JP2003005320A - Internal latent image type direct positive silver halide emulsion and color diffusion transfer photographic sensitive material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an internal latent image type direct positive silver halide emulsion which shortens the time from the start of development to the formation of an appreciable image and ensures improved reciprocity law failure and to provide a color diffusion transfer photographic sensitive material using the emulsion. SOLUTION: The internal latent image type direct positive silver halide emulsion contains an iridium compound in silver halide grains and also contains a compound of formula (I) (where X is O, S or Se; Y is a specified divalent linking group; R is alkylene, alkenylene, aralkylene or arylene; and Z is H, nitro, cyano, sulfonyl, carbamoyl, sulfamoyl, acyloxy, sulfonyloxy, ureido, thioureido, acyl, oxycarbonyl, oxysulfonyl or the like). The color diffusion transfer photographic sensitive material contains the emulsion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an internal latent image type direct positive emulsion and a color diffusion transfer photographic light-sensitive material using the same, and more specifically, it is necessary to form an image by using the emulsion of the present invention. The present invention relates to a color diffusion transfer photographic light-sensitive material having a short time and an improved exposure illuminance dependency.

[0002]

BACKGROUND OF THE INVENTION The present invention relates to a color diffusion transfer photographic light-sensitive element that provides a direct positive photographic image. In the field of silver halide photography, a photographic method capable of obtaining a positive photographic image without intermediate processing for obtaining a negative image or a negative image is a direct photographic method, and a photographic light-sensitive material used in such a photographic method is directly We call it positive photosensitive material. There are several types of direct positive photography, but a method in which a positive emulsion (development occurs in the unexposed area) and a negative dye image forming compound (forms a dye image in the developing area) are combined, a negative emulsion (exposed area). Development takes place) and a positive type dye image forming compound (forms a dye image in an undeveloped area). For the former method, a method in which a silver halide emulsion having a photosensitive nucleus inside a silver halide grain is exposed and developed in the presence of a nucleating agent is often used. For example, US Pat. No. 2,456,953
No. 2,497,875 No. 2,497,876
No. 2,58,982, 2,592,250
Issue 2, Issue 2,675,318, Issue 3,227,552
No., British Patent Nos. 1,011,062 and 1,151,
Examples can be found in No. 363, Japanese Examined Patent Publication No. 43-29405 and the like. The emulsion used here is called an internal latent image type direct positive emulsion. In the above method for obtaining a direct positive image, various reducing agents can be used as the nucleating agent.
Of these, acylhydrazine compounds are particularly effective. U.S. Pat. Nos. 4,030,925 and 4,031,
No. 127, No. 4,245,037, No. 4,255,5
No. 11, No. 4,266,013, No. 4,276,36
No. 4, British Patent No. 2,012,443, a thiourea-bonding type acylhydrazine compound is disclosed in US Pat.
No. 080,270, No. 4,278,748 and British Patent No. 2,011,391B disclose acylhydrazine compounds having a thioamide ring or a heterocyclic group such as triazole or tetrazole as an adsorption group. However, even when these techniques are used, it takes several tens of seconds from the start of development to the formation of a viewable image in an actual color diffusion transfer light-sensitive material system, and there has been a demand for speeding up the process. On the other hand, it is necessary to improve the reciprocity law failure of the silver halide emulsion in order to cope with various photographing conditions.
For this purpose, it is known that it is effective to dope an iridium compound having a halogen as a ligand into a silver halide grain in an ordinary negative type emulsion. For example, Japanese Patent Publication 4
Examples can be found in U.S. Pat. No. 3,4,935, U.S. Pat. No. 4,997,751. Also, Japanese Patent Laid-Open No. 64-52146
The publication discloses an example of doping an internal latent image type direct positive emulsion with an iridium compound. However, when the above iridium compound is added to the internal latent image type direct positive emulsion, the reciprocity law failure characteristic is improved but the time required for image formation is delayed.

[0003]

Therefore, the present invention is
Provided are an internal latent image type direct positive silver halide emulsion and a color diffusion transfer photographic light-sensitive material using the same, which shortens the time from the start of development to the formation of a viewable image and has improved reciprocity law failure. The purpose is to

[0004]

As a result of intensive studies, the present inventors have found that the objects of the present invention can be effectively achieved by the following silver halide emulsions and light-sensitive materials. (1) An internal latent image type direct positive silver halide emulsion containing an iridium compound in a silver halide grain and a compound represented by the following general formula (I).

[0005]

[Chemical 3]

(In the formula, M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group capable of cleaving the MS bond under alkaline conditions. X represents an oxygen atom, a sulfur atom or a selenium atom. Y is

[0007]

[Chemical 4]

(Where R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
R ₆ , R ₇ and R ₈ each represent a hydrogen atom, or a substituted or unsubstituted alkyl group, aryl group, alkenyl group or aralkyl group. ) Represents. R represents a linear or branched alkylene group, a linear or branched alkenylene group, a linear or branched aralkylene group, or an arylene group. Z is a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a substituted or unsubstituted sulfonyl group, carbamoyl group, sulfamoyl group, carbonamide group, sulfonamide group, acyloxy group, sulfonyloxy group, ureido group, thioureido group. Represents a group, an acyl group, an oxycarbonyl group, an oxysulfonyl group, an oxycarbonylamino group or a mercapto group. n is 0
Or represents 1. (2) A color diffusion transfer photographic light-sensitive material comprising the internal latent image type direct positive silver halide emulsion as described in the item (1).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The internal latent image type direct positive emulsion of the present invention.
First, the process of forming core particles, followed by the core particles
For the step of chemically sensitizing the child and the step of finally coating with a shell
The emulsion has a core-shell structure obtained by
Is preferred. Other emulsions applicable to the present invention
Will be described later. The iridium compound used in the present invention is particularly limited.
It is not fixed, for example K₃IrCl₆, K₂Ir
Cl₆, (NH_Four)₂IrCl₆, Na₂IrCl₆, IrC
l_Four, IrBr_Four, IrBr₃・ 4H₂It is possible to use O etc.
it can. Also H₂Iridium complex having O as a ligand
The body can also be used. For example, [Ir (H₂O) C
l_Five]^2-, [Ir (H₂O)₂Cl_Five]^2-, [Ir (H
₂O) Br_Five]^2-, [Ir (H ₂O)₂Br_Four]^-To use
Is preferred. The iridium compounds of the present invention are halogenated
It can be added at any place during the formation of silver particles. Particle formation start
It can also be present in the reaction vessel beforehand.
The addition amount is 1 x 10 per 1 mol of Ag^-9From 1 × 10^-3Mo
You can choose between the two according to your needs. In the present invention,
The compound represented by general formula (I) is used.

[0010]

[Chemical 5]

In the formula, M is a hydrogen atom, an alkali metal atom (eg, sodium atom, potassium atom, etc.), an ammonium group, or a group capable of cleaving an MS bond under alkaline conditions (eg, —CH ₂ CH ₂ CN, -COCH ₃ ,
_{CH 3 SO 2 CH 2 CH 2} - , etc.) represents a. X is an oxygen atom,
Represents a sulfur atom or a selenium atom. Y is

[0012]

[Chemical 6]

Represents In the above formula, R ₁ , R ₂ , R ₃ , R ₄ ,
R ₅ , R ₆ , R ₇ and R ₈ are each a hydrogen atom, a substituted or unsubstituted alkyl group (preferably a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, for example, methyl, ethyl,
Propyl), a substituted or unsubstituted aryl group (preferably a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, for example, phenyl, 2-methylphenyl), a substituted or unsubstituted alkenyl group (preferably having 2 to 2 carbon atoms). 14
Or a substituted or unsubstituted alkenyl group such as propenyl or 1-methylvinyl) or a substituted or unsubstituted aralkyl group (preferably a substituted or unsubstituted aralkyl group having 7 to 21 carbon atoms such as benzyl or phenethyl).
Represents

R is a straight chain or branched alkylene group (preferably a straight chain or branched alkylene group having 1 to 18 carbon atoms, for example, methylene, ethylene, propylene, butylene, hexylene, 1-methylethylene), and A chain or branched alkenylene group (preferably having 2 to 14 carbon atoms)
A straight-chain or branched alkenylene group such as vinylene, 1-methylvinylene), a straight-chain or branched aralkylene group (preferably a straight-chain or branched aralkylene group having 7 to 21 carbon atoms, such as benzylidene), or It represents an arylene group (preferably an arylene group having 6 to 20 carbon atoms, such as phenylene or naphthylene). The above groups represented by R may be further substituted.

Z is a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a substituted or unsubstituted sulfonyl group (for example, methanesulfonyl, ethanesulfonyl,
p-toluenesulfonyl), carbamoyl group (eg unsubstituted carbamoyl, methylcarbamoyl), sulfamoyl group (eg unsubstituted sulfamoyl, methylsulfamoyl), carbonamide group (eg acetamide, benzamide), sulfonamide group (eg methanesulfonamide) , Benzenesulfonamide), acyloxy group (acetyloxy, benzoyloxy), sulfonyloxy group (eg methanesulfonyloxy, p-toluenesulfonyloxy), ureido group (eg unsubstituted ureido, methylureido, ethylureido), thioureido group. (Eg unsubstituted thioureido, methylthioureido), acyl group (eg acetyl, benzoyl), oxycarbonyl group (eg methoxycarbonyl, phenoxycarbonyl), Kishisuruhoniru group (e.g. methoxysulfonyl, phenoxysulfonyl, ethoxysulfonyl) represents an oxycarbonyl amino group (e.g., ethoxycarbonylamino, phenoxycarbonylamino), or a mercapto group. n represents 0 or 1.

In the present invention, the substituent which may be substituted is, for example, an alkyl group, an aryl group, a nitro group,
Sulfonamide group, sulfamoyl group, carbamoyl group, sulfonyl group, acylamino group, acyloxy group,
Examples thereof include an alkoxycarbonyl group and a halogen atom.

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

[0018]

[Chemical 7]

[0019]

[Chemical 8]

The compound represented by the above-mentioned general formula (I) is a Berichte der Deutsche.
nChemischen Gesellschaft)
28, 77 (1875), JP-A-50-37436,
51-3231, U.S. Pat. No. 3,295,976,
U.S. Pat. No. 3,376,310, Berichte der Germany Chen Hemischen Gesellschaft (Beric
hte der Deutschen Chemisc
hen Gesellschaft) 22, 568 (1
889), 29, 2483 (1896), Journal of Chemical Society (J. Chem. So.
c. ) 1932, 1806, Journal of the American Chemical Society (J. Am. Che
m. Soc. 71, 4000 (1949), U.S. Pat. Nos. 2,585,388 and 2,541,924, Advances in Heterocyclic Chemistry.
Chemistry 9, 165 (1968), Organic Synthesis
sis) IV, 569 (1963), Journal of
The American Chemical Society (J. Am.
Chem. Soc. ) 45, 2390 (1923), Chemische Berich
te) 9, 465 (1876), Japanese Patent Publication No. 40-2849
6, JP-A-50-89034, US Pat.
6,467, 3,420,670, 2,27
No. 1,229, No. 3,137,578, No. 3,14
No. 8,066, No. 3,511,663, No. 3,06
0,028, 3,271,154, 3,25
No. 1,691, No. 3,598,599, No. 3,14
No. 8,066, Japanese Examined Patent Publication No. 43-4135, US Pat.
615, 616, 3,420,664, 3,0
71,465, 2,444,605, 2,44
4,606, 2,444,607, 2,93
It can be easily synthesized by the method described in No. 5,404.

In the present invention, the timing of addition of the compound represented by the general formula (I) is not particularly limited. For example, when the emulsion is a core-shell type, the step of forming the core particles and the chemistry of the core particles are It may be added at any of the step of sensitizing, the step of coating with a shell, and after the particle formation (for example, during the chemical aging of the shell surface), but it is particularly preferable to add it at the step of chemically sensitizing the core particles. . The addition amount can be selected as required from 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol per mol of Ag.

Next, the case where the internal latent image type direct positive emulsion of the present invention is a core-shell type will be described. When the internal latent image type direct positive emulsion of the present invention is a core-shell type, the form of the core grains formed in the manufacturing process is not particularly limited, and tabular grains having a main plane of (111) planes,
Grains of any known form such as octahedral grains, cubic grains whose main plane is (100) plane, and tetrahedral grains can be used. The form of the particles after shelling is not particularly limited. However, since it is preferable that the core particles are completely covered by the shelling step, it is advantageous that the shape of the core particles and the particles after shelling have the same surface index of the main surface, which is advantageous for the core particles. After shelling, it is advantageous that the particles grow in a shape similar to a similar shape.
Although the composition of the core particles is not limited, silver iodobromide or pure silver bromide in which 95 mol% or more is composed of silver bromide is preferable from the viewpoint of improving discrimination. The core particles preferably do not contain lattice defects such as edge dislocations and screw dislocations.

The particle size distribution is preferably monodisperse. Here, the monodispersion is defined by obtaining a sphere equivalent diameter (a diameter of a sphere having the same volume) for each particle, and the coefficient of variation thereof being smaller than 15%. The coefficient of variation is defined as a value (σ / A) obtained by dividing the standard deviation σ of the sphere equivalent diameter by the average value A of the sphere equivalent diameter.
It is particularly preferable that the particle size distribution of the core particles is monodisperse and that the particle size distribution after shelling is monodisperse.

In the step of chemically sensitizing the core, it is preferable to add at least one gold sensitizer for aging. Other known sulfur sensitizers, oxidizing agents, and other chemical sensitizers can also be used. As an oxidizing agent, JP-A-61-131
The oxidizing agents described in Nos. 34 and 61-3136 can be used. Japanese Unexamined Patent Publication Nos. 2-191938 and 7
It is preferable to use the thiosulfonic acid compound described in No. 333782 together. The step of chemically sensitizing the core particles is preferably performed by aging at pH 4.5 to 7.0 and pAg 8 to 10. In addition, it is preferable to concurrently use a compound represented by the following general formula (III) in the same step.

General formula (III) A- (W) _n -R ^{100 In} general formula (III), A represents an atomic group containing a group capable of adsorbing to silver halide, and W represents a divalent linking group. , N represents 0 or 1, and R ¹⁰⁰ represents a reducing group.

In the general formula (III), A is specifically a mercapto compound (eg mercaptotetrazole group, mercaptotriazole group, mercaptoimidazole group, mercaptothiadiazole group, mercaptooxadiazole group, mercaptobenzthiazole group, mercaptobenzes). Oxazole group, mercaptobenzimidazole group,
Mercaptotetraazaindene group, mercaptopyridyl group, mercaptoalkyl group, mercaptophenyl group, etc.), thione compound (for example, thiazoline-2-thione group, imidazoline-2-thione group, benzimidazoline-2-thione group, benzthiazoline-2) -Thione group, thiourea group, thioamide group, etc.), compounds that form imino silver (eg, benzotriazole group, tetrazole group, hydroxytetraazaindene group, benzimidazole group, etc.) and the like. Of these, mercapto compounds and thione compounds are preferable.

In the general formula (III), W represents a divalent linking group composed of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom and a sulfur atom, specifically, having 1 to 20 carbon atoms.
Alkylene group (eg, methylene group, ethylene group, trimethylene group, tetramethylene group, hexamethylene group, etc.), arylene group having 6 to 20 carbon atoms (eg, phenylene group, naphthylene group, etc.), —CONR ¹⁰¹ —, —SO ₂ N
^{R 102 -, - O -,} - S -, - NR 103 -, - NR 104 C
O-, -NR ¹⁰⁵ SO _2- , -NR ¹⁰⁶ CONR ¹⁰⁷ -,-
COO-, -OCO- and the like can be mentioned. Where R ¹⁰¹ ,
R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , and R ¹⁰⁷ represent an aliphatic group or an aromatic group. Two or more kinds of each of these groups may be appropriately combined to form a divalent linking group.

R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R
^The aliphatic group represented by ¹⁰⁶ and R ¹⁰⁷ preferably has 1 carbon atom.
To 30 and particularly a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group or aralkyl group having 1 to 20 carbon atoms. For example, methyl group, ethyl group, isopropyl group, t-butyl group, n-octyl group,
n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, allyl group,
2-butenyl group, 3-pentenyl group, propargyl group,
Examples include 3-pentynyl group and benzyl group. R
^The aromatic group represented by ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ and R ¹⁰⁷ is preferably an aromatic group having 6 to 30 carbon atoms, particularly 6 to 20 carbon atoms. A ring or a condensed ring aryl group, and examples thereof include a phenyl group and a naphthyl group.

The precursor of a compound having an adsorbing group to silver halide and a reducing group undergoes a chemical reaction such as a redox reaction or a hydrolysis reaction when added to a silver halide emulsion and has the general formula (III). It releases the compound of For example, thiazolium salts (including benzothiazolium and naphthothiazolium), thiazolins, and thiazolidines that generate a mercapto group as an adsorbing group and a formyl group as a reducing group by a hydrolysis reaction (for example, compound 1
3), and a disulfide compound having a reducing group that cleaves a disulfide group to generate a mercapto group as an adsorptive group. The general formula (II
Specific examples of the compound represented by I) will be given.

[0030]

[Chemical 9]

[0031]

[Chemical 10]

[0032]

[Chemical 11]

A transition metal compound may be added, if desired, at several stages during the production of the silver halide emulsion. For example, US Pat. Nos. 2,448,060 and 3,2.
71,157, 3,367,778, 3,44
7,927, 3,531,291, 3,76
1,267, 3,761,276, 3,85
0,637, 3,923,513, 4,03
5,185, 4,444,874, 4,44
4,865, 4,433,047, 4,39
5,478, British Patents 1,151,782, 1,
529,011, EP 0,336,425,
No. 0,336,426, JP-A Nos. 2-20853, 2-20854, 2-259749, US Pat. Nos. 5,112,732, 6-51423, and 7-3.
The transition metal compounds described in 33767 can be added.

The internal latent image type direct positive silver halide emulsion of the present invention (hereinafter sometimes abbreviated as "internal latent image type silver halide emulsion") is mainly the inside of silver halide grains when imagewise exposed. A silver halide emulsion which forms a latent image on the transparent support, specifically, a certain amount of the silver halide emulsion is coated on a transparent support and exposed to light for a fixed time of 0.01 to 1 second. The maximum density obtained when developed and developed in the following developer A (“internal type” developer) at 20 ° C. for 5 minutes was the same as the above. Defined as having a density of at least 5 times greater than the maximum density obtained when developed in a "mold" developer) at 20 ° C for 5 minutes. Here, the maximum density is measured by a usual photographic density measuring method.

[0035] Developer A   2 g of N-methyl-p-aminophenol sulfite   Sodium sulfite (anhydrous) 90g   Hydroquinone 8g   Sodium carbonate (monohydrate) 52.5g   Potassium bromide 5g   0.5 g of potassium iodide   1 liter with water Developer B   N-methyl-p-aminophenol sulfite 2.5 g   L-ascorbic acid 10g   35 g of potassium metanitrate   Potassium bromide 1g   1 liter with water

Examples of internal latent image type silver halide emulsions include US Pat. Nos. 2,456,953 and 2,59.
A conversion type silver halide emulsion as described in US Pat. No. 2,250,250 and US Pat. No. 3,935,014.
Laminated structure type silver halide emulsions in which the first and second phases have different halogen compositions, or cores obtained by doping a metal ion or chemically sensitized with a shell. / Shell type silver halide emulsion and the like. Among them, as the internal latent image type silver halide emulsion used in the present invention, the core / shell type silver halide emulsion is particularly preferable as described above, and examples thereof include US Pat. Nos. 3,206,313 and 3,317. , 322, 3,761,266, 3,761,276, 3,850,637, 3,923,513, 4,035,185, 4,184,878. No. 4,395,478, No. 4,504,570, JP-A-57-136641, JP-A 61-3137, JP-A 61-299155, JP-A 62-208241 and the like. Some of them are listed.

In order to directly obtain a positive image, a uniform second exposure is applied to the front surface of the exposed layer after image-exposure of the above-mentioned internal latent image type silver halide emulsion (before or during the development treatment). Fogging method ", for example, British Patent No. 1,151,36
No. 3) or in the presence of a nucleating agent (“chemical fogging method”, for example, Research Disclosure, Volume 151, No. 15162,
Pages 76-78), but in the present invention,
A method of directly obtaining a positive image by the "chemical fogging method" is preferable. The nucleating agent used in the present invention will be described later. As described above, in order to directly obtain a positive image using the internal latent image type silver halide emulsion, after the image exposure, before the development processing or during the development processing, the entire surface is uniformly exposed to the second exposure, or It is obtained by carrying out development processing in the presence of a nucleating agent.

Examples of the nucleating agent used in the present invention include hydrazines described in US Pat. Nos. 2,563,785 and 2,588,982, and US Pat. No. 3,227,5.
52, hydrazides and hydrazones, British Patent No. 1,283,835, JP-A-52-69613.
No. 55-138742, No. 60-11837,
62-210451, 62-291637, U.S. Pat. Nos. 3,615,515 and 3,719,494.
Nos. 3,734,738 and 4,094,683.
No. 4,115,122, 4,306,016
Nos. 4,471,044 and other heterocyclic quaternary salt compounds, and sensitizing dye molecules having a substituent having a nucleating action, as described in U.S. Pat. No. 3,718,470. Dyes, US Pat. Nos. 4,030,925 and 4,031,
No. 127, No. 4,245,037, No. 4,255,5
No. 11, No. 4,266,013, No. 4,276,36
4, thiourea-bonded acylhydrazine compounds described in British Patent No. 2,012,443, and U.S. Pat. Nos. 4,080,270 and 4,278,748,
Sialhydrazine-based compounds having a thioamide ring or a heterocyclic group such as triazole or tetrazole bonded as an adsorption group described in British Patent No. 2,011,391B are used. The amount of the nucleating agent used here is preferably an amount that gives a sufficient maximum density when the internal latent image type emulsion is developed with a surface developing solution. In practice, the appropriate content may vary over a wide range because it depends on the characteristics of the silver halide emulsion used, the chemical structure of the nucleating agent, and the development conditions. A range of about 0.1 mg to 5 g per mole is practically useful, preferably about 0.5 mg to 2 g per mole of silver.
When it is contained in the hydrophilic colloid layer adjacent to the emulsion layer, the same amount as described above may be contained with respect to the amount of silver contained in the inner latent type emulsion having the same area.

The method of adding pre-precipitated silver halide grains to a reaction vessel for emulsion preparation is described in US Pat. Nos. 4,334,012, 4,301,241 and 4,150,994. Is more preferable. These can be used as seed crystals, and are also effective when provided as silver halide for growth. In the latter case, it is preferable to add an emulsion having a small grain size. As an addition method, the whole amount may be added at a time, a plurality of times may be added in a divided manner, or the addition may be continuously performed. It is also effective in some cases to add particles having various halogen compositions in order to modify the surface.

Besides the method of adding soluble silver salt and halogen salt at a constant concentration and a constant flow rate for grain growth, British Patent No. 1,
469,480, U.S. Pat. No. 3,650,757,
A particle forming method in which the concentration is changed or the flow rate is changed as described in U.S. Pat. No. 4,242,455 is a preferable method. By increasing the concentration or increasing the flow rate, the amount of silver halide supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied if necessary. Furthermore, when adding a plurality of soluble silver salts having different solution compositions, or when adding a plurality of soluble halogen salts having different solution compositions, an addition method in which one is increased and the other is decreased is also an effective method. Is. A mixer for reacting a solution of a soluble silver salt and a soluble halogen salt is US Pat. Nos. 2,996,287, 3,342,605, 3,415,650 and 3,785,777. , West German Published Patents 2,556,885, 2,555,364
It can be used by selecting from the methods described in No.

During the production of emulsions containing tabular grains,
Add silver salt solution (eg Ag) to accelerate grain growth.
A preferred method is to increase the addition rate, the addition amount, and the addition concentration of the NO ₃ aqueous solution) and the halide solution (for example, KBr aqueous solution). Regarding these methods, for example, British Patent No. 1,335,925 and US Pat. No. 3,672,90 are described.
0, 3,650,757, 4,242,445
No. 5, JP-A-55-142329 and JP-A-55-15812.
The description of No. 4 etc. can be referred to.

The method of adding a chalcogenide compound as described in US Pat. No. 3,772,031 during preparation of an emulsion may be effective. In addition to S, Se and Te, cyanate, thiocyanate, selenocyanate, carbonate,
Phosphate and acetate may be present. Regarding these, US Pat. Nos. 2,448,060 and 2,628,
No. 167, No. 3,737,313, No. 3,772,0
31 and Research Disclosure, 134
Vol., June 1975, 13452, etc.

The silver halide grains have different phases in the inside and the surface, but the silver halide composition inside the grain may be uniform or may be composed of different silver halide compositions. The surface phase may be a discontinuous layer or may have a continuous layered structure. Also, particles having dislocation lines may be used.

It is important to control the halogen composition in the vicinity of the surface of the particle, and when changing the halogen composition in the vicinity of the surface, it is possible to select either a structure enclosing the entire particle or a structure in which only a part of the particle is attached. . For example, it is a case where the halogen composition is changed only on one surface of the tetradecahedral grain composed of the (100) plane and the (111) plane, or the halogen composition is changed on one of the main plane and the side surface of the tabular grain.

Two or more kinds of silver halides having different crystal habits, halogen compositions, grain sizes, grain size distributions, etc. can be used in combination, and they are used in different emulsion layers and / or the same emulsion layer. It is possible to

In the silver halide emulsion of the present invention, it is preferable that the core grains which have been chemically sensitized are coated with the shell, and then the grain surfaces are further chemically sensitized in order to show good reversal performance with high maximum density. . When chemically sensitizing the grain surface, a polymer as described in JP-A-57-13641 may coexist. The above chemical sensitization is based on The Theory of the Photographic by James.
Process, 4th edition, published by Macmillan, 1977, (T.
H. James, The Theory of the Photographic Process,
4th ed., Macmillan, 1977) 67-76 and using active gelatin,
Research Disclosure, Volume 120, 1974
April, 2008; Research Disclosure,
34, June 1975, 13452, U.S. Pat. No. 2,
642, 361, 3,297,446, 3,7
72,031, 3,857,711, 3,90
1,714, 4,266,018, and 3,9
04,415 and British Patent No. 1,315,755.
, PAg 5-10, pH 4-8, and temperature 30-80 ° C., sulfur, selenium, tellurium, gold,
It can be carried out using platinum, palladium, iridium, rhodium, osmium, rhenium, or a combination of a plurality of these sensitizers.

The chemical sensitization in the photographic emulsion of the present invention is F
It can be performed using a metal material such as e, Cr, Mn, Ni, Mo, and Ti, but it is more preferably performed in a non-metal material whose surface is coated with a fluororesin. Examples of the fluororesin material include Teflon (registered trademark) coating materials PFA, TFE, and FEP developed by DuPont.

It is also possible to carry out chemical sensitization in the presence of a chemical sensitization aid. As the chemical sensitization aid to be used, compounds such as azaindene, azapyridazine and azapyrimidine which are known to suppress fog and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitization aids are
US Pat. Nos. 2,131,038 and 3,411,91
No. 4, 3,554, 757, JP-A-58-1265.
36, 62-253159, and "Photographic Emulsion Chemistry" by Daffin, pp. 138-143 (published by Focal Press, 1966).

Japanese Patent Publication No. 58-1410, Mois
ar) et al., Journal of Photographic Science, Vol. 25, 1977, pp. 19-27, silver halide emulsions can reduce and sensitize the inside of grains during the precipitation formation process. . The following reduction sensitization can also be used as the chemical sensitization. U.S. Pat. No. 3,891,
As described in Nos. 446 and 3,984,249, reduction sensitization can be performed by using, for example, hydrogen,
US Pat. Nos. 2,518,698 and 2,743,18
2 and 2,743,183 with reducing agents, or low pAg (eg less than 5) or high p.
Reduction sensitization can be performed by H (for example, greater than 8) treatment. As typical reduction sensitizers, stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds are known. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, or two or more kinds of compounds can be used in combination. As reduction sensitizers, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. Further, the chemical sensitization methods described in US Pat. Nos. 3,917,485 and 3,966,476 can also be applied.

Further, JP-A-61-3134 and 61-3
The sensitizing method using an oxidizing agent described in JP-A No. 136 can also be applied. The oxidizing agent for silver refers to a compound that acts on metallic silver to convert it into silver ions. In particular, a compound that converts extremely fine silver grains, which are a by-product in the process of forming silver halide grains and the process of chemical sensitization, into silver ions is effective. The silver ions generated here may form a poorly soluble silver salt such as silver halide, silver sulfide and silver selenide, or may form a readily soluble silver salt such as silver nitrate. Good. The oxidizing agent for silver may be an inorganic substance or an organic substance. Inorganic oxidizers include ozone, hydrogen peroxide and its adducts (eg Na
BO ₂ · H ₂ O ₂ · 3H ₂ O · 2NaCO ₃ · 3H ₂ O ₂ , N
_{a 4 P 2 O 7 · 2H} 2 O 2, 2Na 2 SO 4 · H 2 O 2 · 2H
₂ O), peroxy acid salts (eg K ₂ S ₂ O ₈ , K ₂ C)
₂ O ₆ , K ₂ P ₂ O ₈ ) and peroxy complex compounds (for example,
K ₂ [Ti (O ₂ ) C ₂ O ₄ ] / 3H ₂ O, 4K ₂ SO ₄ · T
i (O ₂ ) OH.SO ₄ .2H ₂ O, permanganate (eg KMnO ₄ ), chromate (eg K ₂ Cr)
₂ O ₇ ) and other oxyacid salts, iodine and bromine and other halogen elements, perhalogenates (eg potassium periodate), and high valent metal salts (eg potassium hexacyanoferrate), etc. is there. Examples of the organic oxidant include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release an active halogen (for example, N-bromosuccinimide, chloramine T, chloramine B). ) Is mentioned as an example. Preferred oxidizing agents of the present invention are organic oxidizing agents of ozone, hydrogen peroxide and its adducts, halogen elements and quinones. It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. It is possible to select and use the method of performing reduction sensitization after using an oxidizing agent, the reverse method thereof, or the method of coexisting both. These methods can be selectively used in the grain forming step and the chemical sensitization step.

Gelatin is advantageously used as the dispersion medium (protective colloid) used in the preparation of the emulsion of the present invention, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl. Various synthetic hydrophilic polymer substances such as alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc., such as single or copolymers Can be used. Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Photo.Japa.
n, No. 16, an enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzate or an enzymatic hydrolyzate of gelatin may also be used. Although many impurity ions are contained in gelatin, it is also preferable to use gelatin in which the amount of inorganic impurity ions is reduced by ion exchange treatment.

The emulsion of the present invention is preferably washed with water for desalting and then dispersed in a newly prepared protective colloid. The temperature of washing with water can be selected according to the purpose, but it is preferably selected in the range of 5 to 50 ° C. The pH at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 2 and 10. More preferably, it is in the range of 3-8. The pAg at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 5 and 10. As a method of washing with water, a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugation method, a coagulation sedimentation method, or an ion exchange method can be selected and used. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a polymer for washing with water, a method using a gelatin derivative and the like can be selected.

In the present invention, spectral sensitization can be performed using a sensitizing dye. Examples of the sensitizing dye used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, U.S. Pat. No. 4,617,257, JP-A-59-180550 and JP-A-60-140335,
61-160739, RD17029 (1978)
12) 13-12, RD17643 (1978) 23
Examples include sensitizing dyes described in pages.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,9.
77,229, 3,397,060, 3,52
No. 2,052, No. 3,527,641, No. 3,61
7,293, 3,628,964, 3,66
6,480, 3,672,898, 3,67
9,428, 3,703,377 and 3,76
9,301, 3,814,609, 3,83
7,862, 4,026,707, British Patents 1,344,281, 1,507,803, Japanese Patent Publication Nos. 43-4936, 53-12375, and Japanese Patent Laid-Open No. 5-12375.
2-110618 and 52-109925.

Along with the sensitizing dye, a dye that does not have a spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may be included in the emulsion. (For example, U.S. Pat. Nos. 3,615,613, 3,
615, 641, No. 3,617, 295, No. 3, 6
35,721, 2,933,390, 3,74
3,510, those described in JP-A-63-23145, etc.). The timing of adding the sensitizing dye for spectral sensitization to the emulsion may be at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is done after the completion of chemical sensitization and before coating, but US Pat.
It is also possible to add spectral sensitization simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A-58-1139 and JP-A-58-1139.
It can be carried out prior to chemical sensitization as described in No. 28, or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. Furthermore, it is possible to add these said compounds separately, as taught in US Pat. No. 4,225,666, ie to add some of these compounds prior to chemical sensitization and the rest to chemical sensitization. It can be added after the sensation, and can be added at any time during the formation of silver halide grains, including the method disclosed in US Pat. No. 4,183,756. From the viewpoint of achieving the object of the present invention, it is preferable to perform the chemical sensitization step of the shell portion, and it is particularly preferable to add it near the end of chemical sensitization.

The addition amount of the sensitizing dye can be 10 ^-8 to 10 ^-2 mol per mol of silver halide, and more preferable silver halide grain size is 0.2 to 1.2 μm.
In the case of, about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol is more effective.

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In the present invention, various antifoggants and photographic stabilizers can be used for the purpose of preventing sensitivity deterioration and fogging. For example, RD17643
(1978) 24-25, U.S. Pat. No. 4,629,
Nos. 678 and azaindenes, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or mercapto compounds and metal salts thereof described in JP-A-59-111636, JP-A-62. -87
The acetylene compounds described in No. 957 are used. Also, phenethyl alcohol and JP-A-63-25
No. 7747, No. 62-272248, and JP-A-1-
1,2-benzisothiazoline described in 80941
3-one, n-butyl, P-hydroxybenzoate,
It is preferable to add various antiseptics or antifungal agents such as phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole. For details, see European Patent No. 4
36, 938A2, page 150, lines 25-28. These additives are described in more detail in Research Disclosure Item 17643 (1978),
Item 18716 (November 1979) and Item 30
7105 (November 1989), and the relevant portions are summarized in the table below.

[0059]   Types of additives RD17643 RD18716 RD307105                   (December 1978) (November 1979) (November 1989) 1 Chemical sensitizer Page 23 Page 648 Right column Page 866 2 Sensitivity enhancer Page 648, right column 3 Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868     Supersensitizer: page 649, right column 4 Whitening agents Page 24 Page 647 Page 868 5 Fogging prevention 24 to 25 pages 649 right column 868 to 870     Agent, stabilizer 6 Light absorbers, pages 25 to 26, page 649, right column, page 873     Filter ~ Page 650 Left column     Dye, ultraviolet     Line absorber 7 stain page 25 right column page 650 left column page 872     Inhibitor ~ right column 8 Dye image Page 25 Page 650 Left column Page 872     Stabilizer 9 Hardener 26 pages 651 left column 874-875 10 Binder, page 26, ibid., Pages 873 to 874 11 Plasticizer, page 27, page 650, right column, page 876     lubricant 12 Coating aid, pages 26-27 ibid., Pages 875-876     Surfactant 13 Static 27 pages Id. 876-877     Preventive agent 14 Matting agent pp. 878-879

The internal latent image type direct positive silver halide emulsion of the present invention can be used in a conventional light-sensitive material, but it is preferably used in a color diffusion transfer light-sensitive material. Next, the color diffusion transfer photosensitive material of the present invention will be described. The most typical form of the color diffusion transfer material is a color diffusion transfer film unit, and the typical form thereof is that the image receiving element and the photosensitive element are laminated on one transparent support to form a transfer image. It is a form in which it is not necessary to peel the light-sensitive element from the image-receiving element after completion of. More specifically, the image-receiving element comprises at least one mordant layer, and in a preferred embodiment of the light-sensitive element, a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, or a green-sensitive emulsion layer. A combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, or a combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, and a yellow dye image-forming compound in each emulsion layer, A magenta dye image-forming compound and a cyan dye image-forming compound are respectively combined to constitute (here, "infrared light-sensitive emulsion layer" means an emulsion having a maximum spectral sensitivity to light of 700 nm or more, particularly 740 nm or more. Layer). The emulsion of the present invention may be contained in at least one of these photosensitive emulsion layers, but it is preferably contained in all the photosensitive emulsion layers. Then, between the mordant layer and the photosensitive layer or the dye image forming compound-containing layer, a transferred image can be viewed through a transparent support,
A white reflective layer containing a solid pigment such as titanium oxide is provided.

A light-shielding layer may be further provided between the white reflective layer and the photosensitive layer so that the development process can be completed in a bright place. Further, if desired, a peeling layer may be provided at an appropriate position so that all or part of the photosensitive element can be peeled from the image receiving element. Such an embodiment is disclosed in, for example, JP-A-56-56.
67840 and Canadian Patent 674,082.

In another embodiment of the laminate type which is peeled off, at least (a) a layer having a neutralizing function, (b) a dye image-receiving layer, and (a) on a white support described in JP-A-63-226649. c) a release layer, (d) a light-sensitive element sequentially having at least one silver halide emulsion layer combined with a dye image-forming compound, an alkali processing composition containing a light-shielding agent, and a transparent cover sheet. There is a color diffusion transfer photographic film unit characterized by having a layer having a light shielding function on the side opposite to the side where the processing composition is developed.

In another form in which peeling is not necessary, the above-mentioned photosensitive element is coated on one transparent support, a white reflective layer is coated thereon, and an image receiving layer is further laminated thereon. .
US Pat. No. 3,730,7 is disclosed in which an image receiving element, a white reflective layer, a peeling layer and a photosensitive element are laminated on the same support, and the photosensitive element is intentionally peeled from the image receiving element.
18 is described.

On the other hand, there are roughly two typical forms in which a light-sensitive element and an image-receiving element are separately coated on two supports, one is a peeling type and the other is a peeling-free type. is there. Explaining these in detail, in a preferable embodiment of the peelable film unit, at least one image receiving layer is coated on one support, and the photosensitive element is coated on the support having a light shielding layer. Before the exposure is finished, the photosensitive layer coated surface and the mordant layer coated surface do not face each other, but after the exposure is finished (for example, during the development process), the photosensitive layer coated surface is inverted in the image forming apparatus to come into contact with the image receiving layer coated surface. It is devised to be. After the transfer image is completed on the mordant layer, the light-sensitive element is rapidly separated from the image-receiving element. In a preferred embodiment of the peel-free type film unit, at least one mordant layer is coated on a transparent support, and a photosensitive element is coated on a support having a transparent or light-shielding layer. The photosensitive layer coated surface and the mordant layer coated surface face each other and are superposed.

A pressure-rupturable container (processing element) containing an alkaline processing liquid may be combined with the above-mentioned form. Among others, in a peel-free type film unit in which an image receiving element and a photosensitive element are laminated on one support, the processing element is preferably arranged between the photosensitive element and a cover sheet overlaid thereon. Further, in the form in which the light-sensitive element and the image-receiving element are separately coated on the two supports, it is preferable that the processing element is disposed between the light-sensitive element and the image-receiving element at the latest during the development processing. The processing element preferably contains either or both of a light-shielding agent (such as carbon black and a dye whose color changes with pH) and a white pigment (such as titanium oxide) depending on the form of the film unit. Further, in the color diffusion transfer type film unit, it is preferable that a neutralization timing mechanism comprising a combination of a neutralization layer and a neutralization timing layer is incorporated in the cover sheet, the image receiving element, or the light sensitive element.

The dye image-forming material used in the present invention is a non-diffusible compound that releases a diffusible dye (which may be a dye precursor) in connection with silver development, or one in which the diffusivity of itself changes. And "The Theory of the Photographic Process", Part 4
Listed in the edition. All of these compounds can be represented by the following general formula (II). Formula (II) (DYE-Y) _n -Z {DYE represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or a linking group,
Z is related to silver development (specifically, corresponding to or inversely corresponding to a photosensitive silver salt having an image-wise latent image) (DYE-Y)
causes a difference in diffusivity of the compound represented by _n- Z,
Or a group having a property of releasing DYE (diffusible dye or its precursor) and causing a difference in diffusivity between the released DYE and (DYE-Y) _n -Z, and n Represents 1 or 2, and when n is 2, two DYEs
-Y may be the same or different. } According to the function of Z, it is roughly classified into a negative compound that becomes diffusible in the silver developed area and a positive compound that becomes diffusible in the undeveloped area. Specific examples of the negative Z include those that are oxidized as a result of development and cleaved to release a diffusible dye.
Specific examples of Z include U.S. Pat. Nos. 3,928,312 and 3,3,928.
993,638, 4,076,529, 4,1
52,153, 4,055,428, 4,05
3,312, 4,198,235, 4,17
9,291, 4,149,892, 3,84
4,785, 3,443,943, 3,75
1,406, 3,443,939, 3,44
3,940, 3,628,952, 3,98
0,479, 4,183,753, 4,14
2,891, 4,278,750, 4,13
9,379, 4,218,368 and 3,42
1,964, 4,199,355, 4,19
9,354, 4,135,929, 4,33
6,322, 4,139,389, JP-A-53-
No. 50736, No. 51-104343, No. 54-13.
0122, 53-1108827, 56-126
No. 42, No. 56-16131, No. 57-4043,
57-650, 57-20735, 53-6.
No. 9033, No. 54-130927, No. 56-164
No. 342, No. 57-119345 and the like. Among Z of the negative type dye-releasing redox compound, an N-substituted sulfamoyl group (N-
Examples of the substituent include a group derived from an aromatic hydrocarbon ring or a hetero ring. Representative examples of Z are shown below, but the present invention is not limited thereto.

[0067]

[Chemical 12]

For positive type compounds, Angevante Chemie International Edition English (Angev. Chem. Int. Ed. Engl.), 22, 191
(1982). A specific example thereof is a compound (dye developing agent) that is initially diffusible under alkaline conditions but is oxidized by development to become non-diffusible. Effective Z for this type of compound is described in US Pat.
Typical examples are those listed in No. 83606. Also,
Another type is one in which the diffusible dye is released by self-ring closure under alkaline conditions, but the dye is substantially not released when it is oxidized during development. Specific examples of Z having such a function include U.S. Pat. No. 3,980,479, JP-A Nos. 53-69033 and 54-130927, and U.S. Pat. No. 3,421,964.
No. 4,199,355 and the like. Another type is one that does not itself release a dye but releases a dye when reduced. This type of compound can be used in combination with an electron donor to release the diffusible dye imagewise by reaction with the remaining electron donor which has been imagewise oxidized by silver development. For the atomic group having such a function, see, for example, US Pat.
3,753, 4,142,891, 4,27
8,750, 4,139,379, 4,21
8,368, JP-A-53-110827, U.S. Pat. Nos. 4,278,750, 4,356,249, 4,358,535, and JP-A-53-110827.
54-130927, 56-164342, Technical Report 87-6199, European Patent Publication 220746A.
No. 2 etc. Specific examples of Z will be illustrated below, but the present invention is not limited thereto.

[0069]

[Chemical 13]

When this type of compound is used, it is preferably used in combination with a diffusion-resistant electron donating compound (known as an ED compound) or its precursor (precursor). Examples of ED compounds include, for example, US Pat.
263,393, 4,278,750, JP-A-5
6-138736 and the like. The following can also be used as specific examples of another type of dye image-forming substance.

[0071]

[Chemical 14]

For details, see US Pat. No. 3,719,489.
No. 4,098,783. on the other hand,
Specific examples of the dye represented by the above general formula DYE are described in the following documents. Examples of yellow dyes: US Pat. No. 3,597,200,
3,309,199, 4,013,633, 4,245,028, 4,156,609, 4,139,383, 4,195,992, 4 , 148, 641, 4,148, 643, 4,336, 322: JP-A-51-114930.
56-71072: Research Disclosure 1763.
No. 0 (1978) and No. 16475 (1977). Examples of magenta dyes: US Pat. No. 3,453,107,
3,544,545, 3,932,380, 3,931,144, 3,932,308, 3,954,476, 4,233,237, 4 , 255, 509, 4,250, 246, 4,142, 891, 4,207, 104, 4,287, 292: JP-A-52-106727,
53-23628, 55-36804, 56
-73057, 56-71060, 55-13
What is described in No. 4. Examples of cyan dyes: U.S. Pat. Nos. 3,482,972, 3,929,760, 4,013,635, 4,268,625, 4,171,220 and 4,171,220. 242,435, 4,142,891, 4,195,994, 4,147,544, 4,148,642; British Patent 1,551,138.
Nos. 54-99431 and 52-8827.
No. 53-47823, No. 53-143323, No. 5
4-99431, 56-71061; European Patents (EP) 53,037, 53,040; Rese
those described in arch Disclosure 17,630 (1978) and 16,475 (1977). These compounds are disclosed in JP-A-62-215,272, 14
It can be dispersed by the method described on pages 4-146. Further, these dispersions include those disclosed in JP-A-62-215,272.
No. 137-144 may be included.
The internal latent image type direct positive silver halide emulsion of the present invention may also be used in a conventional light-sensitive material. Examples of applicable light-sensitive materials include light-sensitive materials for color and black-and-white printing paper, light-sensitive materials for color slides, and light-sensitive materials for microfilm.

[0073]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Example 1 Preparation of Internal Latent Image Type Direct Positive Emulsion Preparation of Emulsion-H1 Potassium bromide 0.05M, 3,6-dithia-1,8-octanediol 1.3 g, lead acetate 0.13 mg, and Ca content 100 ppm. 70 g of the following deionized gelatin
To 1100 ml of gelatin aqueous solution containing
While maintaining at ℃, pour 0.3M silver nitrate aqueous solution and 0.3M potassium bromide aqueous solution by control double jet method.
86 ml of an aqueous silver nitrate solution was added over 3 minutes while controlling the addition rate of potassium bromide so that Br was 1.40. After aging for a predetermined time, a 0.6 M silver nitrate aqueous solution and a 0.6 M potassium bromide aqueous solution were controlled by a double jet method while controlling the addition rate of potassium bromide so that the pBr would be 1.40. Aqueous solution 630
ml was added over 45 minutes. When the addition was completed, monodisperse octahedral silver bromide crystals with a uniform grain size of about 0.64 μm were produced. The particles generated up to this point are called core particles. Subsequently, the core particles were chemically sensitized under the following conditions. 1. Tank: hemispherical bottom tank whose metal surface is Teflon coated with a fluororesin agent FEP developed by Du Pont to a thickness of 120 μm 2. Stirrer: A seamless propeller type with a Teflon coating on the metal surface. Aging conditions: An aqueous potassium bromide solution was added to the core particle emulsion preparation solution to adjust pBr to 1.15, and then 7 mg of sodium thiosulfate and 90 mg of potassium tetrachloroaurate and potassium bromide were added. 2 g of water 1000
Add 13 ml of an aqueous solution dissolved in ml, and add 110 at 75 ° C.
Heat for minutes. Subsequently, an aqueous potassium bromide solution was added to add p.
After changing Br to 0.95, 1.0M silver nitrate aqueous solution and 1.0M potassium bromide aqueous solution were controlled by the double jet method to adjust the addition rate of the potassium bromide aqueous solution so that pBr would be 0.95. While 440 silver nitrate aqueous solution
ml was added over 40 minutes. This emulsion was washed with water by a conventional flocculation method to obtain gelatin and 2
-Phenoxyethanol and methyl p-hydroxybenzoate were added to obtain monodispersed octahedral silver bromide octahedral crystals of uniform particle size with an average particle size of about 0.8 µm. This process is called a process of covering with a shell.

Preparation of Emulsion-BH1, GH1, and RH1 (Internal Latent Image Type Direct Positive Silver Halide Emulsion-Comparative Example) Emulsion-H1 prepared up to this point was added with sodium thiosulfate 1
00 mg and sodium tetraborate 40 mg water 1000 ml
7 ml of an aqueous solution dissolved in was added, further 8 mg of poly (N-vinylpyrrolidone) was added, and the mixture was aged at 75 ° C. for 100 minutes. Subsequently, the sensitizing dye was added as shown in Table 1. In this way, internal latent image type direct positive silver halide emulsions BH1, GH1, RH1 were prepared.

Emulsion-Preparation of L1 Potassium bromide 0.07M, 1,8-dihydroxy-
26 mg of 3,6-dithiaoctane, 0.47 mg of lead acetate
And deionized gelatin with a Ca content of 100 ppm or less 6
In 1150 ml of a gelatin aqueous solution containing 7 mg, a 0.6 M silver nitrate aqueous solution and 0.1% were added while keeping the temperature at 75 ° C.
Control a 6M potassium bromide aqueous solution by a double jet method while adjusting the addition rate of the potassium bromide aqueous solution so that the pBr would be 1.3.
Added over 0 minutes. Average particle size (sphere equivalent diameter) 0.2
Monodisperse octahedral silver bromide crystals with a grain size of 9 μm were produced. The particles obtained up to this point are called core particles. Then, after completion of the addition, the core particles were chemically sensitized under the following conditions. 1. Tank: hemispherical bottom tank whose metal surface is Teflon coated with a fluororesin agent FEP developed by Du Pont to a thickness of 120 μm 2. Stirrer: A seamless propeller type with a Teflon coating on the metal surface. Aging condition: An aqueous potassium bromide solution was added to the core particle emulsion preparation solution to adjust pBr to 1.15, and then sodium thiosulfate 4 mg and potassium tetrachloroaurate 90 mg and potassium bromide 1. 2 g of water 1000
Add 13 ml of an aqueous solution dissolved in ml and heat at 75 ° C for 80 minutes. Subsequently, 1.0 M silver nitrate aqueous solution and 1.0
Control the aqueous potassium bromide solution of M by the double jet method while adjusting the addition rate of the aqueous potassium bromide solution so that the pBr becomes 1.30.
Added over 4 minutes. This emulsion was washed with water by an ordinary flocculation method, and the above-mentioned gelatin, 2-phenoxyethanol and methyl p-hydroxybenzoate were added thereto to obtain a monodisperse monodisperse powder having an average particle size of about 0.47 μm. A octahedral silver bromide octahedral crystal was obtained. This process is called a process of covering with a shell.

Preparation of Emulsion-BL1, GL1 and RL1 (Internal Latent Image Type Direct Positive Silver Halide Emulsion-Comparative Example) Emulsion-L1 prepared up to this point was added with sodium thiosulfate 1
00 mg and sodium tetraborate 40 mg water 1000 ml
7 ml of an aqueous solution dissolved in was added, further 8 mg of poly (N-vinylpyrrolidone) was added, and the mixture was aged at 75 ° C. for 100 minutes. Subsequently, the sensitizing dye was added as shown in Table 1. In this way, internal latent image type direct positive silver halide emulsions BL1, GL1, RL1 were prepared.

[0077]

[Table 1]

[0078]

[Chemical 15]

[0079]

[Chemical 16]

[0080]

[Chemical 17]

Next, a method for producing the photosensitive element 101 will be described. A 100 μm thick transparent polyethylene terephthalate film support was coated in the following layer structure to prepare Photosensitive Element-101.

Back layer side: (a) Carbon black 6.0 g / m ² and 2.0 g
/ M ² containing light-shielding layer (b) gelatin containing 0.5 g / m ² protective layer

Emulsion layer side: Emulsions BH1, GH1, RH1,
BL1, GL1, and RL1 were used to prepare photosensitive elements having the configurations shown in Tables 2 to 6 below.

[0084]

[Table 2]

[0085]

[Table 3]

[0086]

[Table 4]

[0087]

[Table 5]

[0088]

[Table 6]

The compounds used for preparing the light-sensitive element are summarized below.

[0090]

[Chemical 18]

[0091]

[Chemical 19]

[0092]

[Chemical 20]

[0093]

[Chemical 21]

[0094]

[Chemical formula 22]

[0095]

[Chemical formula 23]

[0096]

[Chemical formula 24]

[0097]

[Chemical 25]

[0098]

[Chemical formula 26]

[0099]

[Chemical 27]

[0100]

[Chemical 28]

The emulsion RL1 of the third layer of the photosensitive element-101 was
For Emulsions RL2, RL3, RL4, and RL5 prepared below
Modified to prepare Photosensitive Elements-102 to 105. Emulsion RL2 90% of silver nitrate used in the preparation of Emulsion RL1
When is added K ₃IrCl₆  10 mg to 1000
The emulsion added with 1.0 ml of an aqueous solution dissolved in
Set to 2. Emulsion RL3 In the preparation method of Emulsion RL1, after forming core particles, core particles
1 g of the exemplified compound C-1 of the present invention before the chemical sensitization of
15 ml of a solution prepared by dissolving
The emulsion prepared in the same process except for adding is called RL3.
It

Emulsion RL4 (Emulsion sample of the present invention) In the preparation method of Emulsion RL1, after forming core particles, core particles
1 g of the exemplified compound C-1 of the present invention before the chemical sensitization of
15 ml of a solution prepared by dissolving
When 90% of the silver nitrate used is added
And K₃IrCl₆10 mg dissolved in 1000 ml water
The emulsion added with 1.0 ml of the liquid is designated as RL4. Emulsion RL5 (Emulsion sample of the present invention) 90% of silver nitrate used in the preparation of Emulsion RL1
When is added K ₃IrCl₆  10 mg to 1000
Add 1.0 ml of an aqueous solution dissolved in ml, and then add particles.
After completion of formation, 1 g of the exemplified compound C-1 of the present invention was added to 10 g.
15 ml of a solution dissolved in 00 ml of methanol was added
The emulsion is RL5.

The image receiving element was prepared as follows. 150μ with 20μm polyethylene laminated on both sides
An image receiving element was prepared by performing the following coating on a paper support of m. Back layer side: (a) Light-shielding layer containing carbon black 2.8 g / m ² and gelatin 4.8 g / m ² (b) Titanium dioxide 4.1 g / m ² and gelatin 1 g
/ M ² white layer (c) gelatin 0.5 g / m ² protective layer image receiving layer side: (1) acrylic acid / butyl acrylate copolymer (molar ratio 8: 2, average molecular weight 50,000) ) 4.0 g / m ² ,
Polyvinyl alcohol (polymerization degree 500, saponification rate 88%)
6.0 g / m ² and the following hardener (A) 0.04 g / m ²
A neutralization layer containing.

[0104]

[Chemical 29]

(2) Diacetyl cellulose (acetylation degree 5
1.3%) 3.5 g / m ² and styrene / maleic anhydride copolymer (molar ratio 1: 1, average molecular weight 10,000)
0) 0.39 g / m ² , the following compound (B) 0.073.
5g / m ² and Coronate HL (trade name, manufactured by Nippon Polyurethane (Ltd.)) 0.098g / m ² neutralization timing layer containing a.

[0106]

[Chemical 30]

(3) Polymer latex (one obtained by emulsion polymerization of styrene / butyl acrylate / N-methylol acrylamide at a polymerization ratio of 49.7 / 42.3 / 8)
1.32 g / m ² , polymer latex (polymerization ratio of methyl methacrylate / acrylic acid / N-methylol acrylamide 93/3/4) 1.32 g / m ² , the following hardening agent (C) 0.162 g / m ² And a neutralization timing layer containing 0.015 g / m ² of the following coating aid (D).

[0108]

[Chemical 31]

(4) The following mordant (E) 3.7 g / m ² ,
Formaldehyde 0.21 g / m ² , the above hardener (A)
0.10 g / m ² , 0.01 g / of the above coating aid (D)
1. m ² , polymer beads of polymethylmethacrylate (average particle size: 11 μm) 0.21 g / m ² and gelatin 2.
Image receiving layer containing 8 g / m ² (mordanting layer)

[0110]

[Chemical 32]

(5) Acrylic acid / butyl methacrylate copolymer (molar ratio 85/15, average molecular weight 100,0
00) 0.06 g / m ² and the following hardener (G) 0.0
A release layer containing 03 g / m ² .

[0112]

[Chemical 33]

The alkaline treatment composition was prepared as follows. An alkali treatment composition was prepared by filling 1 g each of the treatment liquids having the following compositions in a vinyl chloride laminated aluminum foil pod under a nitrogen atmosphere. Treatment liquid Hydroxyethyl cellulose 42 g Zinc nitrate · 6H ₂ O 0.9 g 5-Methylbenzotriazole 5.4 g Benzyl alcohol 3.4 ml Titanium dioxide 1.2 g Aluminum nitrate · 9H ₂ O 15 g Potassium sulfite 1.0 g 1-phenyl-4- Hydroxy-4-hydroxymethyl-3-pyrazolidone 13 g Potassium hydroxide 63 g Water 855 ml

Next, prepared photosensitive elements-101 to 105
Was exposed from the emulsion side through a continuous gray wedge, and then superposed with the image receiving element, and the alkali processing composition was developed between the both elements so as to have a thickness of 60 μm using a pressure roller. Exposure and processing were performed at 25 ° C. For exposure, adjust the illuminance so that the exposure amount is constant.
/ 100 second exposure and 10 second exposure were performed. The standard treatment was to peel off the light-sensitive element and the image-receiving element 90 seconds after the treatment. After the image receiving element was dried, the cyan dye density transferred to the image receiving element was measured with a color densitometer (X-Rite 310 (trade name, manufactured by X-Rite)). Sensitivity is D by standard processing
Defined as the reciprocal of the exposure dose that gives a density of min + 0.5,
It was expressed as a relative value with the value of Sample 101 being 100. The density changes according to the time until the photosensitive element and the image receiving element are peeled off after processing. (The density of the unexposed area decreases when shortened from the standard 90 seconds.) The time until the density of the unexposed area reaches 0.5 is taken as the image appearance after the photosensitive element and the image receiving element are peeled off after processing. It was defined as the time required. Sample 10
With respect to Nos. 1 to 105, the presence or absence of the iridium compound and the compound represented by the general formula (I), 1/100 second exposure sensitivity, 10 second exposure sensitivity, and the time required for image appearance are shown in Table 7 below. Samples 104 and 105 use the emulsion of the present invention in the third layer.

[0115]

[Table 7]

As is clear from Table 7, the internal latent image type direct positive emulsion sample NO. 101 is 1/100
It can be seen that the low-illuminance reciprocity law failure occurs because the sensitivity in the 10-second exposure, which is a low-illuminance exposure, is much lower than the sensitivity in the second-exposure exposure. Comparative sample NO. In No. 102, the low illuminance reciprocity law failure can be reduced by adding the iridium compound, but the time required for the image to appear becomes long. In addition, the comparative sample NO. From the result of 103, the time required for image appearance can be shortened only by adding the compound represented by the general formula (I) of the present invention, but the adverse effect of low illuminance reciprocity law failure becomes very large, and 1 / It can be seen that the 100 second exposure sensitivity is also reduced. On the other hand, the emulsions (Sample Nos. 104 and 105) according to the present invention do not require a long time for an image to appear and have a high exposure sensitivity of 10 seconds, so that the low illuminance reciprocity failure can be effectively reduced. You can see that

[0117]

According to the internal latent image type direct positive silver halide emulsion of the present invention, the time from the start of development to the formation of a viewable image can be shortened, and reciprocity law failure, especially low It has an excellent effect that the reciprocity law failure of illuminance can be effectively reduced. The color diffusion transfer photographic light-sensitive material using the emulsion of the present invention exhibits the above-mentioned excellent effects, and can form a good ornamental image quickly even when the image is taken in an environment of low illuminance.

Claims (2)

[Claims] 1. An internal latent image type direct positive silver halide emulsion comprising a silver halide grain containing an iridium compound and a compound represented by the following general formula (I). [Chemical 1] (In the formula, M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group capable of cleaving the MS bond under alkaline conditions. X represents an oxygen atom, a sulfur atom, or a selenium atom, and Y represents. , [Chemical formula 2] (Here, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R
₈ represents a hydrogen atom, or a substituted or unsubstituted alkyl group, aryl group, alkenyl group or aralkyl group. ) Represents. R represents a linear or branched alkylene group, a linear or branched alkenylene group, a linear or branched aralkylene group, or an arylene group.
Z is a hydrogen atom, a halogen atom, a nitro group, a cyano group,
A substituted or unsubstituted sulfonyl group, carbamoyl group, sulfamoyl group, carbonamido group, sulfonamide group, acyloxy group, sulfonyloxy group,
It represents a ureido group, a thioureido group, an acyl group, an oxycarbonyl group, an oxysulfonyl group, an oxycarbonylamino group or a mercapto group. n represents 0 or 1. ) 2. A color diffusion transfer photographic light-sensitive material comprising the internal latent image type direct positive silver halide emulsion according to claim 1.