JPH03194537A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a sensitive material having high sensitivity, hardly causing fog and hardly undergoing a change in the photographic performance during storage by subjecting an emulsion contained in a silver halide emulsion layer to reduction sensitization in a producing stage and regulating the equilibrium pAg to a specified range. CONSTITUTION:A silver halide emulsion is subjected to a reduction sensitization with dioxythiourea, ascorbic acid or a deriv, thereof in an arbitrary stage during production and the equilibrium pAg is regulated to 7-11. Fine silver nuclei generated by high speed development do not become coarse silver nuclei by growth with the lapse of time and a sensitive material having high sensitivity, hardly causing fog and hardly undergoing a change in the photographic performance during storage is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a high-sensitivity silver halide photographic material that exhibits little fluctuation in sensitivity and fog during storage.

[Prior Art] The basic properties required of silver halide emulsions for photography are high sensitivity, low fog, and fine grain.

In order to increase the sensitivity of an emulsion, it is necessary to (1) increase the number of photons absorbed by a single grain, and (2) increase the efficiency with which photoelectrons generated by light absorption are converted into silver clusters (?1 image). , and (3) it is necessary to increase the development activity in order to effectively utilize the formed latent image.

Increasing the size increases the number of photons absorbed by one particle, but
Decrease image quality. Increasing the development activity is also an effective means for increasing the sensitivity, but in the case of parallel development such as color development, graininess generally deteriorates. In order to increase sensitivity without deteriorating graininess, it is most preferable to increase the efficiency of converting photoelectrons into latent images, that is, to increase quantum sensitivity.To increase quantum sensitivity, recombination, latent image dispersion, etc. It is necessary to eliminate as many inefficient processes as possible. It is known that reduction sensitization, which creates small silver nuclei with no development activity inside or on the surface of silver halide, is effective in preventing recombination.

Attempts at reduction sensitization have been considered for a long time.

Carroll, U.S. Patent No. 2,487,
No. 850, tin compounds, Lowe et al. No. 2,512,925, polyamine compounds, Palens et al.
No. 89,823 disclosed that thiourea dioxide-based compounds are useful as reduction sensitizers. Furthermore, Co
11ier (Korea) is PhotographicS
Science and Engineering Volume 23 1
13 (1979) compares the properties of silver nuclei produced by various reduction sensitization methods. She dimethylamine borane, stannous chloride, hydrazine, high pH
The method of aging, low p, and Ag aging was adopted. The method of reduction sensitization is further described in U.S. Pat. No. 2,518,698;
No. 201,254, No. 3.411.917, No. 3
．． No. 779,777 and No. 3.930.867. Regarding not only the selection of reduction sensitizers but also the improvement of reduction sensitization methods, Japanese Patent Publication Nos. 57-33572 and 58-
No. 1410.

It has been known that reduction sensitization is advantageous for increasing the sensitivity of silver halide emulsions as described above, but when incorporated into light-sensitive materials, the storage stability is extremely poor and it has not been put to practical use. Regarding techniques for improving the storage stability of reduction-sensitized emulsions, see JP-A Nos. 57-82831 and 60-178445.
However, it has not reached a sufficient level of improvement, and there has been a long-awaited technology for improving the storage stability of photographic materials containing reduction-sensitized emulsions.

[Problems to be solved by the invention] In response to the recent demand for high sensitivity and high image quality, conventional reduction sensitization technology suffers from large fluctuations in sensitivity and fog when photosensitive materials are stored over time, making it impractical for practical use. was not suitable.

An object of the present invention is to provide a silver halide photographic material, particularly a silver halide color photographic material, which has high sensitivity, has little fog, and exhibits little fluctuation in photographic performance during storage.

[Means for Solving the Problems] As a result of intensive research to develop a color photographic material that satisfies the above objectives, the present inventors found that (1) at least one halogenated layer on the support; In a silver halide photographic light-sensitive material having a silver emulsion layer, at least one emulsion contained in the emulsion layer is subjected to reduction sensitization in the manufacturing process, and has an equilibrium pAg of 7 to 11. A silver halide photographic material characterized by:

(2) In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one emulsion contained in the emulsion layer is subjected to reduction sensitization during the manufacturing process. 1. A silver halide photographic material characterized by having a water content of 1 to 6%.

(3) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one emulsion contained in the emulsion layer is subjected to reduction sensitization during the manufacturing process. What is claimed is: 1. A silver halide photographic light-sensitive material, characterized in that it has been subjected to the following steps and has an equilibrium pH of 7 or less.

(4) The silver halide photographic material according to any one of claims (1) to 3), wherein the reduction sensitization is performed using at least one kind of ascorbic acid or a derivative thereof.

(5) Claims (1) to 4 characterized in that reduction sensitization has been performed in the presence of at least one compound represented by general formula (1), [■], or (III). ) The silver halide photographic material according to any one of the above.

[1) R-3o! S-M (II) R-3O,SR' (I[I) R-sows-La-ssoz-R”
In the formula, RSR' and R'' may be the same or different,
represents an aliphatic group, an aromatic group, or a heterocyclic group, M represents a cation, L represents a divalent linking group, m is 0 or 1
It is.

The compound of general formula (1) to III) may be a polymer containing a divalent group derived from the structure shown by (1) to I[I) as a repeating unit.

achieved by.

The gist of the idea of the present invention is as follows.

Photographic materials containing reduction-sensitized emulsions tend to fog over time because minute silver nuclei generated by reduction-sensitization are
This is because it grows over time and becomes a large silver nucleus. Therefore, to suppress fogging and sensitivity fluctuations over time, ! ) Setting appropriate storage conditions for photographic materials containing reduction-sensitized emulsions. As necessary conditions for this purpose, the equilibrium pAg and equilibrium PH1 water content of the photosensitive material are specified in detail.

2) The silver nuclei generated by reduction sensitization are produced under controlled conditions, making them difficult to grow over time.

The present invention will be explained in detail below.

The manufacturing process of silver halide emulsions is roughly divided into steps such as grain formation, desalting, chemical sensitization, and coating.
It is divided into maturity, growth, etc. These steps are not performed uniformly; the order of the steps may be reversed, or the steps may be repeated.

The term "reduction sensitization" being carried out during the production process of the silver halide emulsion basically means that it can be carried out at any step. Reduction sensitization can be performed during nucleation, which is the initial stage of grain formation, during physical ripening, or during growth, and can be performed in combination with gold sensitization, which can be performed before or after chemical sensitization. When chemical sensitization is performed, it is preferable to carry out reduction sensitization prior to chemical sensitization in order to avoid undesirable fogging, and the most preferable method is reduction sensitization during the growth of silver halide grains. . Growing refers to methods in which reduction sensitization is performed while the silver halide grains are growing through physical ripening or addition of a water-soluble root salt and a water-soluble alkali halide, and methods in which growth is temporarily stopped during growth. This means that it also includes a method of further growth after reduction sensitization in the state.

The reduction sensitization of the present invention is a method of adding a known reducing agent to a silver halide emulsion, and a low pH of 1 to 7 called silver ripening.
, a method of growing or aging in an Ag atmosphere,
It is possible to choose either a method of growing or aging in a high pH atmosphere of pH 8 to 11, which is called high pH ripening. Moreover, two or more methods can also be used together.

Reduction sensitization can also be carried out by adding a reduction sensitizer.

As reduction sensitizers, mention may be made of stannous salts, amines and polyamines, hydrazine derivatives, formamidine sulfinic acids, silane compounds, borane compounds and ascorbic acid derivatives.

In the present invention, any one of these compounds can be used, and two or more kinds of compounds can be used in combination.

Particularly preferred reduction sensitizers are thiourea dioxide, ascorbic acid, and derivatives thereof (hereinafter referred to as "ascorbic acid compounds").

Specific examples of ascorbic acid compounds include the following.

(A-1) L-ascorbic acid (A-2) Sodium L-ascorbate (A-3
) Potassium L-ascorbate (A-4) DL
-Ascorbic acid (^-5) D-Sodium ascorbate (A-6
) L-ascorbic acid-6-acetate (A-7)
L-ascorbic acid-6-palmitate (A-8)
L-ascorbic acid-6-benzoate (A-9)
L-ascorbine M-6-diacetate (A-10
) The amount of L-ascorbic acid-5,6-o-inpropylidene reduction sensitizer added depends on the emulsion manufacturing conditions, so it is necessary to select the amount added, but in terms of -S, halogenated SN 1
A range of 10-' to 10-'' mole per mole is suitable.

Reduction sensitizers include water, alcohols, glycols,
It can be dissolved in a solvent such as ketones, esters, amides, etc. and added during particle formation.

Particularly preferred is a method in which it is added during grain growth. It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time during particle formation.

Alternatively, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble root salt or a water-soluble alkali halide, and particles may be formed using these aqueous solutions. It is also a preferable method to add in several portions or to add continuously over a long period of time.

The reduction sensitization of the present invention is preferably carried out in the presence of compounds represented by formulas (1), (II) and (III) in the production process of silver halide emulsions.

(1) R-3O, S-M (I[) R-3O, S-R' CI[) R-3o! In the formulas, RSR' and R'' may be the same or different and represent an aliphatic group, an aromatic group, or a heterocyclic group, M represents a cation, and L represents a represents a valent linking group, and m is O or 1.

To explain the compounds of general formulas (1), CU) and (Ill) in more detail, when R, R- and Rt are aliphatic groups, preferably an alkyl group having 1 to 22 carbon atoms, or an alkyl group having 2 to 22 carbon atoms. 22 alkenyl groups and alkynyl groups, which may have substituents. Examples of the alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, and dodecyl. , hexadecyl, octadecyl, cyclohexyl, isopropyl, and t-butyl.

Examples of the alkenyl group include allyl and butenyl.

Examples of the alkynyl group include propargyl and butynyl.

The aromatic groups R, R' and Rt preferably have 6 to 20 carbon atoms, such as phenyl and naphthyl. These may be substituted.

The heterocyclic group of R, R' and R2 includes nitrogen, oxygen,
A 3- to 15-membered ring containing at least one element selected from sulfur, selenium, and tellurium, such as pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, and selenazole. , benzoselenazole, tetrazole, triazole, benzotriazole, tetrazole,
Examples include oxadiazole and thiadeazole.

Examples of substituents for RSR' and R1 include alkyl groups (e.g. methyl, ethyl, hexyl), alkoxy groups (
For example, methoxy, ethoxy, octyl), aryl groups (
For example, phenyl, naphthyl, tolyl), hydroxy group,
halogen atoms (e.g. fluorine, chlorine, bromine, elements, etc.),
Aryloxy groups (e.g. phenoxy), furkylthio groups (e.g. methylthio, butylthio), arylthio groups (
(e.g., phenylthio), acyl groups (e.g., acetyl, propionyl, butyryl, valeryl), sulfonyl groups (e.g., methylsulfonyl, phenylsulfonyl), acylamino groups (e.g., acetylamino, benzamino),
Examples include a sulfonylamino group (methanesulfonylamino, benzsulfonylamino), an acyloxy group (eg, acetoxy, benzoxy), a carboxyl group, a cyano group, a sulfo group, an amino group, and the like.

L is preferably a divalent aliphatic group or a divalent aromatic group. Examples of the divalent aliphatic group of L include *CHt
)-(n=1~12)CHz CH=CH
CHt- -CH, CmiCCH.

Examples of the divalent aromatic group for L include phenylene and naphthylene.

These substituents may be further substituted with the substituents described above.

M is preferably a metal ion or an organic cation. Examples of metal ions include lithium ions, sodium ions, and potassium ions. Organic cations include ammonium ions (e.g. ammonium, tetramethylammonium, tetrabutylammonium)
, phosphonium ion (tetraphenylphosphonium)
, guanidine group, etc.

Specific examples of compounds represented by formula (1), (It) or (III) are listed in Table A, but the invention is not limited thereto.

The compound of general formula (1) can be easily synthesized by the method described in JP-A-54-1019 and British Patent No. 972,211.

The compound represented by the general formula (I), (It) or (I[[) has 10 -1 to 10 -1
It is preferable to add moles, furthermore from 10-6 to 10-
The amount added is preferably from 10% to 10% to 10% to 10% to 1 mole Ag.

The compounds represented by formulas (1) to (III) can be added during the manufacturing process by a method commonly used for adding additives to photographic emulsions.

For example, for water-soluble compounds, make an aqueous solution of an appropriate concentration,
Compounds that are insoluble or sparingly soluble in water are dissolved in a suitable organic solvent that is miscible with water, such as alcohols, glycols, ketones, esters, amides, etc., and does not adversely affect photographic properties. However, it can be added as a solution.

The compound represented by compound (1), (I[) or (DI) may be added at any stage during grain formation of the silver halide emulsion, before or after chemical sensitization. Preferred is a method in which the compound is added before or during reduction sensitization. Particularly preferred is a method in which it is added during grain growth.

Although it is possible to add the compounds (1) to (I) to the reaction vessel in advance, it is preferable to add them at an appropriate time for particle formation. Then, particles may be formed using these aqueous solutions, or compounds [!] may be formed along with particle formation. ] - (II) It is also a preferable method to add the solutions in several portions or to add them continuously for a long period of time.

The most preferred general formula of the compound for the present invention is a compound represented by general formula (1).

Table A (11) CH) SO-S Na (12) C! H5S OZ S Na (L-3)
C YuH, SO, S K (1-4) c4H,so□5Li (1-5) C,H+zSOzSNa (1-6) C,H,,SO,5Na CH3(CHz)scHcHzsOis-NH.

zHs (1-8) C,,H,5OzSNa (19) C+zHzsSO! S N,a (110)
C+&Hff:+S O2S Na(1-12)L
-C4H,SO,5Na(1-13)CH,OCH,C
H, SO! S-NaCHz=CHCHzSOzSNa KSSOz (CHz)zsOzsK Na S S 0z (CH,)4S O,S Na
Na SSO! (CH2)-3 (CHri430! S Na C, HsS O□5-CNyuC* Hlv S O□S CHz CH3C, HsS
O! SCH, CHICN CH3 C4H? S O□5CHCH, CN CyoH, S O□S CH, CH, CHlCH, OHC
zHsS(hscHzc)lzsOzcHzcHzss
O□CJsCHzCLOH CH,S;SQ, (CH,)4SO,5CH3CHas
SO! (CHz) is O□SCH.

x:y=2/1 (molar ratio) Cz Hs SO□5SSOzCzHs(n)C3H
? SO! S S S O2C3Ht(n) In the present invention, the equilibrium pAg value of the photosensitive material is preferably 7 to 11, more preferably 8 to 1O05, particularly preferably 8.5 to 10.5. Equilibrium pAg value is 7.0
If it is less than that, the increase in fog during storage will increase,
If it is larger than 11, the sensitivity decreases significantly during storage.

The equilibrium pAg value here is a value measured as follows. That is, cut out an area such that the volume of all the layers on the photosensitive material layer side coated on the support corresponds to the LED, cut it into small pieces, and immerse it in 50-g of distilled water.
This value is measured when g reaches equilibrium.

In order to adjust the equilibrium pAg value, for example, the p of the coating solution,
Ag may be adjusted with an aqueous solution of silver nitrate or alkali halide. At this time, the pAg of all layers may be adjusted, or only a specific layer (for example, an intermediate layer or a protective layer) may be adjusted.

In the present invention, the moisture content of the light-sensitive material is preferably 1 to 6%, more preferably 2 to 5.5%, particularly preferably 3 to 5%. If the moisture content of the light-sensitive material is less than 1% or more than 6%, fog increases significantly during storage and sensitivity also decreases.

The moisture content here is a value measured by the following method, which is usually called the absolute dry method. That is, 100 d of the photosensitive material coated on the support was cut out, placed in a glass weighing bottle, and
It is obtained by the following formula from the value measured by weight at 5°C and the value measured by weight after being left to stand completely dry at 105°C for 16 hours.

-C A: weight before bone drying B: weight after bone drying C: weighed bottle weight after bone drying The moisture content of the photosensitive material of the present invention can be maintained by sealed packaging.

Sealed packaging in the present invention refers to moisture-proof packaging, which is well known in the field of ordinary packaging. Packaging materials include metals such as aluminum plates, tinplates, and aluminum foils; metal foils; Glass, or polymers such as polyethylene, polyvinyl chloride, polystyrene, polyvinylidene chloride, polypropylene, polycarbonate, polyamide, etc., composite laminate materials (laminate materials in packaging terms) made of various polymers and materials such as cellophane, paper, aluminum foil, etc. is used.

Sealing methods include adhesive methods using various adhesives,
It is possible to use a heat sealing method, a method using a cartridge case, etc., which is common in the photographic industry. Details of these sealing methods are described in "Food Packaging Technology Handbook", Japan Packaging Technology Association (wl), pages 573-6069.

In the present invention, a cartridge case made of a polymer such as polyethylene or polypropylene is preferable for a roll type photosensitive material, and a cartridge case made of a polymer such as polyethylene or the like is preferable for a sheet type photosensitive material.

These sealed packagings may be done in duplicate.

As a packaging method with the moisture content adjusted as in the present invention, the silver halide photographic light-sensitive material may be packaged in a constant temperature chamber, or the moisture content may be adjusted and dried during drying of the photosensitive material. Alternatively, a desiccant such as silica gel may be placed in a sealed container to reduce humidity.

In the present invention, the equilibrium pH value of the photosensitive material is preferably 7.0 or less, more preferably 4.5 to 6.0.
5, particularly preferably 5.0 to 6°3. equilibrium pH
If the value is greater than 7.0, the increase in fog during storage will increase and the sensitivity will also decrease.

The equilibrium PAL value referred to here is a value measured as follows. That is, an area such that the volume of all the layers on the side of the photosensitive material layer coated on the support is 1- is cut out, cut into small pieces, immersed in 50W11 distilled water, and adjusted to pH
After reaching equilibrium, the pH was measured using a pH meter.

In order to make the equilibrium pH value 7.0 or less, for example, the pH of the coating solution can be lowered using an acid (e.g. hydrochloric acid, acetic acid, etc.). The pH value of only the layers (eg, intermediate layer, protective layer) may be lowered.

Preferred embodiments of the invention are as follows.

+11 In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one emulsion contained in the emulsion layer is subjected to reduction enhancement during the manufacturing process. , and the equilibrium pAg is 7-1
1. A silver halide photographic material having a water content of 1 to 6% and an equilibrium pH of 7 or less.

(2) A silver halide photographic light-sensitive material of the above fil, in which reduction sensitization is performed using at least one kind of ascorbic acid or its derivatives.

(3) A silver halide photographic light-sensitive material of the above film, which has been subjected to reduction sensitization in the presence of at least one compound represented by the general formula (1), CI or CIII.

(4) The above (1) is subjected to reduction sensitization with at least one ascorbic acid or its derivative in the presence of at least one compound represented by general formula (1), (It) or (III). ) silver halide photographic materials.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any silver halide such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. The silver halide is silver iodobromide, silver bromide, or silver chlorobromide containing up to 30 mol % of silver iodide.

Even if the silver halide grains used in the present invention are normal crystals that do not contain twin planes, examples such as those explained in the Photographic Society of Japan, Basic Silver Salt Photography of the Photographic Industry (Corona Publishing), p. 163,
For example, a single twin with one twin plane, two parallel twin planes
Depending on the purpose, it can be selected from among parallel multiple twins containing two or more nonparallel twin planes, nonparallel multiple twins containing two or more nonparallel twin planes, and the like. In the case of normal crystals, it is a cube consisting of (100) planes, an octahedron consisting of (111) planes, and Japanese Patent Publication No. 55427.
37, disclosed in Japanese Patent Application Laid-Open No. 60-222842 (1
10) Dodecahedral particles consisting of faces can be used.

In addition, Journal of ImagingScie
nce 30 S247 Page 1 A (hl) plane particle represented by (211) as reported in 1986,
(hhl) plane particle represented by (331), (210)
Although (hkO) plane particles representing the plane and (hkl) plane particles representing the (321) plane require some ingenuity in their preparation methods, they can be selected and used depending on the purpose. (100) plane and (1
11) A tetradecahedral particle in which faces coexist in one particle, (10
Particles in which 0) and (110) planes coexist or (111
Particles in which two planes or a large number of planes coexist, such as particles in which a ) plane and a (110) plane coexist, can also be selected and used depending on the purpose.

The grain size of the silver halide may be fine grains of 1 micron or less, or large grains with a projected area diameter of up to 10 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. good.

A so-called monodisperse silver halide emulsion having a narrow grain size distribution in which 80% or more of all grains fall within ±30% of the average grain size in terms of grain number or weight can be used in the present invention. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are mixed in the same layer or in separate layers in emulsion layers having substantially the same color sensitivity. Can be applied in multiple layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Paul Montell (P.

Glafkides, Chimie et Phys
ique PhotographiquePaul M
ontel 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duffi)
nPhotographic Emulsion Ch
emistry (Focal Press.

1966), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al.
, published by Focal Press (V, L, Zelilva
Net al, Making and Coatin
g Photographic Emulsion F
ocal Press+ 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As a form of simultaneous mixing method, pAg in the liquid phase in which silver halide is produced is
The method of keeping constant is the so-called chondral
A double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

The above-mentioned silver halide emulsion consisting of regular grains can be obtained by controlling 1) Ag and p) 1 during grain formation. For more information, please refer to Photographic Science and Engineering (Photography Science and Engineering).
c5science and engineering
) Volume 6, pp. 159-165 (1962); Journal of Photographic Science
al of Photographic 5cienc
e) + 12 volumes.

pp. 242-251 (1964), U.S. Patent No. 3°655
．． No. 394 and British Patent No. 1,413°748.

Further, tabular grains having an aspect ratio of 3 or more can also be used in the present invention. Tabular grains are described by C1eve Photo-grain [Theory and Practice of Photography J]
phy Theory and Practice (
1930) ), p. 131; Gatoff, Photographic Science and Engineering (C
utoff.

Photographic 5science and
Engineering) *Volume 14, 248-25
7 pages (1970); U.S. Patent Nos. 4,434.226, 4,414,310, 4,433,048,
Same 4. 439°520 and British Patent No. 2,112
, No. 15T. When tabular grains are used, there are advantages such as increased covering power and increased color sensitization efficiency by sensitizing dyes, which are detailed in the above-cited U.S. Pat. No. 4,434,226. .

Tabular grains are preferred as emulsions of the present invention.

In particular, particles with an aspect ratio of 3 to 8 account for 50% of the total projected area.
Tabular grains occupying the above amount are preferable.

These emulsion grains, which may have a -like crystal structure, may have different halogen compositions on the inside and outside, and may have a layered structure, are disclosed in British Patent No. 1.027.
No. 146, U.S. Patent No. 3゜505.068, No. 4,4
44.877 and Japanese Patent Application No. 58-248469. Further, silver halides having different compositions may be bonded by epitaxial bonding (or may be bonded with a compound other than silver halide, such as silver rhodan or lead oxide).

The silver halide emulsion of the present invention preferably has a distribution or structure regarding the halogen composition in its grains.
Typical examples are JP-B No. 4313162 and JP-A No. 61.
-215540, JP-A-60-222845, JP-A-6
These are core-shell type or double-structured particles in which the interior and surface layers of the particles have different halogen compositions, such as those disclosed in Japanese Patent No. 1-75337. In such particles, the shape of the core portion and the overall shape including the shell may be the same or different. Specifically, the core part has a cubic shape, and the shape of the shelled particle may be cubic or octahedral. Conversely, the core may be octahedral and the shelled particle may be cubic or octahedral. Further, although the core portion is a clearly regular particle, the shape of the shelled particle may be slightly distorted or irregular. Moreover, instead of a simple double structure, a triple structure as disclosed in JP-A No. 60-222844 or a more multi-layer structure,
Silver halides having different compositions can be thinly applied to the surface of the core-shell double-structured grains.

In order to give a structure to the inside of a particle, it is possible to create a particle having not only the above-mentioned enveloping structure but also a so-called bonding structure. These examples are disclosed in Japanese Patent Application Laid-Open No. 59-13354.
0, Japanese Patent Publication No. 58-108526, EP199290A2
, Japanese Patent Publication No. 58-24772, Japanese Patent Application Laid-Open No. 59-16254, etc. The crystal to be bonded can have a composition different from that of the host crystal and can be formed by bonding to an edge, part of a corner, or surface of the host crystal.

Such a bonded crystal can be formed even if the host crystal is uniform in terms of halogen composition or has a core-shell structure.

In the case of a bonded structure, a combination of silver halides is naturally possible, but a bonded structure can be obtained by combining a silver halide with a silver salt compound that does not have a rock salt structure, such as Rodan silver or Charcoal #I silver. Further, non-silver salt compounds such as PbO may also be used if a bonded structure is possible.

In the case of silver iodobromide grains having these structures, for example, in a core-shell type grain, even if the core part has a high silver iodide content and the shell part has a low silver iodide content, or conversely, the core part has a low silver iodide content. Grains with a low silver iodide content and a high shell part may be used. Similarly, grains with a bonded structure may have a high silver iodide content in the host crystal and a relatively high silver iodide content in the bonded crystal. It may be a low particle or vice versa.

In addition, the boundaries between particles with these structures with different halogen compositions may be clear boundaries, or may be unclear boundaries due to the formation of mixed crystals due to composition differences, or may be actively continuous boundaries. It may also be one with some structural changes.

The silver halide emulsion used in the present invention is EP-009672.
781, EP-0064412B1, or DB-2.
The surface may be modified as disclosed in JP-A-60-221320, No. 306447C2.

The silver halide emulsion used in the present invention is preferably a surface latent image type emulsion, but an internal latent image type emulsion can also be used by selecting the developer or development conditions, as disclosed in JP-A-59-133542. can. A shallow internal latent image type emulsion covered with a thin shell can also be used depending on the purpose.

It is known that silver halide solvents are useful in promoting ripening. For example, it is known to have an excess of halide ions present in the reactor to promote ripening. It is therefore clear that ripening can be accelerated simply by introducing a halide salt solution into the reactor. Other ripening agents can be used, and these ripening agents can be incorporated in their entirety into the dispersion medium in the reactor before the silver and halide salts are added, and one or more ripening agents can be used. can also be introduced into the reactor along with the addition of halide salts, silver salts or peptizers. As another variant B, the ripening agent can also be introduced independently at the halide salt and silver salt addition stages.

As ripening agents other than halogen ions, ammonia or amine compounds, thiocyanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used.

In the present invention, it is extremely important to perform chemical sensitization such as sulfur sensitization and gold sensitization, and significant effects have been obtained when chemical sensitization is performed. The location where chemical sensitization is applied varies depending on the composition, structure, and shape of the emulsion grains, as well as the intended use for which the emulsion will be used. When chemically sensitizing nuclei are embedded inside grains, they should be embedded shallowly from the grain surface. In some cases, chemical sensitization nuclei may be created on the surface.

Although the effects of the present invention are also effective, particularly preferred is the case where chemically sensitized nuclei are created near the surface. In other words, surface latent image type emulsions are more effective than internal latent image type emulsions.

Chemical sensitization is described by James (T, It, James
), The Photographic Ink Process, 4th edition,
Published by McClammin Publishing, 1977, (T. H. James
, The Theory of the Photog
rapic Process+ 4th edM
acmillan, l 977), pp. 67-76, or as described in Research Disclosure, Vol. 120, 19.
April 1974, 12008; Research Disclosure, 34S, June 1975, 13452, U.S. Patent Nos. 2.642,361, 3,297.446, 3
, No. 772,031, No. 3゜857.711, No. 3,
901.714, 4.266.018, and 3. 904. 415 and British Patent No. 1.31
pAg5~1O1pH as described in No. 5.755
5-8 and temperature 30-80°C, sulfur, selenium,
This can be done using tellurium, gold, platinum, palladium, iridium or a combination of these sensitizers. Chemical sensitization is optimally carried out in the presence of gold compounds and thiocyanate compounds and as described in U.S. Pat.
, 266.018 and 4,054,457, or in the presence of a sulfur-containing compound such as hypo, thiourea-based compounds, rhodanine-based compounds, or in the presence of a chemical sensitization aid. It can also be chemically sensitized. Chemical sensitization aids used include compounds known to suppress capri and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers are:
U.S. Patent No. 2,131°038, U.S. Patent No. 3,411,91
No. 4, No. 3,554.757, JP-A-58-1265
No. 26 and the aforementioned Duffin, "Photographic Emulsion Chemistry", 138
It is described on pages 143 to 143.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadolinthion; azaindene R
: For example, triazaindenes, tetraazaindene I
A number of compounds known as anti-capri agents or stabilizers can be added, such as I (especially 4-hydroxy-substituted (1,3,3a,7)tetraazaindenes), pentaazaindenes, etc. For example, U.S. Patent 3,95
No. 4.474, No. 3,982.947, Special Publication No. 1972-
28.660 can be used.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and others. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus/imidazole nucleus, tetrazole nucleus,
Pyridine nuclei, etc.; Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxane nucleus, etc. Dole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a pyrazolin-5-one nucleus, thiohydantoin tAi, 2-1-oxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, and rhodanine nucleus having a ketomethylene structure. 5-6 such as nuclei, thiobarbic acid nuclei, etc.
Member heterosegmental ring nuclei can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Representative examples are U.S. Patent No. 2.688.545 and U.S. Patent No. 2.9
No. 77.229, No. 3,397,060, No. 3,52
No. 2,052, No. 3,527,641, No. 3,617
, No. 293, No. 3.628.964, No. 3,666.
No. 480, No. 3.672898, No. 3,679,42
No. 8, No. 3,703.377, No. 3,769,301
No. 3814.609, No. 3,837,862,
No. 4.026,707, British Patent 1. 344. 2
No. 81, No. 1,507,803, Special Publication No. 434936
No. 53-12,375, JP-A-52-110,6
No. 18, No. 52-109.925.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

The dye may be added to the emulsion at any stage of emulsion preparation known to be useful.

However, ll'il is carried out after the completion of chemical sensitization and before application, as described in US Pat. No. 3.628.969 and US Pat. 225゜666, the spectral sensitization can be carried out at the same time as the chemical sensitizer, or as described in JP-A-58-113,928. It can be carried out prior to chemical sensitization, or it can be added before the completion of silver halide grain precipitation to start spectral sensitization. It is also possible to add these compounds in portions as taught in U.S. Pat. No. 4,225,666, i.e. some of these compounds are added prior to chemical sensitization and the remainder is added prior to chemical sensitization. It is also possible to add it after the sensitization, as described in U.S. Patent No. 4,18
No. 3.756, and at any time during silver halide grain formation.

The amount added is 4×10-” to 8 per mole of silver halide.
Although it can be used in amounts of X10-3 moles, about 5X10-' to 2X10-' moles are more effective when the silver halide grain size is more preferably 0.2 to 1.2 .mu.m.

The various additives described above are used in the photosensitive material related to the present technology, but various other additives can also be used depending on the purpose.

These additives are described in more detail in Research Disclosure 1tem 17643 (December 1978) and 1tem 18716 (November 1979), and the relevant sections are summarized in the table below.

Chemical sensitizer Sensitivity enhancer Brightener 23 pages 648 pages Right side Same as above page 24 and Stabilizer Stain inhibitor Dye image stabilizer Hardener Binder Plasticizer, lubricant 25 pages Right column 25 pages 26 pages 26 pages 27 pages Page 650 Left-Right Column Page 651 Left Column Same as above Page 650 Right Column Surfactant Various color couplers can be used in the present invention.
RD) PkL17643, described in the patent described in ■-C-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4.022,620, No. 4.3
No. 26,024, No. 4,401゜752, Special Publication No. 5
B-10739, British Patent No. 1,425,020,
Same 1st. No. 476, 760, particularly those described therein are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, for example, US Pat.
, 310.619, 4,351.897, European Patent No. 73,636, U.S. Patent No. 3,061,432
No. 3,725゜067, Research Disclosure 24220 (June 1984), JP-A No. 6
No. 0-33552, Research Disclosure No. 2
4230 (June 1984), JP-A-60-43659
No. 4,500,630, U.S. Pat. No. 4,540
．． Particularly preferred are those described in No. 654 and the like.

Typical examples of cyan couplers include phenolic and nabolimerized dye-forming couplers, such as those described in U.S. Pat.
No. 451,820, No. 4.080.211, No. 4
．． No. 367.282, British Patent No. 2.102,173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-open No. 57-151994
Preferred are those described in No. 57-154234, No. 60-184248, and U.S. Pat.

Couplers that release a nucleating agent or a development accelerator imagewise during development include, for example, British Patent No. 2097.14.
No. 0, No. 2,131,188, JP-A-59-157
Those described in No. 638 and No. 59-170840 are preferred.

Other couplers that can be used in the photosensitive material of the present invention include, for example, the competitive couplers described in U.S. Pat. No. 4,130.427 and the like, and U.S. Pat.
No. 4. No. 338.393, No. 4.310.6
Multi-equivalent coupler described in No. 18 etc., JP-A-60-185
950. DIR redox compounds or DIR coupler-releasing couplers or DIR coupler-releasing couplers or redoxes described in JP-A-62-24252, etc., couplers that release dyes that after separation as described in EP 173.302A, such as R, D.

Magnet 11449, 24241, JP-A-61-20124
Examples include the bleach accelerator-releasing couplers described in No. 7 and the like, such as the ligand-releasing couplers described in U.S. Pat. No. 4,553,477.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters R (e.g., dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate). ), esters of phosphoric or phosphonic acids 11 (e.g. triphel phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate), benzoic acid esters II (e.g. 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (e.g., N,N-diethyldodecanamide, N,N-
diethyl laurylamide, N-tetradecylpyrrolidone), alcohols or phenols (e.g. isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (e.g. bis(2-ethylhexyl) sebacate) , dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (e.g. N,N-diptyl-2-butoxy-5te)
rt-octylaniline), hydrocarbon I! (For example, paraffin, dodecylbenzene, diisopropylnaphthalene), etc. Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower, can be used, and typical examples include ethyl acetate,
Butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate,
Examples include dimethylformamide.

Specific examples of latex dispersion processes, effects, and latex for impregnation include U.S. Pat. It is described in.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

When the present invention is used in color photographic materials, it can be applied to photosensitive materials with various configurations and photosensitive materials in which layer configurations and special color materials are combined.

A typical example is illustrated below. JP 47-49031, JP 49-3843, JP 50-21248, JP 59-38147, JP 59-60437,
JP 60-227256, JP 61-4043, JP 61-43743, JP 61-42657
A combination of the coupling speed and diffusivity of a color coupler and the layer structure, as shown in No. 49-15 of the Special Publication
No. 495, U.S. Pat. No. 3,843,469, in which the same color-sensitive layer is divided into two or more layers, Japanese Patent Publication No. 1983-370
No. 17, Japanese Patent Publication No. 53-37018, Japanese Patent Publication No. 51-49
No. 027, JP-A-52-143016, JP-A-53-
No. 97424, JP-A-53-97831, JP-A-62
Examples include those in which the arrangement of high-sensitivity layers and low-sensitivity layers and the arrangement of layers with different color sensitivities are stipulated, such as No. 200350 and JP-A-59-177551.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, positive 17643, page 28, and same 18716, 6
It is described from the right column on page 47 to the left column on page 648.

The color photographic material according to the present invention includes the above-mentioned RD, N
Development processing can be carried out by the usual method described in pages 28 to 29 of A17643 and 651 left column to right column of Kaimagaku 18716.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains pn buffers such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo[2°2.2]octane) I! Various preservatives such as ethylene glycol, organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, fogging agents such as competing couplers sodium boron hydride, auxiliary developing agents such as l-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphones. Various types of chelates such as acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, and 1-hydroxyethylidene 1
, 1-diphosphonic acid, nitrilo-N,N,N=nitrimethylenephosphone, ethylenediamine-N,N.

Representative examples include N',N'-tetramethylenephosphonic acid, ethylene diamine di(O-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. Although the amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, it is generally less than 31 per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher,
You can also do the following: When reducing the amount of replenishment, it is preferable to prevent evaporation of the solution and air oxidation by reducing the contact area with the air in the processing tank, and by using means to suppress the accumulation of bromide ions in the developer. It is also possible to reduce the amount of replenishment.

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately (bleach-fixing process), or in order to speed up the process, it may be carried out in two ways: bleach-fixing process after bleaching process. Depending on the purpose, treatment may be carried out in consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. Examples of bleaching agents include iron (■) and cobalt (II).
In addition, compounds of polyvalent metals such as chromium (■) and copper (II), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide: dichromate; organic complex salts of iron (III) or cobalt (Ill), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, and 1,3-diaminoacetic acid. Aminopolycarboxylic acids such as propanetetraacetic acid, glycol ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.;
Persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Among these, aminopolycarboxylic acid iron (III) ti salts and persulfates, including ethylenediaminetetraacetic acid iron (DI) complex salts, are preferable from the viewpoint of rapid processing and environmental pollution prevention. Complex salts are particularly useful in both bleach and bleach-fix solutions.

The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (If) complex salts is usually 5.5 to 8, but in order to speed up the processing, it can be processed at an even lower pH. .

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are found in U.S. Pat. No. 3,893.
It is described in the specification in No. 858 and the like. Furthermore, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleach accelerators may be added to the light-sensitive material. agents are particularly effective.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, and ammonium thiosulfate is the most commonly used. Can be used widely. As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of water washing tanks and the quantity in the multistage countercurrent method is
Urnalof the 5ociety of Mo
tion Picture and Te1evi-s
ion Engineers Volume 64, P, 248
-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in JP-A-61-131.632 can be effectively used. Also, JP-A-57-8.542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, "Microbial layer" edited by Sanitation Technology Association It is also possible to use the fungicides described in "Sterilization, Disinfection, and Anti-Mildew Techniques" and "Encyclopedia of Antibacterial and Antifungal Agents" edited by the Japan Antibacterial and Antifungal Society.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can also be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
a for 20 seconds-10 minutes at 15-45°C, preferably 2
A range of 30 seconds and 5 minutes at 5-40°C is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Laid-Open Nos. 57-8.543 and 58-14.83
All known methods described in No. 4, No. 60-220,345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photographic materials for imaging. can.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Typical compounds that may contain pyrazolidones are JP-A-56-64,339 and JP-A-57-144,547.
No. 58115.438, etc.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, the temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time, or vice versa. By lowering the temperature, it is possible to improve *i and improve the stability of the processing solution. In addition, in order to save silver on photosensitive materials, West German Patent No. 2.226,770 or U.S. Patent No. 3
, 674.499 may be carried out using cobalt intensification or hydrogen peroxide intensification.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500.626, JP-A No. 60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in European Patent No. 9-218443, European Patent No. 61-238056, European Patent No. 210,660A2, and the like.

The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 Average iodine content is 20 mol%, average equivalent sphere diameter is 0.8μ
The core-shell ratio was 1=2, the iodine content of the shell was 2 mol%3, and the average iodine content was 10 using controlled double jet method in an aqueous gelatin solution using silver iodobromide double twinned grains of m as seed crystals. Average spherical equivalent diameter that is mol% 1.
An emulsion consisting of 2 μm silver iodobromide twin grains was formed.

After grain formation, the emulsion undergoes the usual desalting and water washing process and is heated to 40°C.
It was redispersed under the conditions of pAg 8.9 and pH 6.1. The emulsion thus produced is designated as Em-1.

On the other hand, 1 minute after the start of shell formation, reduction sensitizers thiourea dioxide and L-ascorbic acid were added at 2X10 per mole of silver.
-' moles were added to prepare emulsions Em-2 and Em-3.

Furthermore, when performing particle formation similar to Em-1, thiosulfonic acid compound 1-2.1-6 was added 1 minute before the start of shell formation.
．． The emulsions in which grains were formed by adding 3 x 10 -' mol of Em 1-16 per mol of silver to a reaction pot were designated as Em4-6.

Next, when performing particle formation similar to Em-1, thiosulfonic acid compound 1-2.1-6 was added 1 minute before the start of shell formation.
．． 1-16 was added per mole of silver into the reaction pot, and after the start of shell formation, thiourea dioxide and L-
Emulsions 7 to 12 were prepared using ascorbic acid in a manner of 2 x 10-'' moles per silver mole, respectively.

Emulsions 1 to 12 thus prepared were each optimally sensitized with gold and sulfur using sodium thiosulfate and chloroauric acid.

Next, the emulsion and protective layer were coated on the triacetylcellulose film support provided with the undercoat layer in the coating amounts shown in Table 1-2. At this time, a certain amount of a 1% solution of potassium bromide or a 1% solution of silver nitrate was added to the protective layer, and Table 1
A coated sample having the composition and equilibrium pAg shown in -3 was prepared.

Place one of these samples in a -8°C 10% freezer.
The other sheet was stored in an environment at 45° C. and 60% for 14 days, exposed to light for sensitometry, and subjected to the next color development process.

Table 1-1 Agent reduction sensitizer Em-1 2 Thiourea dioxide 3 L-Ascorbic acid 7 Thiourea dioxide 10 L-Ascorbic acid Table 1-2 (1) Emulsion layer 0 emulsion...shown in Table 1-1 Emulsion 1-12 Milk thiosulfonic acid compound (!I11.7xlO-''mol/d) 0 tricresyl phosphate (1. 10 g'/rrf) 0 gelatin (2. 30 g/rrr) (2)
Protective layer 02, 4-dichlorotriazine-6-hydroxy-s-
Triazine sodium salt (0.08g/r/) O gelatin (1.80g/i) 0 coupler (1.5xlO-3 mol/n?) Table 1
-3 Sample inhibition Emulsion used 2m-1 2m-2 2m-4 Reduction sensitizer Thiourea dioxide L-7 Scorbic acid thiosulfonic acid compound equilibrium Ag 6゜7゜9゜10゜11゜6゜7゜9゜10 Table 1-3 Continued Sample magnet Emulsion used Reduction sensitizer Thiosulfinic acid compound Em-7 Thiourea dioxide equilibrium Ag 6.

7.

9.

10.

II.

6.

7.

9.

10.

11.

6.

7.

9.

10.

11.

6.

7.

9.

10.

11.

Table 1-3 continued Sample seed Emulsion used Reduction sensitizer 2m-9 2m-10 2m-11 2m-12 thios road 7 Compound equilibrium Ag 6.

7.

9.

1 0.

11.

6.

7.

9.

10.

11.

6.

7.

9.

10.

11.

6.

7.

9.

10.

11.

The concentration of the treated sample was measured using a green filter.

The results of the photographic performance obtained are shown in Table 1-4.

Processing method Step Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38"C 45d lOL
Bleach 1 minute 00 seconds 38℃ 20d4
L bleach fixing 3 minutes 15 seconds 38°C 30d8L water washing (11 40 seconds 35”C
(4 L countercurrent piping system from 21 to (1).

Washing (2) 1 minute 00 seconds 35°C 30d4L Stable 40 seconds 38°C 20d4L Drying 1 minute 15 seconds 55°C Replenishment amount per 1m length in 35s Next, write down the composition of the treatment solution.

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriamine 1.0 1.1-1-Hydroxyethyl pentaacetate 3.0 3.2 Lyden-1.1-diphosphonic acid sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide
1.4 0.7 Potassium iodide
1. Add hydroxylamine 2.4 2.8 sulfate 4-(N-ethyl-4,55,5 N-β-hydroxyethylamino) 2-methylaniline sulfate water to 1. Office lady 1. OLp H
10,0510,10 (Bleach solution) Common to mother liquor and replenisher (unit: g) Ferric ethylenediaminetetraacetate 120.0 Ammonium dihydrate Ethylenediaminetetraacetic acid disodium 1O10 Lium Ammonium chloride bromide 100.0 Ammonium nitrate Bleach accelerator 10 .0 0.005 Mol ammonia water (27χ) 15.0
m Add water 1. OLpH
6.3 (Bleach-fix solution) Common to mother liquor and replenisher (unit: g) Ferric ethylenediaminetetraacetate 50.0 Ammonium dihydrate Ethylenediaminetetraacetic acid disodium 5.0 Lium salt Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution 240. 0 d (70%) Ammonia water (27χ) 6.0
dAdd water to 1.0 LpH
7,2 (Water wash) Mother liquor and replenisher common tap water was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400 manufactured by Rohm and Haas). Water was passed through the packed hotbed column to reduce the concentration of calcium and magnesium ions to 3/L or less, and then 20 g/L of sodium isocyanurate dichloride and 0.0 g/L of sodium sulfate were added. 15 g/l was added.

The pH of this solution was in the range of 6.5-7.5.

(Stabilizing solution) Common to mother solution and replenisher solution (unit: g) Formalin (
37%) 2.0 m polyoxyethylene-p-mo 0.3 tunonylphenyl ether (average degree of polymerization 10) ethylenediaminetetraacetic acid di-sulfur 0.05 Add thorium salt water 1. OLpH
s, o-s,.

pH6.3 Exposure was carried out by ordinary wedge exposure at 1/100 second.

The light source used was one whose color temperature was adjusted to 4800 @ using a filter, and blue light was extracted and used using a blue filter (Fuji Photo Film @ BPN42). Sensitivity was compared based on fog and optical density of 0.2.

The sensitivity of the sample after storage in the freezer and the fogging sensitivity of the sample after storage in the freezer are taken as the standard "0" and 45°C to 6
Fog (Δfog) and sensitivity (ΔS) after storage at 0% for 14 days are shown in Table 1-4.

Table 1-4 shows that samples with equilibrium pAgs other than 7 to 11 had a significant increase in fog or a decrease in sensitivity, and reduction sensitization was performed on samples with pAg other than 7 to 11.
It can be seen that samples falling between g7 and g11 have high sensitivity and small fluctuations in fog sensitivity.

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■Example-2 Among the samples prepared in Example 1, a sample with an equilibrium pAg of 9°0 was selected and tested under conditions B (25°C x 10%) and conditions B (25°C).
°C x 30%), C condition (25°C x 50%), D condition (25°C x 70%), E condition (25'CX 75%)
The humidity was adjusted in the dark for 3 days. After some samples were sampled for moisture content measurement and sealed in an aluminum can in a dark place, 1) 4
Samples kept at a temperature of 5°C for 14 days and samples kept at a temperature of 5°C for 14 days were subjected to imagewise exposure for sensitometry in the same manner as in Example 1, and then subjected to development processing and density measurement. went.

The results obtained are shown in Table 2-1.

From Table 2-1, reduction sensitization was applied and the water content was 1 to 6%.
It can be seen that the sample has high sensitivity and has small fog and sensitivity fluctuations.

Example 3 Emulsions 1-12 prepared in Example 1 were optimized for each emulsion using sodium thiosulfate and chloroauric acid. A sulfur-sensitized emulsion was prepared.

Then, in the same manner as in Example 1, the emulsion and protective layer were coated on a triacetyl cellulose film support provided with an undercoat layer in the coating amounts shown in Table 1-2. At this time, varying amounts of dilute hydrochloric acid were added to the protective layer to prepare coated samples having the composition and equilibrium pH shown in Table 3-1.

Among these samples, one was stored in a -80°C CIO% freezer and the other was stored in a 45°C 60% environment for 14 days, and then exposed, developed, processed, and processed in the same manner as in Example-1. Concentration measurements were taken.

The results are shown in Table 3-2. From Table 3-2, reduction sensitization was performed,
In addition, it can be seen that samples with an equilibrium pH of 7 or less have high sensitivity and small fluctuations in capri and anger.

Iris Example 4 On a subbed cellulose triacetate film support,
Sample 401, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is g/g for silver halide and colloidal silver.
Amounts of silver expressed in rd units, coupler additives and gelatin in g/m, and sensitizing dyes expressed in moles per mole of silver halide in the same layer. .

1st layer: Halley silane prevention layer black colloidal silver Silver coating amount 0°2 Gelatin 2.2 UV-10,l UV-20,2 Cpd-10,04 Cpd-20,02 Solv-10,30 Solv-20,01 2nd layer: Intermediate layer fine grain silver iodobromide (Agl 1.0 mol%, equivalent sphere diameter 0
゜07μm) Silver coating amount 0.15 Gelatin 1. 0ExC-
40,03 Cpd-30,2 31L First red-sensitive emulsion layer Silver iodobromide emulsion (Ag 15.0 mol%, surface height Agl type, equivalent sphere diameter 0°9 pm, coefficient of variation of equivalent sphere diameter 21%, flat plate grains, diameter/thickness ratio 7°5) Silver coating amount 0.42 Silver iodobromide emulsion (Ag 14.0 mol%, internal high AgI type, equivalent sphere diameter 0°4 μm, coefficient of variation of equivalent sphere diameter 18%, Dodecahedral particles) Silver-shaped cloth It 0.40 Gelatin 1. OE x
S -14,5X10-'mol Ex S -21,
5X10-'mol ExC-30,4xlO-'mol ExC-10,50 ExC-20,11 ExC-30,009 ExC-40,023 Solv-10,24 4th layer: 2nd red-glare emulsion layer Silver bromide emulsion (Ag 18.5 mol%, internal high Agl type, equivalent sphere diameter l.

0 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter/thickness ratio 3°0) Silver coating amount 0.85 Gelatin
0. 7ExS-13X10
-'MoleExS-21xlO-'MoleExS-30,3X10-'MoleExC-10,
10 ExC-20,05 ExC-40,025 Solv-10,10 5th layer: Third red-sensitive emulsion layer Em-1 described in Example-1 Coefficient of variation of equivalent sphere diameter 28%, plate-like grain, diameter /thickness ratio 6.0) Silver coating amount 1,50 0,6 2X10-' mole 0.6 X 10-' mole 0.2 Gelatin xS-1 xS-2 xS-3 ExC-2 ExC-4 ExC-5 Solv-1 Solv-2 6th layer: Intermediate layer gelatin Cpd-4 Solv-1 7th layer: 1st green emulsion layer Odor Silveride emulsion (Agl 5°0 mol 1.00, 10, 1%, surface height Agl type, equivalent sphere diameter 0°9 μm, coefficient of variation of equivalent sphere diameter 21%, tabular grains, diameter/thickness ratio 7゜0) Silver coating amount 0.28 silver iodobromide emulsion (Ag + 4.0 mol%, internal high Agl type, equivalent sphere diameter 0゜4 μm, coefficient of variation of equivalent sphere diameter 18%, dodecahedral grains) Silver coating Amount 0.16 Gelatin 1.2ExS-5
5XIO-'mol ExS-62X10-'mol ExS-71 Silver bromide emulsion (Ag 18.5 mol%, internally high iodine type, equivalent sphere diameter 1°0 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 3.0) Silver coating amount 0, 57 Gelatin 0.35E x S
-53,5XIO-'mol Ex S -61,4X10-'mol Ex S-
70,7X10-'mol ExM-10,12 ExM-20,01 ExM-30,03 Solv-10,15 Solv-40,03 9th layer: Intermediate layer gelatin 0. 5Solv
-10,02 10th layer: 3rd green-sensitive emulsion layer example-] Silver coating N1.3 Gelatin 0.8xS-5 xS-6 xS-7 ExM-4 xC-4 ExM-6 Cpd- 5 Solv-1 11th layer: Yellow filter layer Cpd-60,05 Gelatin 0.5Solv-
10,1 12th layer: Intermediate layer gelatin 0.5Cpd-3
0,1 13th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion (Ag 12 mol%, uniformly iodine type, equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 25%, tabular grains, diameter/ Thickness ratio 7.0) 2X10-'mol 0.8X10-'mol 0.8X10-'mol 0,04 0.005 0,01 0,01 0.2 Silver coating amount 0. 2 Gelatin 1.0ExS-8
3X10-'mol ExY-10,6 ExY-20,02 Solv-10,15 14th: Second blue-sensitive emulsion layer silver iodobromide hole M (Agf 19.0 mol%, internal height Ag
L-shaped, equivalent sphere diameter 1°0 μm, coefficient of variation of equivalent sphere diameter 16%, octahedral particles) Silver coating amount 0.19 Gelatin 0.3E x S
-82xlO-'mol ExY-10,22 Solv-10,07 15th layer: Intermediate layer fine grain iodobromide ll (Ag1 2 mol%, uniform iodo type,
Equivalent sphere diameter 0.13 μm) Silver coating amount 0.2 Gelatin 16th layer: Third blue emulsion layer Em-1 described in Example-1 Silver coating amount Gelatin xS-9 xY-1 olv-1 17th Layer: 1st protective layer gelatin V-1 V-2 olv-1 olv-2 18th layer: 2nd protective layer fine particle chloride l! (Equivalent sphere diameter 0 μm) Silver coating amount Gelatin polymethyl methacrylate particles (diameter 1.5 μm) 0, 36 1, 55 0.5 1.5X10-' mole 0.2 0, 07 0, 36 0.7 0. 2 W-10,02 H-10,4 Cpd-71,0 In addition to the above, each layer contains B-1 (total 0.20 g/po), 1
．． 2-benzisothiazolin-3-one (about 200 ppm on average based on gelatin), n-butyl p-hydroxybenzoate (about 1.000 ppm), and 2-phenoxyethanol (about 10,000 ppm on average) were added.

Next, samples 402 to 405 were prepared by adding a certain amount of a 1% silver nitrate solution or a sodium bromide solution to the 17th layer of sample 401 to change the equilibrium pAg value.

Furthermore, Em-1 of the 5th layer, 10th layer, and 16th layer was added to Example 1.
Change to Em2.3, 4, 7.10 created in
Samples 406 to 430 with different Ag values were created. The contents are shown in Table 4-1.

One of these samples 401 to 430 was placed in an 8°C 10% freezer, and the other was placed in a 45°C 60% environment.
4800° Kl/100 seconds I CMS after storage for 4 days
Exposure for sensitometry was given under the conditions of Example 1.
The same development process was performed. However, the time for color development was 3 minutes and 15 seconds.

Capri of the sample after storage in the freezer, sensitivity is the standard "Fog after storage for 14 days at 45°C - 60% as OJ (
Δfog) and sensitivity (ΔS) are shown in Table 1-4.

Table 1-4 shows that samples with ipAg other than 7 to 11 had a significant increase in fog or a decrease in sensitivity, and reduction sensitization was applied to the samples.
It can be seen that samples with Ag between 7 and 11 have high sensitivity and small variations in capri and sensitivity.

Table 4 2m-1 2m-2 2m-3 2m-4 6゜7゜9゜10゜11゜6゜7゜9゜10゜11゜6゜7゜9゜10゜11゜6゜7゜Table 4 -1 Continuation m 9゜10゜11゜m-7 Thiourea dioxide 6゜7゜9゜10゜11゜m L-7 Scorbic acid 6゜7゜9゜10゜1゜Fake Chikari 38 '8 8 Kei 8 c; ci c; ci c; ci
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Example 5 Among the samples prepared in Example 4, a sample with an equilibrium pAg of 9°0 was selected and subjected to conditions A (25°C
C x 30%), C condition (25°C x 50%), D condition (2
5°C x 70%) and E conditions (25 x 75%) for 3 days in the dark. After some samples were sampled for moisture content measurement, they were sealed in aluminum cans in a dark place, and 1) samples were placed at a temperature of 45°C for 14 days, and 1) samples were placed at a temperature of 5°C for 14 days. Imagewise exposure for sensitometry was applied in the same manner as in Example 1, and development processing and density measurement were performed.

The results obtained are shown in Table 5-1.

From Table 5-1, reduction sensitization was applied and the water content was 1 to 6%.
It can be seen that the sample has high sensitivity and small fluctuations in capri and sensitivity.

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l F-OH61@Example 6 For sample 401, caustic soda 1 was added to the 6th layer and the 17th layer.
Samples 432 to 434 were prepared by adding a certain amount of % solution or diluted hydrochloric acid to change the equilibrium pH value.

Furthermore, Em-1 of the 5th layer, 10th layer, and 16th layer was added to Example 1.
Change to Em2, 3.4.7.10 created in
Samples 435 to 448 with different H values were created. The contents are shown in Table 6-1.

Of these samples, one was stored in a -8°C CIO% freezer and the other was stored in a 45°C 60% environment for 14 days, and then exposed, developed, and processed in the same manner as in Example-4. Concentration measurements were taken.

The results are shown in Table 6-2.1 From Table 6-2, reduction sensitization was performed,
It can also be seen that samples with an equilibrium pH of 7 or less have high sensitivity and small fluctuations in fog.

Table 6-2 2m-I 2m-2 2m-3 2m-4 2m-7 2m-10 Thiourea Dioxide L-7 Scorpic Acid Thiourea Dioxide L-7 Scorbic Acid Table 6-1 2m-1 2m Thiourea Dioxide 2m L-7 Scorbic acid 2m 2m-7 Thiourea dioxide 2m-10 L-7 Scorbic acid 0.10 0.08 0.62 0.08 0.52 0.07 0.12 0.05 0.42 0.06 0.06 0.36 0.06 0.05 0.10 0.08 0.64 0.07 0.51 0.06 0.14 0.05 0.41 0.07 0.05 0.32 0. 06 0.05 0.09 0.60 0.06 0.49 0.07 0.13 0.06 0.40 0.06 0.06 0.35 0.06 0.05 Comparative example of the present invention Comparison of the present invention Example Comparative Example of the Invention UV-1 of the Invention: CHs v 2 : xC xC xM H3 0OCHs H xC H (n)C+tH*s xC-3 CH! xC-4 n+1 xM-2 Shil xM-3 xM xM pd-1 pd H xM xY-1 pd-2 pd-6 H Shi-1113 cp d-5 OH OH pd-7 Φ CaF+ vsOJHc)IzC)IzCHzOCHt
CHtN(CHs) 3CHz=CH5OxCHtCO
NH-CHtCHxI=CH5OzCl1gCONH-
CHxxS-1 xS-2 xS-3 olv olv-2 ol xS-5 xS-6 xS-7 xS

Claims (5)

[Claims] (1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one emulsion contained in the emulsion layer is subjected to reduction sensitization during the manufacturing process. and the equilibrium pAg is 7 to 11.
A silver halide photographic material characterized by: (2) In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one emulsion contained in the emulsion layer is subjected to reduction sensitization during the manufacturing process. 1. A silver halide photographic material characterized by having a water content of 1 to 6%. (3) In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one emulsion contained in the emulsion layer is subjected to reduction sensitization during the manufacturing process. 1. A silver halide photographic material having an equilibrium pH of 7 or less. (4) The silver halide photographic material according to any one of claims (1) to (3), wherein the reduction sensitization is performed using at least one kind of ascorbic acid or its derivatives. (5) Claims (1) to (4) characterized in that reduction sensitization has been performed in the presence of at least one compound represented by the general formula [I], [II] or [III]. ) The silver halide photographic material according to any one of the above. [I] R-SO_2S-M [II] R-SO_2S-R^1 [III] R-SO_2S-L_m-SSO_2-R^2
In the formula, R, R^1, and R^2 may be the same or different and represent an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. The compounds of general formulas [I] to [III] may be polymers containing divalent groups derived from the structures represented by [I] to [III] as repeating units.