JPS59212827A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain an image high in contrast and low in fog by adding a specified compd. and iodide to a silver chloride emulsion contg. a rhodium salt. CONSTITUTION:A water-soluble rhodium salt is added by using an inactive gelatin, etc. as a suspension medium in the process for forming silver halide grains contg. >=50mol% silver chloride, and a compd. represented by general formula I or II is added from the grain forming process to the chemical sensitizing process just before the start of sulfur sensitization, and a water-soluble iodide is added from the grain forming process to the end of the chemical sensitizing process. In formula I and II, Z1 is thiazole, selenazole, oxazole, or imidazole, each optionally having a condensed ring; Z2 is a nonmetallic atomic group necessary for completing a 5- or 6-membered hetero ring; X1, X2 are each O, S, Se, or N-RO; Y is O or S; R1, R2, R5, R6 are each lower alkyl, alkenyl, or aryl; R3 is H or same as R1; and (n) is 0 or 1.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide photographic material, more specifically, a silver halide photographic material capable of stably obtaining photographic images with high contrast and low capri. Regarding.

(Prior art) In general, silver halide photographic light-sensitive materials with high contrast are used for forming photographic images such as characters and halftone images in photolithography, and for forming fine line images in ultra-precision photolithography. is used. A silver halide photographic material used for such purposes is, for example, one that has an average grain size of 02μ, a narrow grain distribution, a uniform grain shape, and contains no chloride (φσ). ) is used, for example, a photosensitive material consisting of a silver chlorobromide emulsion having a content of at least 50 mol %, and this photosensitive material is processed with an alkaline hydroquinone developer having a low concentration of sulfite ions. A method of obtaining a 1i171 image with high contrast, high sharpness, and high resolving power, such as a halftone dot image or a fine line image, is being carried out in L. This type of photosensitive material is widely known as a squirrel type 6 material. In the above-mentioned true plate-making process, a continuous tone original is printed on a halftone dot image F9. r
J culm, 4 - corresponds to a 41 degree change in continuous gradation of the manuscript.
119- is included, which transforms it into a set of halftone dots with an area proportional to 119-. Such a conversion method involves photographing the original through an intersection screen or a direct screen using a type-sensitive yC material, and then processing a special phenomenon. A common method is to form a halftone image. The developer fψ used in the special development process of df1 above has been conventionally called a contagious developer or a lithium-type developer. Regarding this contagious developer or lithium-type developer, -r+t, 3i1J, G.N.C., ``Journal of the Franklin Institute,'' Vol. 239, 221.
(1945), ':L! , qualitatively refers to a developer that uses hydroquinone as a developing agent and has a low sulfite ion concentration.

In the normal ゛q true plate making process, a large amount of developer is required to carry out continuous photolithography processing using an automatic developing machine using the above-mentioned Lith developer. Therefore, a control method for keeping the quality of the developer constant during continuous processing has become extremely important, and a great deal of effort has been made to develop this control method.

One such method of improvement is that, depending on the rate at which the developer activity has changed during the development process and the rate at which it has been fatigued due to oxidation, the original activity can be restored to The method of correcting the condition by using the necessary replenishment fluid to revive the condition has not been widely adopted.

[7 However, the above method controls the replenishment air of the developer, and the developing device and place 331! It has the disadvantage that the operation is complicated.

On the other hand, it is possible to produce high-contrast images by using a special lithium developer (I-size is processed with a non-lithium developer with a high sulfite ion concentration, so-called phenidone, hydroquinone type developer, or methol-hydroquinone type developer). A method for obtaining 1 gA is also known 2). That is, a silver halide photograph 11t exposed by a 11'r three-point generator which is a device a that forms a halftone image using a laser yC having a coherent output wavelength. A method is also known in which a high-contrast image is obtained by processing the C-containing material with a non-lithographic developer.

F) As is clear from the above, there are two known methods for obtaining high-contrast images: processing with a lithium developer and processing with a non-lithium developer.
In recent years, there has been a demand for silver halide photographic materials that can provide high contrast images regardless of which developer is used.

In order to achieve this, there is a method of adding a polyalkylene oxide compound to an emulsion with a high silver chloride content, but on the other hand, silver halide photographic light-sensitive materials containing the above compound was unsatisfactory because it had the drawbacks that non-Lith type developers had the disadvantages of reduced contrast and increased fog.

In order to eliminate this drawback, it is known to use, for example, cadmium salts as tone control agents.

However, silver halide photographic materials containing cadmium salts leak out during processes such as development, fixing, and washing, causing environmental pollution and adversely affecting the human body.
Although characteristics with high contrast and little fogging can be obtained, this is not preferable in reality.

Furthermore, for example, the use of rhodium salts is described in U.S. Pat. If a separate sensitization method is used to increase the image quality, fog will increase [7] and a satisfactory result will not be obtained. Furthermore, it has the drawback of not being stable and causing softening during storage. Furthermore, JP-A-54-103.01.8 discloses a method for improving the storage stability by using a hydroxyazaindolizine compound at 911 physical heat 1+'yJ, but it is unsatisfactory. It was something.

(Object of the Invention) The object of the present invention is to provide a silver halide photographic material with high contrast and no fog (tl), and furthermore, it can be processed with a lithium type developer or a non-lithium type developer. It is an object of the present invention to provide a silver halide photographic page-sensitive material (;) which can provide images with high contrast and less fog even when the image is used.

(Structure of the Invention) The halide photosensitive yC material of the present invention forms halocopper chloride grains having a silver chloride content of 50 mol% or more using inert gelatin, an inert gelatin derivative, or a mixture thereof as a suspending medium. step, and sulfur sensitization is applied to the halochloride ε14.
(ii) In the emulsion process time series including the chemical sensitization process including
(b) Adding at least one compound represented by the following general formula [I] or group] during the period from the particle formation step to before the start of sulfur sensitization in the chemical sensitization step, (c) Particle formation The scraps of the silver halide emulsion obtained by the manufacturing method including the emulsion step according to the present invention, which is characterized in that each step of adding water-bath iodide is performed between the steps and the end of the chemical sensitization step, is used as a support. It is obtained by using the silver halide photographic light-sensitive material shown above.

The grain formation process is a process for adjusting the composition, grain morphology, grain distribution, etc. of silver halide grains in accordance with photographic purposes, and
``By mixing a soluble silver salt and a halide in a solution system, rapid precipitation occurs until the bath solubility product of silver halide in the solution system is satisfied, grain growth ends, and precipitation equilibrium is reached. After the precipitation equilibrium, so-called A-stored ripening occurs in which small particles dissolve and large particles grow due to the solubility pressure difference depending on the size of the particles.

Precipitate formation and analysis according to the present invention
It refers to the light 1t11 until reaching the precipitation equilibrium that satisfies the product,
Generally considered within a few minutes.

In the general formula [I] 3, Z and G can each be substituted with 1. Kukehi [tt-converted thiazole nucleus, selenazole nucleus, oxazole nucleus, imidazole nucleus, benzthiazole nucleus, benzselenazole nucleus, benzoxazole nucleus, benzimidazole nucleus, naphthothiazole cedar, naphthoselenazole nucleus, naphthoxazole nucleus Mari Gl 7) Represents a group of nonmetallic atoms required to complete the imidazole nucleus, and substituents include, for example, alkyl groups (e.g., methyl group, ethyl group, etc.), halogen atoms (
Examples include chlorine atom, bromine atom, etc., alkoxy groups (e.g., methoxy group, ethoxy group, etc.), aryl groups (e.g., phenyl group, tolyl group, hydroxyphenyl group, etc.), carbonyl group (e.g., phenylcarbonyl group, etc.). be able to. In addition, X is an oxygen atom, a sulfur atom, a selenium atom, or an N-R4 group [R4 is a substituted or unsubstituted lower alkyl group (e.g., methyl group, ethyl group, propyl group, hydroxyethyl group, carboxyethyl group, etc.), alkenyl (e.g., allyl group N?) or aryl group (e.g., phenyl group, hydroxyphenyl group, tolyl group, etc.)], and R and R each represent a substituted or unsubstituted lower alkyl group (e.g., methyl group, ethyl group, etc.). ,
butyl group, benzyl group, hydroxyethyl group, carboxypropyl group, lower alkyl group with one sulfonic acid, etc.)
, an alkenyl group (e.g. allyl group, etc.), or an aryl group (e.g. phenyl group, tolyl group, hydroxyphenyl group, carboxyphenyl M, etc.), and R3 is a hydrogen atom or a substituted or substituted device (7'). 7
/L represents a kill group (for example, a methyl group, an ethyl group, a hydroxyethyl group, etc.), an alkenyl group (for example, an allyl group, etc.), or an aryl group (an example is a phenyl group, etc.).

General formula [■] 6 In formula 2. represents a group of nonmetallic atoms required to complete a substituted or unsubstituted 5-membered or G16-membered heterocyclic nucleus, examples of which include pyridyl, quinolyl, thiazole, selenazole, oxazole, imidazole, etc. .

X again! is an oxygen atom, sulfur atom, selenium atom or N-
R represents a group (R? represents a substituted or unsubstituted lower alkyl group, alkenyl group, or aryl group; these specific examples are the same as R4), and Y represents an oxygen atom or a sulfur atom. ), R6 and R6 each represent a substituted or unsubstituted lower alkyl group, alkenyl group or aryl group, specific examples of R3 are the same as R, and specific examples of R6 are the same as R3. be.

Further, n represents 0 or 1.

The present invention will be explained in more detail below.

The inert gelatin of the present invention has a low content of inhibitory substances and reducing substances in gelatin, and only needs to be essentially inactive.Generally, the raw material for making gelatin is skin or bone, and hydroceratin and oscelatin are used. It is called ingelatin, and it is also called acid-treated gelatin or alkali-treated gelatin when it is treated with acid or alkali during the manufacturing process. Contains many substances and reducing substances.

The inert gelatin used in the present invention can be treated with an acid or an alkali, and if necessary, treated in an oxidizing environment such as hydrogen peroxide treatment, and the treated gelatin can be purified using activated carbon or an ion exchange resin. It is something. In other words, the inert gelatin used in the present invention is gelatin] g
It is gelatin that has been processed and purified so that it contains less than 10 μg per gelatin.
? At the same time, the reducing substances in the gelatin that have been treated are reduced and become photographically inactive.

The d-derivative of inert gelatin used in the present invention, the gelatin is converted into phenylcarbamylation, acylation, phthalation, or the polymerizable monomer having an ethylene group such as methacrylic acid, methacrylic acid ester, or acrylic acid ester is converted into gelatin. This includes graft combinations. As will be described later, the derivative gelatin can be used not only in the particle forming step of the present invention, but also as a hydrophilic colloid in the chemical sensitization step and for preparing a coating solution.

The amount of nucleobases in the inert gelatin or its dα conductor used in the present invention is as described above! If the content is more than 7t, the object of the present invention cannot be achieved.

The water-soluble rhodium salt used in the present invention includes all conventionally known rhodium salts, but typically rhodium chloride, rhodium trichloride, rhodium ammonium chloride, etc. can be used.

Rhodium h;11 is present during the particle formation step,
In particular, it is desirable to have it present during precipitation formation and growth of gold halide 14, but the present invention also includes its presence during growth due to Ostwald ripening caused by the difference in solubility pressure between large and small silver halide grains.

Usually, it is preferable to add it in a halide solution for producing silver halide, but other methods can be selected as appropriate depending on the method of mixing silver halide. For example, a method of pre-existing an inert gelatin (or its derivative) containing a halide in an aqueous solution as a forward mixing method, a method of pre-existing an inert gelatin (or a derivative thereof) in an aqueous solution containing a halide in a simultaneous mixing method, Alternatively, when the halide is added in several parts, it may be added by containing it in any divided solution. The amount of rhodium salt used can be adjusted to the desired contrast, capri, sensitivity, etc.

The compounds represented by the general formula [I] or [II] used in the present invention include methanol, ethanol, fluorinated alcohol, methyl cellosolve, acetone, acetic acid, sodium acetate, citric acid, sodium citrate, ethylene glycol, and triethanol. FS 7JII can be prepared by dissolving it in a solvent such as amine or water, or dispersing it in gelatin or a high molecular weight polymer. The addition amount varies depending on the sensitivity to which the 6-halide I:i emulsion of the present invention is applied, but is usually in the range of 5 x 10 to 5 x 10 mol per mol of silver halide. used in

The timing of adding the above compound is determined from 1υJ when silver halide completes precipitation and growth in the grain formation process and begins growth due to Ostwald ripening caused by the difference in solubility pressure caused by the size of the grains. This is a chemical sensitization step jjJ up to the time when a sulfur sensitizer is added as a chemical sensitizer in the sensitization step, but preferably this is the chemical sensitization step stage. If it is necessary to replenish the amount added, it may be added during the emulsion preparation process.

Further, two or more of these compounds may be used in combination, or they may be added in large numbers in several batches as a single solution or as a mixed solution in the above process range.

The general formula [I] or [II] included in the present invention is shown below.
] Specific examples of compounds represented by σ) are given below, but are not limited to these.

00H, 0nOH O0H7OH,OH knee. 4 H 00H20H2CIICH.

S　Og　K O(OH, HaOH1 0 0, H.

0 0 H20H2CHs ■ -11 0011, -C11==, (!)+2 0 021-15 i -14 I 17 a,
n.

So, Na O, H town 1 O)1. OH, OH ) -230H.

OH20T (20HH 3Og N a OH, 0H20H OOH, OH, OH 00H, -0H=OH.

I-4 I 1 0 C) i2C! H,OH 00H,000H OC! ,H.

0 0H, -0H=OH.

0　0,I(.

As water-soluble iodides used in the present invention, alkali metal salts such as IJium, potassium iodide, etc. Examples include alkaline earth metal salts such as magnesium chloride, calcium iodide, and ammonium iodide. These compounds are preferably added in the form of an aqueous solution in the iH sensitization step after grain formation IIJ has entered Ostwald ripening, but they may be added particularly in the chemical sensitization step before the addition of a chemical sensitizer. preferable. Further, it may be added before or after the compound represented by the general formula [IT or [II], as long as it is in the chemical sensitization process stage.

Silver halide 1 as a water-soluble iodide compound used in the present invention
The amount is 10 to 10 moles per mole, preferably 10 to 10 moles, and if it is more or less than this, it is difficult to obtain the effects of the present invention.

Various sulfur-containing compounds can be used as the sulfur-sensitizing compound used in the present invention. For example, thio (sodium chloride, ruthiocarbamide, thiourea,
Allyl isothiacyanate, etc. Furthermore, US Patent No. 1.5'
74,944 inches, 2.2' / No. 8,947, 2
, 410゜689, same: 3,189.458, same 3
, 501, 313, etc., are used. The present invention includes sodium thiosulfate '&;'
1 of the above sulfur & compounds per mole of silver halide
A range of 0 to 10 moles, preferably 10 to 10 moles, is useful.

The sulfur sensitization according to the present invention may be used in combination with gold sensitization, sensitization with gold sensitization, or selenium sensitization. Compounds such as chloroauric acid, potassium chloromerite, potassium chloroaurate σ1, alkali metal salts such as chloroauric acid σ1,
Potassium aurithiocyanate, 2-oresulfobenzothiazole methyl chloride, etc. have U.S. patents 2 and 5.
97. R,”= (54th, No. 2,507,915,
The gold compound described in No. 2,399,083 may also be used.

As the gold compound used in the present invention, a range of 10 to 10 moles per 51 moles of halogenated C] is preferable, and < is preferably in the range of 10 to 10 moles. The use of alkali metal salts can bring about significant effects of the present invention.

Examples of the silver halide used in the silver halide emulsion layer constituting the silver halide photographic material of the present invention include silver chlorobromide, silver chloroiodide, silver chloroiodobromide, gold chloride, etc. Included are those used in conventional silver halochloride photographic emulsions.

In particular, when used as a sensitive material for scanners and photosensitive materials for radiography that are exposed using a halftone dot generator using an argon laser or helium neon laser as a light source, the silver halide composition is a salt with a high silver chloride content. A silver bromide emulsion (having at least a silver chloride content of 50 mol % or more) is suitable.

These silver halides may be coarse-grained or fine-grained and can be prepared by any known method, such as U.S. Pat.
No. 92,250, No. 3,276.8 '77, No. 3.
317, r522, 2,222,264, 3,
No. 320,069, 3. zo6,313 or [
Journal of Photographic Science (
J, Phot, SQi) J Volume 12, No. 5 (
It can be prepared by the method described in (September, October issue), 1964, pages 242-2.51.

Furthermore, silver halide prepared by different methods can be used after being moistened.

In the present invention, the silver halide contained in the silver halide emulsion layer has an average grain size of 0.05 to 1.5 microns, preferably 0.1 to 0.5 microns, although it is not limited to this.
5 microns and 14) at least 75% of the total number of particles
halogenated particles having a particle size of preferably 80% or more or 0.5 to 1.5 times the average particle size, preferably 06 to 14 ia 1i. 9J preferably includes IJ.

According to a most preferred embodiment of the present invention, the silver halide used in the present invention has an average grain size of 01-0 to 0;3μ, and 80% or more of all grains have an average grain size of 0. It is silver chlorobromide or silver chloride having a grain size of .6 to 14 times.

In addition to the rhodium of the present invention, atoms of iridium, A-sumilum, bismuth, cobalt, nickel, palladium, ruthenium, iron, copper, zinc, lead, cadmium, etc. may be contained in these silver halide crystal grains. It is preferable that these atoms be contained in equal moles.

In addition, it may be surface latent (elephant Qtj) or internal latent image type. Silver halides prepared by various different methods may be mixed. Crystal habits include cubic, octahedral, and 14
There are no restrictions on the shape, whether it is a face piece or a sphere.

In the present invention, the above-mentioned inert gelatin, a derivative thereof, or a mixture thereof is specified as the hydrophilic colloid in the suspending medium during the particle formation step, but in other steps, the above-mentioned suspension may be used. Other hydrophilic colloids can be used in desorbing and displacing the suspension medium from the silver halide or in supplementing the suspension medium. Alternatively, hydrophilic colloids other than inert gelatin or derivatives thereof may also be used in photographic functional layers other than the emulsion layer (for example, an image preservation layer, an intermediate layer, an antihalation layer, etc.).

Examples of the hydrophilic colloid include general photographic gelatin or hydrophilic colloids other than gelatin, such as colloidal albumin, agar, acacia, alkinoic acid, hydrolyzed cellulose acetate, acrylamide, imidized polyimide, Examples include polyvinyl alcohol, hydrolyzed polyvinyl acetate, and gelatin derivatives.

As the gelatin derivative, for example, US Pat. No. 2,614
, 928 So, 2,525. '753, etc. 2. [1] Fuconinyl gelatin, acylated gelatin, phthalated gelatin, or
．． F1a B, 521)-υ゛, 2.831. '76
Polymerizable monomers having an ethylene group, such as styrene, acrylic ester, MEC 1-noric acid, and methacrylic ester, as described in No. 7), are grafted onto gelatin. Examples include those that match.

The photosensitive material according to the present invention has at least one layer of halogenated f! Although the hydrophilic colloid layer including the 14 emulsion layer is not included, a protective layer having an appropriate film thickness on the layer height 1, that is, preferably O'~10μ,
It is particularly preferable that a ceratin protective layer (0.8 to 2 μσ) is coated.

The hydrophilic colloid CJ-Ct used in the present invention, if necessary, each fI! X photographic additives, e.g. 11 Seratin self 1 plasticizer, hardener, surfactant, image discount, ultraviolet "p"
11M agent, anti-stain agent, pH adjuster, antioxidant 1L
Agents, antistatic agents, thickeners, graininess improvers, dyes, mondants, brighteners, development speed regulators, matting agents, etc. can be used within the range that does not impair the effects of the present invention.

Among the above-mentioned various additives, those which can be particularly preferably used in the present invention as thickeners or plasticizers include, for example, U.S. Pat. , No. 904, 604, JP-A-4B
-63715, Japanese Patent Publication No. 45-15462, Belgian Patent No. '762,833, US Patent No. 3.7 fi'
il, No. 410, Perky National Patent No. 558,143, such as styrene-sodium maleate copolymer, textan sulfate, etc. Hardening agents include aldehyde, epoxy, and ethylene. imine type, active halogen type, vinyl sulfone type, incyanate type,
18 each for sulfonic acid esters, carbodiimides, mucochloric acid, acyloyl, etc.! Film agents and ultraviolet absorbers include, for example, compounds described in U.S. Patent No. 3,253.921, British Patent No. 1,309,349, etc.
In particular, 2-(2'-hydroxy-5-tertiary butylphenylnopenzotriolizole, 2-(21-hydroxy-31
, 51-G3 (Sibyl phenylnopenzotriazole, 2-(2-hydro)
(2'-Hydroxy-3', 5'-di-tertiary butylphenyl)-5-chlorobenzotriazole, etc., and as the dye, U.S. Pat.
Compounds described in '7 2.9' (No. 18, German Patent No. 10,990, U.S. Patent No. 3,048,48'7, U.S. Patent No. 515,998, etc.) using I
14, and these compounds may be contained in a protective layer or a G intermediate layer. Furthermore, improvements in permeability to coating aids, emulsifiers, processing liquids, etc., and antifoaming agents. 1
Surfactants used to control various physical properties of photosensitive dyes include:
United Kingdom 1'] No. 54B, 532, 1. ,216,3
B No. 9, U.S. 1 revision 3,0 26, 202, same 3,
51 4, 2 9 3, Special Publication No. 4.4-26580, No. 43-17922, No. 43-17926, No. 4
3-13166 inches, 4 8-2 0 7 8 5, French FI Q'! White t'r 2 o 2.

Can anionic, cationic, nonionic or amphoteric compounds described in Patent No. 588, Perky National Patent No. 7'73,459, No. 17j 1987-101118, etc., be used? Among these, anionic surfactants containing sulfone groups, such as succinic acid ester sulfonates, alkylnaphthalene sulfonates, alkylbenzene sulfonates, and the like are particularly preferred. ′
-J: As an anti-static agent,
59, JP 48-89979, U.S. Patent No. 2,88
No. 2,157, No. 2,972,535, Japanese Unexamined Patent Publication No. 1972-
20785 Kano, 48-4:3130, 4B-90
No. 391, Special Publication No. 46-24], No. 59, No. 46-39
No. 312, No. 48-43809, JP-A-4'7-33
627, etc., and as a matting agent, for example, British 1st ``Patent No. 1,221,980''
No. 2,992.101, U.S. Patent No. 2,992.101, U.S. Pat.
No. 884-, French Patent No. 1,395. ．． Compounds described in No. 544, Tokko Sho+, No. 8-43125, etc., especially silica gel with a particle size of 05 to 20 μ, 0.5 to 20 μ
Examples include polymers of polymethyl methacrylate having a particle size of . Examples of the support used in the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, such as polyethylene terephthalate (17-)
Waiting c71 polyester film, polyamide film,
polypropylene film, polycarbonate film,
Typical examples include polystyrene film and the like, and these supports can be used as appropriate depending on the purpose of use of the silver halide photographic light-sensitive phase material.

IJ≠, 1・K used for developing the sensitive C material of the present invention
! Examples of the developer that can be contained in the liquid include the following.

Typical examples of HO-(OH,=CH-〇H) developing agents include catechol, e''') JD-Ru6 and its derivatives, such as ascorbic acid, hydroquinone, chlorohydroquinone, Bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2
, 5-dimethylhydroquinone, 2,3-dibromohydroquinone, 2,5-sibidroxyacetophenone,
2,5-diethylhydroquinone, 2,5-cyp-
7-enethylhydroquinone, 2,5-dibenzoyl-minohydroquinone, catechol, 4-chlorocatechol, 3-phenylcatechol, 4-phenyl-catechol, 3-methoxy-catechol, 4-acetyl-pyrogallol, 4-(2'- Hydroxybenzoyl nobirogallol, sodium ascorbic acid, etc.

HO-(C1, (=OH)□-NH, type developer,
Typical examples include ortho and para aminophenols or aminovirazone, 4-aminophenol, 2-amino-6-phenylenephenol, 2-amino-4-chloro-6-phenyl Phenol, 4-ami/-2-phenylphenol, 3,4-diaminophenol, 3-methyl-4,6-diaminophenol, z,
4-Diaryomylsorcinol, 2.4.6-)riaminophenol, N-methyl-p-amino/7-ethyl, N-β
-Hydroxyethyl-p-aminophenol, p-hydroxyphenylaminoacetic acid, 2-aminonaphthol, etc.

As a H,N-(0H=OH,lI,-NH, type developer, for example, 4-reminnow 2-methyl-N,N-di:■-
thylaniline, 2.4-diamino-N, N-diethylaniline, N-(4-amino-3-methylphenyllamorpoline, p-phenylenediamine, 4-amino-N,
N-dimethyl-3-hydrolyniline, NNN'N'
Tetramethylparaphenylenediamine, 4-amino-N
-ethyl-N-(β-hydroxyethylaniline, 4-amino-N-ethyl-
(β-methoxyethyl)-3-methyl-aniline, 4-
Amino-3-methyl-N-ethyl-N-(β=methylsulfonamidoethyl)-aniline, 4-methyl/-N-butyl-N-7-sulfophthyl-aniline, 1-(4-aminophenyl)-pyrrolidine , 6-7 minnow 1-ethyl,
1, 2,3.4-tetrahydroquinoline, 9-aminoylolidine, etc.

Examples of heterogeneous developers include 1-phenyl-3-
Pyrazolidone, 1-phenyl-4-amino-5-pyrazolone, 1-(p-aminophenynoly-3-amino-2-
Pyrazoline, 1-phenyl-3-methyl-4-minor 5-pyrazolone, 5-minouracil, 5-amino-2
, 4,6-)lihydroxyphyrimidene, etc.

Others: The Theory of James, T.H.
The Photographic Process 4th Edition (The T
hoory of the Photographic
Process.

F'ourth Editi, on) No. 291-334
Pages and Journal of the American Chemical Society
Developers such as those described in Ericsson Chemical Society, Volume 73, Page 3100 (1951) can be advantageously used in the present invention.

These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. Furthermore, even if sulfites such as sodium sulfate, potassium sulfite, ammonium sulfite, etc. are used as a preservative in the present p-solution used in the present invention, the effects of the present invention will not be diminished. This can be mentioned as one of the features of the present invention.Hydroxylamine and hydrazide compounds may also be used as a protective layer.Other general black and white +1.1. f?;
・Adjustment of pH using caustic alkali, alkali carbonate, or amines used in Floodwater and buffing, and suppression of angular development such as Bromkali and organic development such as Benzol, IJ, etc. Metal ion scavengers such as ethylenediaminetetraacetic acid, methanol, ethanol, benzyl alcohol, development accelerators obtained from polyalkylene oxide, sodium alkylarylsulfonate, natural bonins, sugars or alkyl esters of the above compounds, etc. It is optional to add surfactants such as glutaroldehyde, hardening agents such as formalin and glyoxal, and ion 41 degree adjusting agents such as sodium sulfate.

The photosensitive material according to the present invention can be processed under various conditions of 4''n.The processing temperature is preferably, for example, development f! It is common to complete the process within 3 minutes, but it is particularly preferable to complete the process within 2 minutes, which often brings about good results.In addition, processing steps other than development, such as washing with water, stopping + I.
-, It is optional to adopt steps such as stabilization, fixation, and if necessary, preduration and neutralization, and these steps can be omitted as appropriate. Furthermore, these processes include so-called manual development processes such as plate development and frame development, roller development,
It may be a hanger development or a mechanical U-image.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples. The technical scope of the present invention is not limited to the same extent by the following Examples, but can be applied to a wide variety of practical applications.
is useful.

Example Four types of emulsions, Ea and Eb, were prepared before the light-sensitive material.

] 1C and 1k were prepared.

Preparation of Emulsion Ka (Particle Formation) Ossein gelatin (containing adenine, 500 gl per gram gelatin) was prepared by the lime method using cow bones.
μj? ) 160 g dissolved in 3.5 d of pure water, sodium chloride 3 (log, potassium chloride 83 g and potassium hexachlororhodate 12 hydrate 100 g) were dissolved in 3.5 d of pure water.
Haloid liquid containing μy in 4.71% pure water and 6% FF b) @II 1 kg dissolved in 4.71% pure water FF
'i: Using the same n,'r mixing method, keeping the saccharine and the pen f at 60℃ for 5 minutes.
'4A, t, 4. with an average particle size of 0.2511. Silver 7L
ffi'1 (AgQ/, 70 mol%, AgBr 30 mol%) was prepared. Five minutes after the end of mixing, 4-hydroxy-6-methyl-1,3,3a,'7-chitrazaindene 3q was added. After the mixture was returned to room temperature to stop the growth of the 7 particles and washed with demineralized water, the above-mentioned 7-in-1 gelatin B39 was added and dispersed as dispersed gelatin.

Preparation of emulsion Eb The method was the same as that for emulsion Ea, but the ceratin used was treated with hydrogen peroxide to decompose the nucleobases and reducing substances in the ceratin, and then both ions were exchanged! Processed and purified with resin, adenine and guanine are 5 μg per duram gelatin.
It contained the following I71.

Preparation of Emulsion Ec Emulsion Ec was prepared in the same manner as Emulsion Ea, except that the silver halide composition was 30 mol% AgJ and 70 mol% AgBr.

Preparation of Emulsion Kd Emulsion Kd was prepared in the same manner as Emulsion Eb, except that the silver halide composition and 1. Aging of emulsion Ka (chemical sensitization) Emulsion Ea was aged for 5 minutes, Qil l, and the following conditions were applied: AgC was 130 mol%, AgBr was 70 mol%. ...
, and Ea5 were obtained.

After adjusting the ripening emulsion Ea of the Fiat emulsion to pH 6.0, keeping it at 55'C for 15 minutes, adding sodium thiosulfate for 18 seconds, and further adding sulfur and gold for 60 minutes. After sensitization ripening, 4-hydroxy-
6-methyl-1,3,3a,'7-titrasaindene 2
g and 30 g of 10% geladine were added.

Ripening of Ea2 emulsion Chemical sensitization was carried out in the same manner as emulsion Eal, but here, after adjusting the pH, 5 orng of the compound of the present invention [IJ-2] was added and ripening was carried out.

Aging of emulsion Ea, 3 Emulsion Chemically sensitized in the same way as emulsion Ka2, but after adding compound [■]-2, 200 m9 of potassium iodide was added, ripening was carried out for 15 minutes, and sulfur gold was increased by 1·-φ. .

Aging of Ka4 emulsion Chemical amplification was carried out in the same manner as emulsion ma3, but compound [ff] -3 was added instead of compound U = 2 for ripening.

Aged emulsion Fa5 was compound sensitized in the same manner as emulsion Ea, 3, but compound [IJ-2
and 15 mg of compound [II]-3
1j1+ and ripening was performed.

Eb is processed in the same way as TCFL, and Et)1, E
Emulsions of b2, ... and Eb5 were obtained.

Similarly, in the emulsion of Ec and Kd, Ea3 and 2(
(After processing, emulsions of Ec3 and Ea3 were obtained.

To each of the above emulsions, saponin was added as a coating aid, and a combination of polyethylene glycol and styrene maleic acid as a thickener was added to the lithium developability enhancer molecule gt3o0o, and the viscosity was adjusted to 11 centimeters.

Separately, prepare a gelatin solution for storage membranes containing a coating aid adjusted to pH 5.7 and viscosity of 8 cm, and use corona discharge to make the surface hydrophilic and apply a latex layer to the undercoated gelatin solution. Protective film solution on polyethylene terephthalate support just before coating? Polmaldehyde and bisaziridine (methine chain 6) as 1ilI inhibitors
Coated with the addition of Ag fjl 3.5g/m,',
; φ membrane, gelatin was applied in 4 layers so that the adhesion amount was 1.0'j/rrt, and dried.

After exposing the above test sample to a tungsten light source through a step wedge, it was developed for 20 seconds at 38°C with a developer having the composition shown below, and then fixed, washed with water, dried, and then sensitized (IJ-).
The results are shown in Table 1.

Developer Table 1 From the results shown in Table 1, it can be seen that the emulsion processed through the process according to the present invention has high contrast and low fog, and is extremely effective as a sensitizing technique.

Furthermore, when treated with a squirrel-type developer/liquid, the sample of the present invention is
It gave favorable results for the same poems as the f table.

(Effects of the Invention) At the same time, the object of the present invention is achieved, and at the same time, images with high contrast, high sensitivity, and low fog can be obtained by using a non-Lith type developer. Low management effort and developer consumption cost; Bq
I was able to bring 1.

Agent Yoshimi Kuwahara

Claims (1)

[Claims] A step of forming halosilver chloride grains having a silver chloride content of 50 mol% or more using inert gelatin, an inert gelatin derivative, or a mixture thereof as a suspending medium, and sulfur sensitization of the silver halochloride. In the emulsion process time sequence including chemical sensitization process including (a) addition of a water-soluble rhodium salt in the grain formation process, (b) sulfur sensitization from the grain formation process to the chemical sensitization process. At least one compound represented by the following general formula [I] or [TI] is added during the period before the start, and (c) jRJ from the particle formation step to the end of the chemical sensitization step.
1. A silver halide photographic element comprising a layer of a silver halide emulsion on which a water-soluble iodide is added. General formula [I] Horse [in the formula 21 is a substituted or unsubstituted thiazole nucleus, selenazole nucleus, oxazole nucleus, imidazole nucleus, benzthiazole cedar, benzselenazole nucleus, benzoxazole nucleus, henraimidazole nucleus, Represents a group of nonmetallic atoms required to complete a naphthothiazole nucleus, naphthoselenazole nucleus, naphthoxazole nucleus, or naphthoimidazole nucleus, where X is an oxygen atom, a sulfur atom, a selenium atom, or an N-R4 group (R4 is substituted or unsubstituted represents a substituted lower alkyl group, alkenyl group or aryl group, R9 and R3 each represent i; 11-substituted or unsubstituted lower alkyl group, alkenyl group & or aryl group, Rs represents a water atom or lkoha!r-l
represents a substituted or unsubstituted lower alkyl group, alkenyl group or aryl group. ] General formula [■] 1 6 L formula 2. represents a group of nonmetallic atoms required to complete a substituted or unsubstituted 5- or 6-membered heterocyclic nucleus;
, represents an oxygen atom, a sulfur atom, a selenium atom, or a N-R, group (R7 does not represent a substituted or unsubstituted lower alkyl group, alkenyl group, or aryl group), , y represents an oxygen atom or a sulfur R6 and Ro each represent a substituted or unsubstituted lower alkyl group, alkenyl group or aryl group, and n represents 0 or 1.]