver bromide content of such a localized silver bromide phase can be determined by the X-ray diffraction method (for example, described in "New Experimental Chemistry Course 6, Structural Analysis, edited by the Chemical Society of Japan", Maruzen) or the XPS method ( For example, it can be analyzed using a method such as "Surface Analysis - 1MA, Application of Auger Electron/Photoelectron Spectroscopy" published by Kodansha, and its presence can also be detected using an electron microscope.

In the present invention, various methods can be used to form the above-described localized silver bromide phase or localized metal salt phase. For example, a method of mixing soluble silver salt and soluble bromide or metal salt on one side. Alternatively, a localized compound can be formed by reacting by a simultaneous mixing method. Localized particles can also be formed using a so-called halogen conversion method, which involves converting already formed silver halide into silver halide having a smaller solubility product. Alternatively, by mixing and ripening already formed silver halides having different halogen compositions, recrystallization can be caused to form a localized silver halide. When forming a localized silver chlorobromide phase on the surface of silver chloride grains, fine particles of silver bromide with a relatively small particle size are added to the already formed silver chloride grains.
It is preferable to cause recrystallization and form localized crystals by ripening.

Timing of addition of a halide compound solution to form a localized compound, addition of a poorly soluble halide, addition of a silver salt solution/halogen salt solution, addition of fine grain silver halide, etc., ripening time/temperature or addition time - By changing the silver ion concentration during ripening and changing the degree of halogen conversion or recrystallization, it is possible to control the emulsion so that it has the desired performance.

The emulsion having localization as described above may contain silver iodide, and it is preferable that silver iodide is also localized. In the present invention, the content of silver iodide is 0 to 3 mol. %, more preferably 0 to 1 mol %, most preferably 0 to 0.
It is 6 mol%.

In addition to the various silver halides mentioned above, the silver halide emulsion of the present invention may also contain inorganic silver salts other than silver halides, such as silver rhodan and silver phosphate.

The external shape of the crystal grains of the silver halide emulsion of the present invention can be in the shape of so-called regular grains such as a cube, octahedron, dodecahedron, or rhombidodecahedron, or in the shape of a spherical, tabular, etc. It is also possible to take an irregular particle shape. In addition, these silver halide grains may be grains with more complex shapes that have a combination of these crystal faces, or even grains with higher-order crystal faces. They may be mixed.

Further, in the emulsion used in the present invention, tabular grains having an average aspect ratio (ratio of circular diameter/grain thickness to the main plane of the grain) of 5 or more, particularly preferably 8 or more, account for 50% or more of the total projected area of the grains. If the emulsion is such that it can be processed quickly, it is advantageous for rapid processing.

The size distribution of silver halide grains may be wide or narrow, but so-called monodisperse emulsions are preferable in terms of sensitivity stability.The standard deviation S of the diameter distribution when the projected area of silver halide grains is converted into a circle is The value S/ divided by the average diameter d
d is preferably 20% or less, more preferably 15% or less.

Silver halide grains having a regular crystal shape are preferably used in the present invention in terms of number of grains or weight.
A monodisperse silver halide emulsion containing 0% or more, more preferably 70% or more, still more preferably 90% or more, and especially cubic or tetradecahedral silver halide having (100) crystal planes. In the grains, it is preferable to use an emulsion in which the above-mentioned localization is present in a portion corresponding to a corner or an edge of a cube.For localization of a metal salt, it may be present on a (100) plane other than edges or corners, for example. In the present invention, such discontinuously isolated localization on the surface of silver halide grains, which is preferable in the present invention, is caused by changing the silver ion concentration, hydrogen ion concentration, temperature, or time to the emulsion containing the silver halide grains as the substrate. It is possible to form bromine ions or metal ions through halogen conversion, etc. by supplying bromine ions or metal ions while controlling the
It is preferable to feed the system while stirring the system sufficiently. At the same time, it is also preferable to feed the ions at a low concentration or gradually. An organic halogen compound or a halogen compound covered with a semi-permeable capsule membrane can also be used.

In addition, silver ions and halogen ions are supplied to an emulsion containing silver halide grains in the substrate while controlling the silver ion concentration, etc., and silver halide is grown on a fixed grain site per gram, or By mixing silver halide crystals that are finer than the silver halide grains and growing silver halide in limited areas such as the edges and corners of the silver halide grains on the substrate through recrystallization, localization can be achieved. can be formed. In this case, a silver halide solvent may be used in combination if necessary.

Also, Japanese Patent Application No. 62-263318, No. 62-3292
65 and 63-7861 can be used in combination, and similar to silver bromide microcrystals, silver iodobromide, silver chlorobromide, etc. It can also be prepared using microcrystals.

The grain size of the silver halide crystals contained in the silver halide emulsion used in the present invention is preferably from 0.05 μm to 2 μm, more preferably from 0.1 μm to 2 μm, on the average diameter of the volume equivalent region.
It is preferably 1.5 μ or more.

The silver halide emulsion of the present invention contains P, GIaf-kide.
Written by srChemie et Ph1s-ique
Photographique” (Paul Mo
nte1 Publishing, 1967), Photogra-phic Emulsion by G. F. Duffin
Chemist-ry” (Focal Pres.
(1966), V. L. Zelikman
et al.Making and Coat
ing of Photographic Emul
sion” (Focal Press, 1964)
It can be prepared using the method described in 2010).

The preparation method may be any of the acidic method, neutral method, ammonia method, etc., but the acidic method and the neutral method are particularly preferred in the present invention in terms of reducing fog, and in order to obtain high sensitivity. It is also preferable to prepare under a hydrogen ion concentration lower than neutrality, and to obtain a silver halide emulsion by reacting a soluble silver salt and a soluble halide salt, either the so-called one-sided mixing method, simultaneous mixing method, or a combination thereof can be used. 0 particles may be used under conditions of excess silver ions and 1
It is also possible to use the so-called back mixing method in which 0
In order to obtain an emulsion of monodisperse grains preferred in the present invention, it is preferable to use a simultaneous mixing method. One form of the simultaneous mixing method is a method of keeping the silver ion concentration constant in the liquid phase in which silver halide is produced; That is, it is more preferable to use the so-called Chondrold double jet method. By using this method, it is possible to obtain a silver halide emulsion which is preferred for the present invention and has a regular silver halide crystal shape and a narrow grain size distribution.

In the process of grain formation or physical ripening of silver halide, cadmium salt, zinc salt, lead salt, thallium salt, or the above-mentioned iridium salt or its complex salt,
A rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof may be present together.

During or after grain formation, a silver halide solvent (for example, known ones such as ammonia, thiocyanate, U.S. Pat.
No. 0, JP-A-53-82408, JP-A-53-144
319, JP-A-54-100717, JP-A-54-155828, etc.) may be used, and when used in combination with the above method, the silver halide crystal shape becomes regular. Silver halide pores preferred for the present invention having a narrow grain size distribution can be obtained.

In order to remove soluble salts from the emulsion after physical ripening, Nudel water washing, flocculation sedimentation, ultrafiltration, or the like can be used.

The emulsion used in the present invention is sulfur-sensitized or selenium-sensitized,
Chemical sensitization can be carried out by reduction sensitization, noble metal sensitization, etc. alone or in combination. That is, active gelatin and compounds containing sulfur compounds that can react with silver ions (for example, thio'f
fL salts, thiourea compounds, mercapto compounds, rhodanine compounds, etc.), and reducing substances (such as stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, ascorbic acid). etc.), and metal compounds (for example, the above-mentioned total complex salts, metal salts of group Ⅰ of the periodic table such as platinum, iridium, palladium, rhodium, iron, etc., or complex salts thereof, etc.)
In the emulsion of the present invention, sulfur sensitization or selenium sensitization is preferably used, and it is also preferable to use these together with gold sensitization. Further, during these chemical sensitizations, it is preferable to have a hydroxyazaindene compound or a nucleic acid present in order to control sensitivity and gradation.

The silver halide grains used in the present invention include metal ions other than silver ions (for example, metal ions of group Ⅰ of the periodic table, metal ions of group
The sensitivity stabilization effect of the present invention can be better exhibited under various conditions by containing transition metal ions of group 1V, lead ions of group 1V, gold ions and copper ions of group 1) or complex ions thereof. These preferred metal ions or one ion thereof may be contained in the entire silver halide grain, in the localized phase described above, or in other phases.

Among the metal ions or complex ions thereof, those selected from iridium ions, palladium ions, rhodium ions, zinc ions, iron ions, platinum ions, gold ions, copper ions, etc. are particularly useful. Desired photographic properties are often obtained by using these metal ions or complex ions in combination rather than singly, and it is possible to change the type and amount of added ions between the localized phase and other parts of the particle. Preferably, it is particularly preferable that iridium ions and rhodium ions be contained in the localized phase.

In order to incorporate metal ions or complex ions into the localized phase of silver halide grains or other parts of the grains, the metal ions or complex ions can be added to the silver halide grains during physical ripening before, during, or after formation. 9 When forming a localized phase with fine silver bromide particles, the same method as above can be used. How to silver bromide or iodide? It is also possible to add relatively sparingly soluble bromides of metal ions other than silver salts, such as those mentioned above, to solid or powdered silver chloride grains. In the present invention, emulsions prepared in such a manner that metal ions may be added while forming a localized phase are used as high silver chloride emulsions sensitized in the red to infrared region. Problems such as high sensitivity, sensitivity stability, and latent image stability are comprehensively improved, and the characteristics of high silver chloride emulsions regarding rapid processing can be fully exhibited.

In the red to infrared sensitization of the present invention, supersensitization using a compound represented by the general formula (IX) shown below is particularly useful for M-band sensitization.

General formula (Do In the formula, A□ represents a divalent aromatic residue, R91, Ra
t, R92 and R44 are each a hydrogen atom, a hydroxol group, an alkyl group, an alkoxy group, an aryloquino group, a halogen atom, a heterocyclic nucleus, a heterocyclylthio group, an arylthio group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group , represents an aryl group or a mercapto group, and these groups may be pentasubstituted.

However, at least one of A, , R9+, nqx, Rts, and R94 has a sulfo group.

xl and Y drop each represent -CH= -N-,
9. At least one of and Yl represents -N-.

More specifically, in the format (■), -A and 1- represent divalent aromatic residues, and these are -sosM groups [where M is a hydrogen atom or a cation that provides water solubility (e.g., sodium, potassium, etc.). ), may also include ].

1, 1- is, for example, the following -Aqt- or -A9. −
Selected ones are useful. However, R93, R9゜R
When 1ff or k does not contain a group,
-A9. - is selected from the group -A q z-.

-A,,-.

50, n O.J. Such.

Here, M represents a hydrogen atom or a cation that provides water solubility.

A9. - R1, R92, R93 and n94 are each a hydrogen atom, a hydroxyl group, an alkyl group (the number of carbon atoms is preferably 1 to 8), such as a methyl group, an ethyl group, an n-7'ropyl group, an n-butyl group, etc. ), alkoxy groups (preferably 1 to 8 carbon atoms, e.g. methoxy, ethoxy, propoxy, butoxy, etc.), aryloxy groups (e.g. phenoxy, naphthoxy, 0-)lyloxy, P-sulfophenoxy groups), halogen atoms (e.g. chlorine atoms, bromine atoms, etc.), heterocyclic nuclei (e.g.
morpholinyl group, piperidyl group, etc.), alkylthio group (e.g. methylthio group, ethylthio group, etc.), heterosocrylthio group (e.g. benzothiazolylthio group, benzimidazolylthio group, phenyltetrazolylthio group, etc.), arylthio group (e.g. phenylthio group) group, tolylthio group), amino group, alkylamino group or 110 alkylamino group (e.g. methylamino group, ethylamino group, propylamino group, dimethylamino group, diethylamino group, dodecylamino group, cyclohexylamino group,
β-hydroxyethylamino group, di(β-hydroxyedyl)amino group, β-sulboethylamino group), arylamino group, or HA arylamino group (e.g. anilino group, o-sulfoanilino group, m-sulfoanilino group) , p-sulfoanilino group, 0-)luidino group, m-
Toluidino group, P-) Luidino group, 0-carboxyanilino group, m-carboxyanilino group, p-carboxyanilino L O-chloroanilino group, m-chloroanilino group, p-chloroanilino group, p-aminoanilino group, 0
-anisidino group, m-anisidino group, p-anisidino group, 0-acekminoanilino group, hydroxyanilino group,
disulfophenylamino group, naphthylamino group, sulfonaphthylamino group), heterocyclylamino group (e.g. 2-benzothiazolylamino group, 2-pyridylamino group, etc.) 1.1 YIA or TL IA-free aralkylamino group (for example, benzylamino group, 0-anisylamino group, m-anisylamino group, p-anisylamino group, etc.), aryl group (for example, phenyl group, etc.), and mercapto group.

R, , R, , k, R94 may be the same or different from each other * A ? When +- is selected from the group -Ag2-, at least one of R11, Ro, R1 and R94 has the above sulfo group (which may be a free acid group and may form a salt). It is necessary to do so. X9. and Yv+ represent -CH- or ~N-, preferably those in which X, 1 is -Cll-1, Y□ is N- are used.

Next, specific examples of compounds included in the general formula ([X) used in the present invention will be given. However, the present invention is not limited only to these compounds.

(A-1) 4.4'-bis(2,6-di(2-naphthoxy)pyrimidin-4-ylamino)stilbene-2,2'-disulfonic acid disodium salt (A-2)4. , i'-bis[2,6-di(2-naphthodelamino)pyrimidin-4-ylaminocostilbene-22'-disulfonic acid disodium salt (A-3) 4.4'-bis(2,6 -dianilinopyrimidin-4-ylamino)stilbene-2,2'-disulfonic acid disodium salt (A-4) 4.4'-bis(2-(2-naphthylamino)-6-anilinobyrimidine-4 -ylaminostilbene-22'-disulfonic acid disodium salt (A-5) 4,4'-bis(2,6-diphenoxypyrimidin-4-ylamino)stilbene-2,2'-disulfonic acid triethylammonium salt (A-6) 4.4'-bis[2,6-di(benzimidazolyl-2-thio)pyrimin 4-ylaminocostilbene-22' nosulfonic acid disodium salt (A-7) 4.4'-bis [4,6-di(benzothiazolyl-2-thio)pyrimidin-2-ylaminocostilben-2,2'-disulfonic acid disodium salt (A-8) 4,4'-bis[4,6-di(benzothiazolyl -2-amino)pyrimidine 2-ylaminocostilbene-2゜2'-disulfonic acid cinamonium salt (A-9) 4,4'-bis[4,6-di(naphthyl-2
-oxy)pyrimidin-2-ylaminocostilbene-2,2'-disulfonic acid disodium salt (A-10) 4.4'-bis(4,6-diphenoxypyrimidin-2-ylamino)stilbene-2 , 2'-disulfonic acid disodium salt (A-11) 4,4'-bis(4,6-cyphenylthiopyrimidin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (A-12 >4.4'-bis(4,6-dimercaptopyrimidin-2-ylamino)biphenyl-2,2'-disulfonic acid disodium salt 4.4'-bis(4,6-dianilino-triazine-2 -ylamino)stilbene-2,2'-disulfonic acid disodium salt 4.4'-bis(4-anilino-6 hydroxytriazin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt 4.4 '-Bis[4,6-di(naphthyl-2-oxy)pyrimidin-2-ylamino]bibenzyl-2,2'-disulfonic acid di-tutorium salt 4,4'-bis(4,6-dianilinopyrimidine- 2-ylamino)stilbene-2,21-disulfonic acid cinamium salt 13) 14) 15) (A-16) (A-17) 4.4'-bis[4-chloro-6-(2-
naphthyloxy)pyrimidin-2-ylamino)biphenyl-2,2'disulfonic acid disodium salt (A-18) 4,4'-bis[4,6-di(l-phenyltetrazolyl-5,000)pyrimidine -2-ylaminocostilbene 2.2'-disulfonic acid disodium salt (A-19) 4.4'-bis[4,6-di(peppimidapril-2-thio)pyrimidin 2-ylaminocostilbene- 2゜21-Disulfonic acid disodium salt (A-20) 4.4'-bis(4-naphthylamino 6-
Anisotutriazin-2-ylamino)stilhene-2,2'-disulfonic acid disodium salt Among these specific examples, (A-1) to (A-6) are preferred, particularly (A-1) and (A-1). -2), (A4), (A-
5), (A-9), (A-15), and (A-20) are preferred.

The compound represented by the general formula ([X) is 0.00% per mole of halogenated ffft. An amount of 1 to 5 g is used, and the amount used is advantageously in the range of about 5 times to 2000 times, preferably 20 times to 1500 times, by weight relative to the enhancing dye.

Next, compounds that are preferably used in combination with the above compounds will be explained.

The following general formula (X
), (XI) or (Xn) is preferably added, and the amount added is preferably 1X10-' to 5X10-' mol per mol of silver halide, more preferably 1X10-' to 1 x10-' mol is particularly preferred.

General formula (X) In the formula, R1゜1 is an alkyl group, alkenyl group represents an aryl group, XI. .

represents a hydrogen atom, an alkali metal atom, an ammonium group, or a precursor; the alkali metal atom is, for example, a sodium atom, a potassium atom, etc., and the ammonium group is, for example, a tetramethylammonium group, a trimethylbenzylammonium group, etc. Precursor is a group that can become x1□-day or an alkali metal under alkaline conditions.
For example, it represents an acetyl group, a cyanoethyl group, a methanesulfonylethyl group, etc.

Among the above R3゜, alkyl groups and alkenyl groups include unsubstituted forms and 1ZIA forms, and also include alicyclic groups. Substituents for substituted alkyl groups include halogen atoms, nitro groups, cyano groups, Hydroxyl group, alkoxy group, aryl group, acylamino group, alkoxycarbonylamino group, ureido group, amide group, heterocyclic group, acyl group, sulfamoyl group, sulfonamide group, thioureido group, carbamoyl group, alkylthio group, arylthio group, hetero Ring thio groups, and also carboxylic acid groups, sulfonic acid groups or salts thereof, etc. can be added earlier.

The above ureido group, thiourido group, sulfamoyl group, carbamoyl group, and amino group include those of device IA, N-alkyl 1ZIA, and N-aryl WIA, respectively. Examples of the aryl group include phenyl group. Examples of the rILIA group include alkyl groups and the 11A group of the alkyl groups listed above.

-Format (XI) vinegar.

L represents a divalent linking group, R11+ represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, R++
+ alkyl group, alkenyl group and X are general formula (X)
It is synonymous with that of

A specific example of the divalent linking group represented by the above R'
R'R'R'OR”N-C-
N--S--CH-1-〇-2 etc. and these as a set R'SR
The combination of "R" + 1" can be mentioned.

n represents 0 or 1, and R6, R1, and R-rich each represent a hydrogen atom, an alkyl group, or an aralkyl group.

General formula (XIT) In the formula, R1! + and X 1ml is − form (X) R
Synonymous with Ol and xlo-, L is general formula (XI)
It is synonymous with that of Rtsu has the same meaning as R58, and may be the same or different.

Below - format (X), - format (XI) and - melon style (X ■
) Specific examples of compounds are listed below, but the invention is not limited to these.

C11゜1 NIICOCIh C11゜In the present invention, the oxygen volume fraction is defined as the temperature at which a certain oxygen-containing gas reaches an arbitrary temperature when the number of oxygen molecules per unit volume of the atmosphere at 25°C and 1 atmosphere is expressed as 21%. and how many oxygen molecules are contained in the same unit M under atmospheric pressure is numerically expressed in a direct proportional relationship. This can be thought of as the product of oxygen abundance ratio and pressure, but
This allows the amount of oxygen contained per volume in a certain gas to be displayed in an easy-to-understand manner relative to the atmosphere.

For example, if the atmosphere containing 21% oxygen at 1 atm is expanded to 0.5 atm, the oxygen volume fraction will be 10.5%, and the volume ratio of air and nitrogen at 1 atm will be 1:1.
If mixed at , the oxygen volume fraction will be the same <10.5%.

In the present invention, the oxygen volume fraction can be controlled by various generally well-known methods. Oxygen may be removed by physical or mechanical methods, or by chemical methods. Specifically, oxygen may be removed by mixing other gases that do not contain oxygen with the atmosphere as described above. Alternatively, oxygen may be replaced, vacuum deaeration may be performed, oxygen may be replaced with a gas that does not contain oxygen after vacuum deaeration, oxygen may be reacted with other compounds or elements, or gaseous Something like MJBI or an oxygen pump may also be used.

In the present invention, a deoxidized state refers to a state in which there is less oxygen than the atmosphere, and the oxygen volume fraction is preferably about 2% or less, more preferably as low as possible, more preferably 1% or less, and 0. 5% or less is more preferable.In order to obtain the lowest possible oxygen volume fraction for a photosensitive material, the photosensitive material can be stored or packaged in a nitrogen atmosphere from which oxygen has been removed from the beginning, for example, or it can be stored or packaged in a nitrogen atmosphere. It can also be obtained by enclosing iron powder or other oxygen scavenger together when storing it in a sealed container or sealing it. This method is particularly preferred since it facilitates creating oxygen-free conditions in the packaged form.

Such a deoxidizing state may be applied after the photosensitive material is coated until it is processed into a product form, or may be applied to the packaging state of the product itself.

Furthermore, it is also preferable that the deoxidized state be maintained after the package is opened for use of the photosensitive material.

The deoxidizing state of the present invention may be applied during part or all of the oxidation period from coating production to use of the photosensitive material, thereby improving the performance of the photosensitive material while in that state. The objective of the present invention of preventing changes can be achieved.

A vacuum pump, an oxygen separation membrane, or a solid oxygen pump can be used to maintain a deoxidized state in order to prevent changes in performance after opening the package when using the photosensitive material. These devices can be incorporated into devices that expose and process photosensitive materials, or can be used independently.

When these devices are incorporated into equipment, it is useful to connect them to a photosensitive material holder, cartridge, magazine, etc. inside an exposure device or attached to the exposure device.

Vacuum degassing using a vacuum pump also removes water contained in the photosensitive material, which may inhibit the curing reaction of the gelatin used when energized, and cause problems such as fogging and curling. However, it may be advantageous in maintaining good retention of the photosensitive material, which is the object of the present invention.

In order to accomplish the purpose of the present invention in the form of packaging for photosensitive materials, a material made of polymer or metal foil that does not allow oxygen to pass through or has a low oxygen permeability is used as the packaging material, and the photosensitive material is hermetically sealed with this material. Then, before or after sealing, a deoxidized state can be created in the package using the method described above.

Polymers that can be used for this purpose include polymers with low oxygen permeability such as polyvinylidene chloride, polyethylene terephthalate, nylon, and polyvinyl alcohol, and polymers with high oxygen permeability such as polyethylene. However, those copolymerized or blended with the above-mentioned polyvinyl alcohol can also be used very preferably. In addition, polyvinyl chloride, polyvinyl acetate, polypropylene, etc. can also be used.

Moreover, aluminum, lead, etc. can be used as the metal foil.

The use of packaging materials from composite materials of polymer and metal foil laminated together as described above does not give very good results for the purposes of the present invention.

It is also preferable to use two or more packaging materials, for example, in a double or more packaging form, instead of using only one packaging material as described above.

In order to seal the packaging material, a method of heat-sealing a polymer or the like as described above may be used.

Example 1 Silver halide color photographic materials as shown in Table 1 were prepared. This sample was designated as A.

The silver halide emulsions shown below were used in each layer.

Emulsion for layer containing cyan coupler: Add 30 g of lime-treated gelatin to 10,100 O of distilled water, dissolve at 40°C, adjust the pH to 3.8 with sulfuric acid, and add 5.5 g of sodium chloride and N,N-dimethylimidazolidine. Add 0.02 g of -2-thione and bring the temperature to 52.5°C.
It was raised to . Dissolve 62.5 g of silver nitrate in 750 ml of distilled water and 21.5 g of sodium chloride in 500 ml of distilled water.
The solution dissolved in ml was added to and mixed with the above solution for 40 minutes while maintaining the temperature at 52.5°C. Furthermore, a solution of 62.5 g of silver nitrate dissolved in 500 ml of distilled water and 21.5 g of sodium chloride were added.
g dissolved in 300 ml of distilled water were added and mixed at 52.5°C over 20 minutes.

During this addition and mixing, l
Iridium dipotassium hexachloride at 0-8 moles of XlO-8 moles of Ag, and potassium hexacyanoferrate (JT) at 1.5XiO-5 moles of 1 mole of Ag were added.

When the obtained emulsion was observed under an electron microscope, it was found to be about 0.
The emulsion consisted of cubic grains with an average side length of 46 μm and a coefficient of variation of grain size distribution of 0.09.

After demineralizing and washing this emulsion with water, a monodisperse silver bromide emulsion (containing 1.2 x 10-4 mol of iridium dipotassium hexachloride 1 mol Ag) containing 0.2 g of nucleic acid and an average grain size of 0.05 µm was mixed with silver halide. .0 mol% was added, chemically sensitized with 2 x 10-6 mol/mol Ag of triethylthiourea, and compound (V-23> was added at 5 x 10-6 mol/mol A g, compound ( I-1) as l, I
X 10-3 mol/Mo1IyA g, compound (F-1
) was added in an amount of 1,8×10 −3 mol and 1 mol of Ag to prepare an emulsion.

Emulsion for magenta coupler-containing layer: Add 30g of lime-treated gelatin to 1100o+ distilled water, dissolve at 40°C, then add 5.5g of sodium chloride and N,N.
--Dimethylimidazolidine-2dione, 0.02 g, was added and the temperature was raised to 50<0>C. A solution prepared by dissolving 62.5 g of silver nitrate in 750 ml of distilled water and 21.5 g of sodium chloride.
A solution obtained by dissolving 5 g in 500 ml of distilled water was added to and mixed with the above solution for 40 minutes while maintaining the temperature at 50°C. Furthermore, a solution in which 62.5 g of silver nitrate was dissolved in 500 ml of distilled water and a solution in which 21.5 g of sodium chloride was dissolved in 300 ml of distilled water were added and mixed at 50 DEG C. over 20 minutes.

In this addition and mixing, 1
．． 2×10 −8 mol 1 mol Ag of iridium dipotassium hexachloride and 1.8×10 −5 mol 1 mol Ag potassium hexacyanoferrate(II) were added.

When the obtained emulsion was observed under an electron microscope, it was found to be about 0.
The emulsion consisted of cubic grains with an average side length of 44μ and a coefficient of variation of grain size distribution of 0.08.

After demineralizing and washing this emulsion with water, a monodisperse silver bromide emulsion (containing 1.5×10 −4 mol of iridium dipotassium hexachloride 1 mol Ag) containing 0.2 g of nucleic acid and an average grain size of 0.05 μm was added with silver halide. .5 mol % was added, chemically sensitized with 2.4 x 10 -6 mol 1 mol Ag in the form of triethylthiourea, and further compound 1 (V-46) was added to 1. lX10-
5mol/moJ Ag, compound (I-1) 0.6X10
-3 mol/mole 8g, compound 1 (F-1) 0.9X
10-3-[:/I.

An emulsion containing 1 mol of Ag was prepared.

Emulsion for yellow coupler-containing layer: Compound (V-40) and compound (■-41) were added in place of compound (V-46) to an emulsion prepared in the same manner as the emulsion for magenta coupler-containing layer described above. 0
, 6 x 10 -4 mol of 1 mol of Ag were added, and an emulsion was prepared with the only difference being that the compound (F-1> was not added).

These samples are coated with compounds (
D-1), (D-2), (D-3), (D-4), (D
-5) and (D-6) at 0 and 016 g/n, respectively.
r, 0.006g/rr? , 0, oosg/rr? ,0
．． 013g/rrr, 0.018g/i, 0.022g
/rrr.

Further, the following three types of compounds were used as a hardening agent for gelatin in a molar ratio of 3:2:1.

l-12 NHCOCH2 02 CH=CH2 CH2 NHCOCH2 SO2CH=CH2 OCH2S 02 CH=CH2 CH2SO2C) (=CH2 After coating and preparing this sample A, 25°C relative humidity 60%
After being left under these conditions for 3 days, they were stored at 25°C for 4 weeks under the storage conditions shown in Table 2, and their photographic properties were compared.

(D l) (D-2) (D 3) (D-4) (D-5) (D-6) (1-1) CF-1) (S-1) (S-3) CHfC00CHICIIC411? (CII*)h CHfC00CHICIIC411? Js C00CIItCHCall* (CIri? Cl1-C) IC@l1rt \/ (H-1) 11+1 11 (H-2) l1 H (H-3) 01 Summer (H-4) n11 (X-4) (A -1) H I (B-1) (P-1) 1←CIICIIt+- ■ C0NllCa11g (t) Molecular weight approximately 60,000 (E-1) Table 2 For each sample stored under these conditions 1 to 10, Using laser diodes with emission wavelengths of 670 nm, 750 nm, and 810 nm, scanning exposure was applied through an optical wedge at 400 dpi with an average exposure time of 2 x 10-7 seconds per pixel, and after 3 seconds, the following color development treatment l was applied. did.

Processing process Temperature Color development 50℃ Bleach fixing 50℃ Rinse 1 40℃ Rinse 2 40℃ Rinse 3 40℃ Dry 90℃ time 9 seconds 12 seconds 5 seconds 5 seconds 5 seconds 9 seconds Color developer Ethylenediamine-N,N.

N-,N--tetramethylenephosphonic acid N,N-di(carboxymethyl) hydrazine N,N-diethylhydroxylamine oxalate 1-liethanolamine sodium sulfite potassium chloride potassium bromide potassium carbonate N-ethyl-N -(β-methanesulfonamidoethyl)- 3-methyl-4-aminoaniline sulfate WHITEX-4 (manufactured by Sumitomo Chemical) Add water to adjust pH to 10°5, 0 1.4 000 05 3°4°g g 4g g 1g g Bleach-fix ammonium thiosulfate (55wt%) 100ml Sodium sulfite 17.0g Ammonium ethylenediaminetetraacetate (III) acetate 55.0g Sodium ethylenediaminetetraacetate 5.0g Ammonium bromide 40.0g Glacial acetic acid
Add 9.0 g water
1000 ml Adjusted to pH 5.80 Rinse solution Ion-exchanged water (calcium ions 3 ppm or less, magnesium ions 2 ppm or less) Measure the cyan, magenta, and yellow concentrations of the sample through treatment step 1 using a TCD densitometer manufactured by Fuji Photo Film Co., Ltd. The obtained sensitivities are shown in Table 3. Sensitivity is sample A
The sensitivity of each coloring layer of the sample was stored frozen at -16° C. while the samples were stored under storage conditions 1 to 10. The sensitivity of each coloring layer was expressed as 100 in relative terms.

Table 3: Samples stored under storage conditions 4 to 10 of the present invention showed a clear decrease in sensitivity for samples stored under comparative conditions 1 to 3, whereas samples stored under frozen conditions had almost the same sensitivity as samples stored frozen. It shows.

Furthermore, by comparing storage conditions 4 and 5 of the present invention, it is found that as long as the oxygen volume fraction is almost the same, the same storage improvement effect can be obtained regardless of the method used to obtain it. It shows.

Furthermore, by comparing storage conditions 9 and 10 of the present invention, it is understood that the amount of oxygen present almost determines the storage stability of the photosensitive material.

The effect of the storage conditions of the present invention is due to the shorter wavelength of approximately 670 nm.
8, which has a longer wavelength than the yellow coloring layer spectrally sensitized with a carbocyanine sensitizing dye that gave a spectral sensitivity peak of .
It is understood that the effect is remarkable in the cyan color-forming layer that has been spectrally sensitized with a tricarbocyanine sensitizing dye that has a spectral sensitivity peak at 35 nm.

And the effective oxygen volume fraction to obtain the effects of the present invention is approximately 2%.
It can also be understood by comparing storage conditions 1, 3, 4, etc. that the storage conditions are below that level.

From the above results, it was understood that the means of the present invention is effective in maintaining stable performance of silver halide photographic materials using the infrared spectral sensitizing dye specified in the present invention.

It was also shown that the sample according to the present invention can be rapidly processed as in processing step 1.

Example 2 The treatment step 1 performed in Example 1 was changed as follows to create treatment step 2, and samples 1 to 10 used in Example 1 were
processed. Exposure was performed in the same manner as in Example 1.

Temperature Color development 35℃ Bleach fixing 35℃ Rinse 1 25℃ Rinse 2 25℃ Rinse 3 25℃ Kui-Ho 45 seconds 45 seconds 30 seconds 30 seconds 30 seconds Drying 80℃ 60 seconds Processing step 1 The processing time was 45 seconds, forming the image very quickly, whereas processing step 2 took 4 minutes. Regarding sensitivity due to differences in storage conditions, almost the same results as in Example 1 were obtained.

Regarding the sensitivity difference itself, the difference in sensitivity between samples was larger when processed in processing step 1 of Example 1, and was slightly smaller in processing step 2.

Example 3 Compound (V-23) used for spectral sensitization of the silver halide emulsion of the cyan coloring layer of Sample A prepared in Example 1,
An emulsion was prepared in which the compound (V-46) used for spectral sensitization of the silver halide emulsion of the magenta color-forming layer was replaced with the compounds shown in Table 4 in equimolar amounts, and the same photosensitive materials B to Sample A were prepared. F was produced.

Table 4 λmax represents the spectral sensitivity peak wavelength in nl.

Using these samples B-G, tests similar to those conducted under storage conditions 1 and 6 of Example 1 were conducted. The treatment was carried out in the same manner as in Example 2.

Table 5 shows the results regarding sensitivity changes after storage. The sensitivity was expressed relative to the sensitivity of each coloring layer of the sample stored frozen at -16°C as 100.

Table 5: Samples stored under storage conditions 6 of the present invention do not have lower sensitivity compared to samples stored under storage conditions 1 outside of the present invention, and maintain approximately the same to slightly higher sensitivity than samples stored frozen. You can see that it's sagging.

The tricarbocyanine sensitizing dye or the hexamethine merocyanine sensitizing dye used in the cyan coloring layer both have spectral sensitivities at longer wavelengths than the sensitizing dye used in the magenta coloring layer. It is understood that when a sensitive dye is used, the effect of improving storage stability of the present invention is large.

This tendency was also confirmed when comparing among the sensitizing dyes used in the cyan coloring layer. It is understood that the effects of the present invention are significant in light-sensitive materials having a spectral sensitization region in the infrared region.

Example 4 Compounds (V-31), (V-34), ( V-3
Emulsions with equimolar substitution were prepared according to 5), and light-sensitive materials H to J similar to Sample B were produced.

Using these samples flH to J, storage conditions 1 of Example 1 were
Tests similar to those conducted for and 6 were conducted. The treatment was carried out in the same manner as in Example M2.

Table 6 shows the results regarding sensitivity changes after storage. The sensitivity was expressed relative to the sensitivity of each coloring layer of the sample stored frozen at -16°C as 100.

Table 6 Samples stored under storage condition 6 according to the present invention do not have lower sensitivity compared to samples stored under storage condition 1 outside the present invention, and maintain approximately the same to slightly higher sensitivity than samples stored frozen. You can see that it's sagging.

(Effects of the Invention) According to the present invention, changes over time in the photographic properties of a silver halide photographic material spectrally sensitized to an infrared wavelength region can be prevented. Thereby, it is possible to provide an infrared spectral sensitized photosensitive material that always has a constant high sensitivity.

Claims (10)

[Claims] (1) In a method for packaging or storing a silver halide photographic material, at least one photosensitive layer of the silver halide photographic material is sensitized by a tricarbocyanine sensitizing dye or hexamethine merocyanine that provides a spectral sensitivity peak at 720 nm or more. The silver halide photographic light-sensitive material is spectrally sensitized with at least one sensitizing dye selected from a dye, a pentamethine rhodacyanine sensitizing dye, or a heptamethine rhodacyanine sensitizing dye, and the silver halide photographic light-sensitive material is in a deoxidized state. A method for packaging or storing a silver halide photographic material, characterized in that the material is packaged or stored in a. (2) The method for packaging or storing a silver halide photographic material according to claim (1), wherein the deoxidized state is an oxygen volume fraction of 2% or less. (3) The method for packaging or storing a silver halide photographic material according to claim (1) or (2), wherein the deoxidized state is created by an oxygen scavenger. (4) The method for packaging or storing a silver halide photographic material according to claim (1) or (2), wherein the deoxidized state is created by a solid oxygen pump. (5) The method for packaging or storing a silver halide photographic material according to claim (1) or (2), wherein the deoxidized state is created by vacuum degassing. (6) A method for packaging a silver halide photographic material according to claim (1) or (2), wherein the deoxidized state is created by an air substitution operation with an inert gas other than oxygen; Preservation method. (7) The halogen according to any one of claims (1) to (6), wherein the deoxidized state is an oxygen volume fraction of 2% or less, and at the same time, the equilibrium relative humidity is 20% or less. A method for packaging or storing silver chemical photographic materials. (8) The silver halide photographic light-sensitive material has at least two photosensitive layers having a spectral sensitivity peak at 720 nm or more, and each photosensitive layer contains at least one of a cyan coupler, a magenta coupler, or a yellow coupler. The method for packaging or storing a silver halide photographic material according to any one of claims (1) to (7), wherein the material is a silver halide color photographic material. (9) The silver halide photographic light-sensitive material consists of at least three photosensitive layers containing silver chlorobromide or a silver chloride emulsion with an average silver chloride content of 10 mol% or more, and each photosensitive layer contains a cyan coupler and a magenta coupler. or yellow coupler, and the three photosensitive layers each have three light wavelength regions of 650 to 690 nm, 72 nm,
The silver halide photographic material according to any one of claims (1) to (8), which is a silver halide color photographic material having different spectral sensitivity peaks at 0 to 790 nm and 770 to 850 nm. packaging or storage methods. (10) Patent claim (1) characterized in that the silver halide photographic material comprises at least one photosensitive layer containing silver chlorobromide or a silver chloride emulsion with an average silver chloride content of 96 mol% or more. ) to (9). A method for packaging or storing a silver halide photographic material according to any one of (9).