JPH02199450A - Direct positive photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the sensitivity of the photosensitive material from degrading and to prevent the min. image density from increasing in spite of long-term exposing at a low illuminance by chemically sensitizing core particles by specifying the concn. of bromine ions within a specific range. CONSTITUTION:This photosensitive material is provided with >=1 layers of photosensitive layers contg. internal latent image type silver halide emulsions which are not previously fogged on a substrate. The emulsions are formed of >=2 layers of core/shell structures and the cores are formed by chemical sensitization by specifying the concn. of the bromine ions t 5.0X10<-4> to 2.0X10<-2>mol/l. A gold sensitizer and sulfur sensitizer are usable for the purpose of the sensitization and the nucleus forming agent expressed by the formula, etc., may be added to the photosensitive material. In formula, R<21> denotes an aliphat. group, arom. group, etc.; R<22> denotes H, alkyl, etc.; G denotes carbonyl, sulfonyl, etc.; both of R<23>, R<24> denote H or one denotes H and the other denotes alkyl sulfonyl, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a direct positive photographic light-sensitive material, in particular a non-fogged internal latent image type halogenated material having a core/shell structure and less affected by exposure conditions. The present invention relates to a direct positive photographic material having a photosensitive layer containing a silver emulsion.

BACKGROUND OF THE INVENTION Photographic methods that provide direct positive images without the need for reversal processing steps or negative film are well known.

Excluding special methods, the methods used to create positive images using conventionally known direct positive silver halide photographic materials can be mainly divided into two types, considering their practical usefulness. can.

One type uses a silver halide emulsion that has been fogged in advance and uses solarization or the Burschel effect to destroy fog nuclei (latent images) in exposed areas, thereby obtaining a positive image directly after development. be.

The other type uses an unfogged internal latent image type silver halide emulsion and directly obtains a positive image by carrying out surface development after or while carrying out fogging treatment after image exposure.

The internal latent image type silver halide photographic emulsion is a type of silver halide photographic emulsion in which photosensitive nuclei are mainly inside the silver halide grains and a latent image is mainly formed inside the grains upon exposure. say.

This latter type of method is more sensitive to boat fishing than the former type of method, and is suitable for applications requiring high sensitivity, and the present invention relates to this latter type of method.

Various techniques have been known for directly forming positive images using internal latent image type silver halide emulsions, such as U.S. Pat. No. 2,592.250;
No. 466.957, No. 2゜497.875, No. 2
, No. 588,982, No. 3,317,322, No. 3. 761. No. 266, No. 3,761,276, No. 3,796.577 and British Patent No. 1. 1
51. No. 363, No. 1,150,553 (No. 1,
011.062) The main ones are those described in each specification etc.

For details on the direct positive image formation mechanism, see
The Theory of the Photographic Process by T. H. James
of The Photographic Pr
This can be achieved by subjecting a silver halide photosensitive material to a fogging process or subjecting it to a surface color development process while subjecting it to a capri process, and then subjecting it to bleaching and fixing (or bleach-fixing). After bleaching and fixing, washing and/or
Or a stabilization treatment is applied.

Furthermore, it has been proposed to use a core/shell type emulsion in direct positive photographic materials. This emulsion has a core of silver halide grains whose surfaces have been chemically sensitized.
It consists of grains on which silver halide is further deposited to form a shell, and is unique in that it has internal sensitivity by actively introducing photosensitive nuclei inside.

(Problems to be Solved by the Invention) Conventionally used internal latent image emulsions with a core/shell structure have low sensitivity and soft contrast when exposed for long periods of time at low illuminance, so the minimum image density Dmin becomes higher,
The disadvantage is that the image quality deteriorates.

Furthermore, when the temperature during exposure of this emulsion is high, the sensitivity decreases, the tone becomes soft, and the image quality deteriorates.

In order to eliminate such defects, silver halide grain 4th edition,
Chapter 7, pages 182-193 and U.S. Patent No. 3,761,
It is described in No. 276, etc.

In other words, fog nuclei are selectively generated only on the surface of the silver halide grains in unexposed areas due to the surface desensitization effect caused by the so-called internal latent image generated inside the silver halide by the initial imagewise exposure. It is believed that a photographic image (direct positive image) is then formed in the unexposed area by subjecting it to a conventional so-called surface development process.

As mentioned above, as a means for selectively generating fog nuclei, a method of applying a second exposure to the entire surface of the photosensitive layer, which is generally called a "photofogging method" (for example, British Patent No. 1,151,3
63) and a nucleating agent (un
creating agent) is known. This latter method is discussed, for example, in ``Research Disclosure'' (Research Disclosure).
Closure) Magazine, Volume 151, No. 151
62 (issued November 1976), pages 76-7.

In order to directly form a positive color image, a method of doping internal latent image elements with metal ions is known, but the effect is not sufficient.

Furthermore, it takes a long time to prepare an emulsion with a core/shell structure, and it has been desired to shorten this time.

The object of the present invention is to overcome the drawbacks of the internal latent image type emulsion having a core/shell structure described above.

[Means to solve the problem]

The above-mentioned object of the present invention is to provide a direct positive photographic light-sensitive material having a photosensitive layer containing at least one unfogged internal latent image type silver halide emulsion on a support. The emulsion has a core/shear structure consisting of at least two layers, and the core has a bromide ion concentration of 5.0.
This is achieved by a direct positive photographic light-sensitive material characterized by being chemically sensitized under conditions of x10-4 to 2.0 x 10-'' mol/l.

The unfogged internal latent image type silver halide emulsion used in the present invention is an emulsion containing silver halide in which the surface of the silver halide grains is not fogged in advance and the latent image is mainly formed inside the grains. However, more specifically,
A certain amount (0.5 to 3
g/rrf), exposed to light for a fixed time of 0.01 to 10 seconds, and developed in the following developer A (internal type developer) at 18°C for 5 minutes to obtain a normal photographic density. The maximum density measured by the measuring method is obtained when a silver halide emulsion coated in the same amount as above and exposed in the same manner is developed in the following developer B (surface type developer) at 20"C for 6 minutes. Those having a concentration at least 5 times greater than the maximum concentration are preferred, and more preferably those having a concentration at least 10 times greater.

Internal developer A Metol 2g Sodium sulfite (
anhydrous) 90 g hydroquinone
8g Soda carbonate (-water salt)
52.5gKBr 5
gKI O,5
g0×10−3 to 1.4×10−2 mol/I! , is. The ripening temperature is preferably 55°C or higher and 100°C or lower,
More preferably, the temperature is 65°C or more and 100°C or less. The most preferable temperature is 70°C or more and 100°C or less. The optimum ripening time varies depending on the temperature and the amount of chemical sensitizer, but is approximately 10 minutes to 5 hours. The pH is preferably 2 to 9.

For chemical sensitization of the core particles mentioned above, a conventional chemical sensitizer can be used. Column line 18 to lower right column line 16, or H, Frieser (H9Frieser)
n der Photography Pro
zesse mit Sflbenhalogenid
The compounds described on pages 675-734 of (Academiasch Verlagsgesellschaft 196B) can be used. That is, chemical sensitizers include sulfur sensitizers, reduction sensitizers, and noble metal sensitizers (particularly with the addition of gold sensitized water.
4Hz 0 35 gKBr
Add 1g water
II! .

The internal latent image type silver halide grains of the present invention contain at least 2
It is a core/shell type consisting of layers.

The internal latent image type silver halide grains having this core/shell structure can be formed by a hitherto known method for producing a core/shell type emulsion.

To explain in more detail about the internal latent image type silver halide grains of the present invention, after the core grains are formed, the core grains have a bromide ion concentration of 5.0 x 10-4 to 2.0 x 10-4.
Chemical sensitization is carried out under the condition of 2 mol/l. The bromide ion concentration is preferably 2.0 x 10-4 to 1.7 x 10-2 mol/
! , more preferably a 5° agent), and among these, it is desirable to use a gold sensitizer or a sulfur sensitizer.

Chemical sensitization using a gold sensitizer as described above in the present invention,
That is, gold sensitization is a compound containing gold ions, such as AuCj! 4-, AuBr4-1Au(SCN)-,
The acid of Au(CN)z-, Au(SzOs)z' or its potassium or sodium salt is preferably added in an amount of 5 x 10-6 to 5 x 10-' mol, more preferably lXl0 per 1 mol of silver in the core particle. -4 to 1 x 10-3 mol, which can be carried out by adding to the emulsion according to the usual method (
For example, T, H.

James 'fJA, The Theory of the Photographic Process
of thePhotographic Processes
s) J 1977, Maca+illanPubl
Publishing Co, Inc., No. 154-15
5 pages, “Research Disclosure” magazine (7643,
(See page 23).

In the aging of the core in the present invention, a sulfur sensitizer, a reduction sensitizer, etc. can be used in combination with the gold sensitizer.

Examples of the sulfur sensitizer include sulfur compounds that can react with active gelatin and silver, such as thiosulfates, thioureas, mercapto compounds, and rhodanines. Examples of the reduction sensitizer include reducing substances such as stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, and silane compounds.

The average grain size of silver halide grains (in the case of spherical or near-spherical grains, the grain diameter is taken as the grain size, and in the case of cubic grains, the ridge length is taken as the grain size, and the projected area cannot be calculated as the average): 2. It is preferably 0 μ or less and 0.1 μ or more, and particularly preferred is 1. 2μ or less 0. It is 2μ or more. The particle size distribution may be narrow or wide, but in order to improve graininess and sharpness, the particle number or weight should be within ±40% (more preferably within ±30%, most preferably within ±30%) of the average particle size. It is preferable to use a so-called "monodisperse" silver halide emulsion in the present invention, which has a narrow grain size distribution in which 90% or more, particularly 95% or more of the total grains fall within the range (preferably within ±20%). The surface of the silver halide emulsion used can also be chemically sensitized by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination.

The silver halide emulsion used in the present invention includes US Pat.
No. 95478, No. 3761276, JP-A-51-2
．． As described in 16136 etc., manganese,
It is also possible to incorporate copper, cadmium, zinc, lead, bismuth, or metals from group II of the periodic table.

The photosensitive material of the present invention has the following general formula (N-I) or (
It is preferable to contain a compound represented by the compound represented by N-II) as a nucleating agent.

General formula (N-I) ■ R' (In the formula, Z represents a group of nonmetallic atoms necessary to form a 5- to 6-membered heterocycle, and Z is substituted with a substituent. Also, the target is photosensitive materials. In order to satisfy the desired gradation, two or more types of monodisperse silver halide emulsions with different grain sizes in emulsion layers having substantially the same color sensitivity or multiple grains of the same size but with different sensitivities are placed in the same layer. They can be mixed or coated in separate layers.Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be mixed or used in a layered manner.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, dodecahedral, dodecahedral, etc.).
), or may have an irregular crystal shape such as a spherical shape, or may have a composite shape of these crystal shapes. Further, tabular grains may be used, and in particular, an emulsion may be used in which tabular grains having a length/thickness ratio of 5 or more, particularly 8 or more occupy 50% or more of the total projected area of the grains.

An emulsion consisting of a mixture of these various crystal forms may also be used.

may have been done. R+ is an aliphatic group, and R2 is a hydrogen atom, an aliphatic group, or an aromatic group. R1 and R2 may be substituted with a substituent. Further, R2 may further be combined with a heterocycle completed by Z to form a ring. However, at least one of the groups represented by R1, R2, and Z contains an alkynyl group, an acyl group, a hydrazine group, or a hydrazone group, or R1 and R2 form a 6-membered ring, and have a dihydropyridinium skeleton. form. Furthermore, at least one of the substituents of RIR2 and Z may have a group that promotes adsorption to silver halide. Y is a counter ion for charge balance, and n is O or 1.

More specifically, the heterocycle completed by Z includes, for example, quinolinium, benzothiazolium, benzimidazolium, pyridinium, thiazolinium, thiazolium, naphthothiazolium, selenazolium, benzoselenazolium, imidazolium, tetrazolium, indo Mention may be made of rhenium, pyrrolinium, acridinium, phenanthridinium, isoquinolinium, oxacillium, naphthooxacillium and benzoxacillium nuclei. Substituents for Z include alkyl, alkenyl, aralkyl, aryl, alkynyl, hydroxy, alkoxy, aryloxy, halogen atom, amino, alkylthio, arylthio, acyloxy, acylamino, sulfonyl, sulfonyloxy, sulfonylamino, carboxyl, acyl, carbamoyl. , sulfamoyl, sulfo, cyano, ureido, urethane, carbonate, hydrazine, hydrazone, or imino group. As the substituent for Z, for example, at least one substituent is selected from the above substituents, but in the case of two or more substituents, they may be the same or different. Moreover, the above-mentioned substituents may be further substituted with these substituents.

Further, as a substituent for Z, a heterocyclic quaternary ammonium group completed with Z via a suitable linking group may be included. In this case, it takes a so-called dimer structure.

Preferred examples of the heterocycle completed by Z include quinolinium, benzothiazolium, benzimidazolium, pyridinium, acridinium, phenanthridinium, and isoquinolinium nuclei. More preferred are quinolinium and benzothiazolium, and most preferred is quinolinium.

The aliphatic groups of R1 and R2 are an unsubstituted alkyl group having 1 to 18 carbon atoms and a substituted alkyl group having 1 to 18 carbon atoms in the alkyl portion. Examples of the substituent include those described as the substituent for Z. Furthermore, R2 can be combined with the heterocycle completed by Z to form a ring.

The aromatic group represented by R2 has 6 to 20 carbon atoms, such as phenyl group and naphthyl group. Examples of the substituent include those described as the substituent for Z. R2 is preferably an aliphatic group, most preferably a methyl group, substituted methyl, or a ring formed by bonding with a heterocycle further completed by Z.

At least one of the groups represented by R', R'' and Z has an alkynyl, acyl, hydrazine, or hydrazone group, or R1 and R2 form a 6-membered ring to form a dihydropyridinium skeleton. However, these may be substituted with the group described above as a substituent for the group represented by Z.

The number of substituents on the groups or rings represented by R1, R2 and Z is preferably an alkynyl group or an acyl group, or R1 and R2 are linked to form a dihydropyridinium skeleton. , and further contains at least one alkynyl group, most preferably a pucopagyl group. The adsorption promoting group to silver halide in the substituents of R1, RZ and Z includes X'-(-L I-)- Those represented by r- are preferred, where Xl is a group promoting adsorption to silver halide, Ll is a divalent linking group, and m is O or 1.

Preferred examples of the adsorption promoting group to silver halide represented by XI include a thioamide group, a mercapto group, and a 5- to 6-membered nitrogen-containing heterocyclic group.

These may be substituted with the substituents for Z. The thioamide group is preferably an acyclic thioamide group (e.g. thiourethane group, thiourido group, etc.)
It is.

The mercapto group of
,4-thiadiazole,2mercapto-L 3,4-
oxadiazole, etc.) are preferred.

The 5- to 6-membered nitrogen-containing heterocycle represented by Xl is composed of a combination of nitrogen, oxygen, sulfur, and carbon,
Preferred are those that produce iminosilver, such as hensitriazole and aminothiatriazole.

The divalent linking group represented by Ll includes C1N, S,
It is an atom or atomic group containing at least one type of 0.

Specifically, for example, alkylene group, alkenylene group, alkynylene group, arylene group, O--5-1-N H-
1-N-1-Co-1SO□- (these groups may have a substituent), alone or in combination. Preferred examples of the combination include -CCNH- HCNH SO□NH CNH -NH3O□NH (al(arylene) HCNH CNH-).

(Arylene) Counter ions Y for charge balance include, for example, bromide ion, chloride ion, iodide ion, p-toluenesulfonate ion, ethylsulfonate ion, perchlorate ion,
Trifluoromethane sulfate (N-1 (N ■-2) (N ■-3) Examples include phonate ion, thiocyanide ion, boron tetrafluoride ion, and phosphorus hexafluoride ion.

These compounds and their synthesis methods can be found in, for example, Research Disclosure.
e) Magazine No. 22,534 (published January 1983, 5
0-54), and No. 23. 213 (1983
Patents cited in Japanese Patent Publications No. 49-38,164, No. 52-19,452, published in August 2013, pp. 267-270),
52-47,326, JP-A-52-69,613, JP-A-52-3,426, JP-A-55-138.742,
No. 60-11°837, U.S. Patent No. 4,306,01
No. 6, and No. 4,471,044.

Specific examples of the compound represented by general formula (N-1) are listed below, but the invention is not limited thereto.

(Ni-4) (N-I-5) (N-I-6) (N ■ H (N ■ (N ■ し1j21.:1.lj (N I-13) (N-1 (N ■ N ■ (N ■ (N ■ [N ■ (N I-17) (N ■ (N-1-19) (N-■-20) General formula (N-11) R"-N-N-G- R'' R23R24 (wherein R'' represents an aliphatic group, aromatic group, or heterocyclic group; R22 is a hydrogen atom, alkyl, aralkyl, aryl, alkoxy, aryloxy, amide group, etc.).

Among these, ureido groups and sulfonylamino groups are particularly preferred.

These groups may be linked to each other to form a ring when possible.

R'' is preferably an aromatic group, an aromatic heterocycle, or an aryl-substituted methyl group, and more preferably an aryl group (eg, phenyl group, naphthyl group, etc.).

Among the groups represented by R22, preferred are a hydrogen atom, an alkyl group (e.g. methyl group), an aralkyl group (e.g. 2-hydroxybenzyl group, etc.), or an aryl group (e.g. 2-hydroxymethylphenyl group). etc.), and a hydrogen atom is particularly preferred.

As the substituent for R22, in addition to the substituents listed for R2+, for example, acyl, acyloxy, alkyl or aryloxycarbonyl, alkenyl,
Alkynyl and nitro groups are also applicable.

These substituents are further substituted with these substituents or represent an amino group; G is carbonyl, sulfonyl, sulfoxy, phosphoryl, or iminomethylene group (HN=C)
R23 and R'' are both hydrogen atoms, or one is a hydrogen atom and the other is any one of alkylsulfonyl, arylsulfonyl, or acyl group. However, forms containing G, R23, R'' and hydrazine nitrogen may form a hydrazone structure (,:N-N=(,:2).The above-mentioned groups may be substituted with a substituent if possible.) To explain in more detail, R2I is a substituted It may be substituted with a group, and examples of the substituent include the following. These groups may be further substituted. For example, alkyl, aralkyl, alkoxy, alkyl or aryl substituted amino, acylamino, sulfonylamino,
It may be a ureido, urethane, aryloxy, sulfamoyl, carbamoyl, aryl, alkylthio, arylthio, sulfonyl, sulfinyl, hydroxy, halogen atom, cyano, sulfo, carboxyl group or phosphoric acid group. Further, if possible, these groups may be linked to each other to form a ring.

R21 or R22, especially R2+, may contain a diffusion-resistant group such as a coupler, a so-called ballast group, and is particularly preferably linked with a ureido or sulfonylamino group.

Group x2 that promotes adsorption to the surface of silver halide grains
→ You may have L2-+-1-r. Here, X2 has the same meaning as Xl in general formula (N-1), and is preferably thioamide (excluding thiosemicarbazide and its substituted products), mercapto, or a 5- or 6-membered nitrogen-containing heterocyclic group. R2 represents a monovalent linking group, and has the general formula (N
It has the same meaning as L' in -1). m2 is 0 or 1.

More preferably, x2 is an acyclic thioamide group (e.g., thioureido group, thiourethane group, etc.), a cyclic thioamide group (i.e., a mercapto-substituted nitrogen-containing heterocycle, such as 2-mercaptothiadiazole, 3-mercapto-1,
2,4-) lyazole, 5-mercaptotetrazole,
2-mercap)-1,3,4-oxadiazole, 2-
mercaptohenzuoxazole, etc.) or nitrogen-containing heterocyclic groups (eg, benzotriazole, benzimidazole, indazole groups, etc.).

The most preferable X2 varies depending on the photosensitive material used. For example, when using a color material (so-called coupler) that forms a dye through a coupling reaction with an oxidized form of a p-phenylenediamine developer in a color sensitive material, X2 is a mercapto-substituted nitrogen-containing heterocycle or an imino A silver-forming nitrogen-containing heterocycle is preferred. Furthermore, when using a coloring material (so-called DRR compound) that generates a diffusible dye by cross-oxidizing with an oxidized developer in a color sensitive material, X2 is an acyclic thioamide group or a mercapto-substituted nitrogen-containing heterocycle. preferable.

Furthermore, in a black-and-white sensitive material, x2 is preferably a mercapto-substituted nitrogen-containing heterocycle or a nitrogen-containing heterocycle forming iminosilver.

R'' and Rza are most preferably hydrogen atoms.

G in general formula (N-I[) is 60.
No. 638, No. 4,478,928, and No. 2,
No. 563,785 and No. 2,588°982.

Specific examples of compounds represented by the general formula (N-old) are shown below. However, compounds other than the compounds shown below can also be used in the present invention.

(N-n-1) (N-11-2) Most preferred.

Moreover, as a compound represented by the general formula [N-11),
More preferred are those having a silver halide adsorption group, and those having a ureido or sulfonylamino group.

Examples of these compounds and their synthesis methods include, for example, U.S. Pat. No. 4,030,925, U.S. Pat. No. 4,080,
No. 207, same No. 4. 031゜127, same No. 3,71
No. 8,470, No. 4゜269.929, No. 4,2
No. 76.364, No. 4,278,748, No. 4,
No. 385.108, No. 4,459,347, No. 4,
No. 478.922, No. 4,560,632, British Patent No. 2,011,391B, JP-A-54-74゜729
No. 55-163,533, No. 55-74.536
No. 60,179,734, etc.

Other hydrazine-based nucleating agents include, for example, JP-A No. 5
No. 7-86,829, U.S. Patent No. 4,5 (N-n-3) (N-If-4) (N-n-5) (N-]1 / CH,0H (N ■ (N ■ ( N ■ (N These nucleating agents are preferably added to the latent silver halide emulsion layer, but other nucleating agents may not be added as long as they diffuse and adsorb to the silver halide during coating or processing. For example, the layer
It may be added to an intermediate layer, undercoat layer or back layer.

The amount of nucleating agent used is 10-8 per mole of silver halide.
~10-2 mol is preferred, more preferably 10-7
~10-3 mol.

Moreover, two or more types of nucleating agents may be used in combination.

In the present invention, in order to further promote the action of the nucleating agent, the following nucleating promoters can be used.

Nucleation accelerators include tetrazaindenes, triazaindenes, and pentazaindenes having at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group, and JP-A-63-Sho. 10
Compounds described in Publication No. 6656 (pages 6 to 16) can be added.

Specific examples of the nucleation accelerator are listed below, but the invention is not limited thereto.

(A-1) 3-mercapto-1,2,4-triazolo(
4,5-a) Pyridine (A-2) 3-mercapto-1,2,4-)riazolo(
4,5-a) pyrimidine (A-3) 5-mercapto-1,2,4-) can be used in light-sensitive materials, such as internal latent image type silver halide emulsion layers and other hydrophilic colloid layers (intermediate layer, protective layer, etc.).

Particularly preferred is a layer in or adjacent to a silver halide emulsion layer.

A variety of color couplers can be used to form direct positive color images in the present invention. A color coupler is a compound that generates or releases a substantially non-diffusible dye through a coupling reaction with an oxidized form of an aromatic primary amine color developer, and is itself a substantially non-diffusible dye. Preferably, it is a compound. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolones or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are given in Research Disclosure magazine Nα17643 (published December 1978) p.25
, Section ■-D, No. 18717 (published in November 1979) and JP-A No. 6, Zoro CI, 5-a) Pyrimidine (A-4) 7-(2-dimethylaminoethyl) 5-mercapto-1, 2,4-) Riazolo[1,5-a) Pyrimidine (A-5) 3-Mercapto-7-methyl-1,2゜4-
Triazolo(4,5-a) pyrimidine (A-6) 3.6-dimercabuto 1.2.4 triazolo(4,5-b) pyridazine (A, -7) 2-mercapto-5-methylthio-1°3
．． 4-deadiazole (A-8) 3-mercapto-4-methyl-1,24-triazole (1-9) 2-(3-dimethylaminopropylthio)
-5-Mercapto-1,3,4-thiadiazole hydrochloride (A-10) l-(2-morpholinoethylthio)5-mercapto-1,3,4-thiadiazole hydrochloride nucleation promoter is used in photosensitive materials. 2-21
No. 5272 and the patents cited therein.

Card couplers for correcting unnecessary absorption in the short wavelength range of the generated dyes, couplers whose coloring dyes have appropriate diffusivity, colorless couplers, and DIR couplers that release a development inhibitor upon coupling reaction. or polymerized couplers can also be used.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

A color antifogging agent or a color mixing inhibitor can be used in the light-sensitive material of the present invention.

Representative examples of these are JP-A-62-215272 No. 185~
It is described on page 193.

A color enhancer can be used in the present invention for the purpose of improving the color development of the coupler. A typical example of a compound is JP-A No. 6
Examples include those described in No. 2-215272, pages 121 to 125.

The light-sensitive material of the present invention includes a substance that prevents irradiation and halation, an ultraviolet absorber, a plasticizer, a fluorescent whitening agent, a matting agent, an air fog prevention agent, a coating aid, a hardening agent,
Antistatic agents, slippery improvers, etc. can be added.

Representative examples of these additives are published in Research Disclosure Magazine No. 17643-XI [[(1978, 1
February issue) p25-27, and p.18716 (19
Published in November 1979) on pages 647-651.

The invention is also applicable to multilayer, multicolor photographic materials having two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. The preferred order of layer arrangement is red sensitivity, green sensitivity, and blue sensitivity from the support side, or green sensitivity, red sensitivity, and blue sensitivity from the support side. Furthermore, each of the above-mentioned emulsion layers may be made up of two or more emulsion layers having different sensitivities, and a non-light-sensitive layer may be present between two or more emulsion layers having the same color sensitivity. Typical examples include film, color reversal vapor, and instant color film. It can also be applied to full-color copying machines and color hard copies for storing images on CRTs. The present invention also applies to "Research Disclosure" magazine No. 17.
It can also be applied to black-and-white photosensitive materials using a three-color coupler mixture described in L23 (published July 1978).

Furthermore, the present invention can also be applied to black and white photographic materials.

Examples of black-and-white (B/W) photographic materials to which the present invention can be applied include JP-A-59-208540 and JP-A-60-26.
Examples include B/W direct positive photographic light-sensitive materials (for example, X-ray light-sensitive materials, duplex light-sensitive materials, micro-sensitive materials, photographic light-sensitive materials, and printing light-sensitive materials) described in No. 0039.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, aminophenol compounds are useful, but p-phenylenediamine compounds are also suitable. a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer,
It is usual that each blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation agent,
It is preferable to provide an auxiliary layer such as a backing agent and a white reflective layer as appropriate.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are disclosed in Research Disclosure Magazine No. 17643.
■ Items listed in section (December 1978) p. 28, European Patent No. 0,102,253, and JP-A-61-
97655. Also, Research Disclosure Magazine No. 17643
The coating method described in Section V, pages 28 to 29 can be used.

The present invention can be applied to various color photosensitive materials.

For example, color compounds for slides or televisions are preferably used, and a typical example is 3-methyl-4
-amino-N, N-diethylaniline, 3-methyl-
4-Amino-N-ethyl-Nβ-hydroxyethylaniline, 3-methyl 4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-
Mention may be made of amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or P-)luenesulfonates. These compounds are used depending on the purpose2
It is also possible to use more than one species in combination.

The pH of these color developing solutions is 9 to 12, preferably 9.5 to 11.5.

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

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose.

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

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnal of the 5ociety of M
tion Picture and Televisi
on Engineers Volume 64, P248-2
53 (May 1955 issue).

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent.

On the other hand, various known developing agents can be used to develop the black-and-white light-sensitive material of the present invention. That is, polyhydroxybenzenes such as hydroquinone, 2
-Chlorohydroquinone, not intended to be used.

Example 1 Preparation of Emulsion EM-1 An aqueous solution of potassium bromide and silver nitrate was vigorously stirred into an aqueous gelatin solution and added simultaneously over a period of 15 minutes at 75°C. Silver bromide particles were obtained. During the formation of the particles, 0.3 g of 3,4-dimethyl-1,3-thiazoline-2-thione per mole of silver was added to an aqueous gelatin solution. After desalting the resulting emulsion in a conventional manner, an aqueous potassium bromide solution was added to adjust the bromide ion concentration to 1.1X10-'' mol/l. 6 mg of sodium thiosulfate and 7 mg of sodium thiosulfate were added per 4 moles of silver. A chemical sensitization treatment was performed by sequentially adding chloroauric acid (tetrahydrate) and heating at 75°C for 30 minutes.

The particles obtained in this way are used as cores and further grown in the same precipitation environment as the first time, until the average particle size is 0. A 7μ octahedral monodisperse core/shell silver bromide emulsion was obtained. The coefficient of variation in particle size was approximately 10%. After desalting this emulsion in a conventional manner, the emulsion is mixed with 2-methylhydroquinone, catechol, pyrogallol, etc.; aminophenols such as p-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.; Pyrazolidones, such as 1-phenyl-3-pyrazolidones, 1
-Phenyl-4,4'-dimethyl-3-pyrazolidone, 1
-Phenyl-4-methyl 4-hydroxymethyl-3-pyrazolidone, 5°5-dimethyl-1-phenyl-3-pyrazolidone, etc.; Ascorbic acids, etc. can be used alone or in combination. Also, Japanese Patent Publication No. 58-55928
Developers listed in this issue can also be used.

For detailed examples of developers, preservatives, buffers, and development methods for black and white photosensitive materials, and how to use them, see
Research Disclosure” Magazine No. 17643
(Published in December 1978) It is described in sections X■ to XXI.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples. However, the present invention is limited to these examples only, and chemical amplification is carried out by adding 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mole of silver and heating at 60°C for 60 minutes. Sensitivity treatment was carried out to obtain an internal latent image type silver halide emulsion.

How to make emulsion EM-2 An aqueous solution of potassium bromide and silver nitrate was simultaneously added to an aqueous gelatin solution over 10 minutes at 50°C with vigorous stirring to form octahedral silver bromide particles with an average particle size of 10.25μ. I got it.

During the formation of these particles, 0.1 g of 3.4-
Dimethyl-1,3-thiazoline-2,000 ions was added to an aqueous gelatin solution. After desalting the obtained emulsion in a conventional manner, an aqueous potassium bromide solution was added to adjust the bromide ion concentration to 1.5×10 −2 mol/I! , was adjusted. Chemical sensitization treatment was carried out by sequentially adding 5 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mole of silver and heating at 75°C for 30 minutes.

The particles obtained in this way are used as cores and further grown in the same precipitation environment as the first time, until the average particle size is 0. A 4μ octahedral monodisperse core/shell silver bromide emulsion was obtained. The number of particle size variations was approximately 10%. After desalting this emulsion in a conventional manner, 2.5 mg of sodium diosulfate and 2.5 mg of chloroauric acid (tetrahydrate) per mole of silver were added to the emulsion and heated at 60°C for 60 minutes. A chemical sensitization treatment was performed to obtain an internal latent image type silver halide emulsion.

How to make comparative emulsion A-1: The bromide ion concentration during chemical sensitization of the core was set to 2゜5X10.
-2 mol/I! , and chemical sensitization treatment at 75°C180
It was prepared in the same manner as emulsion EM-1 except that the emulsion was prepared for 1 minute.

How to make comparative emulsion A-2: Set the bromine ion concentration during chemical sensitization of the core to 2°7×10
-”mol/I!, and chemically sensitized at 75°C180
It was prepared in the same manner as emulsion EM-2 except that the emulsion was prepared for 1 minute.

Paper support laminated on both sides with polyethylene (thickness 10
A color photographic light-sensitive material was prepared by coating the following 1st to 14th layers on the surface (0 micron) and 15th to 16th layers on the back side. 1st layer coated cyan coupler (ExC-1,
2,3 1:1:0.2) ...0
．． 30 Anti-fading agent (Cpd-1, 2, 3, 4 equivalents)...
・0.18 Anti-stin agent (Cpd-5) ・・・0.003
Force puller dispersion medium (Cp d-6)...0.03
Coupler solvent (Solv-1, 2, 3 equivalents) - 0
．． 12 4th layer (high sensitivity red sensitive layer) Silver bromide spectrally sensitized with red sensitizing dye (ExS-1, 2, 3) ...0.14 gelatin
...1.00 cyan coupler (E
xC-1,2,3 1:1:0.2)
...0.30 anti-fading agent (Cpd-1,2,3,4
Equivalent)...0.18 Coupler dispersion medium (Cpd-6)...0.03 Coupler solvent (Solv-1, 2, 3 equivalent)...0.
12 The polyethylene on the right uses titanium oxide as a white pigment,
In addition, a trace amount of ultramarine is included as a dye for bluing (the angle of the surface of the support is 88.0, -0.2 for L", a", b" systems).
It was 0, -0.75. ) (Photosensitive layer composition) The components and coating amount (g/rr? unit) are shown below. Regarding silver halide, the coating amount is shown in terms of silver.

The emulsions used in each layer were emulsion EM-1 for the high-speed layer and emulsion EM-2 for the low-speed layer. However, as the emulsion for the 14th layer, a Lippmann emulsion without surface chemical sensitization was used.

1st layer (antihalation layer) Black colloidal silver...0.10 Gelatin...-0,70 2nd layer (
Intermediate layer) Gelatin...0.70 Third layer (low sensitivity red sensitive layer) Silver bromide spectrally sensitized with red sensitizing dye (ExS-1, 2, 3)...0.04 Gelatin
...1.00 Fifth layer (intermediate layer) Gelatin ...1.00 Color mixing prevention agent (Cpd-7) ...0.08 Color mixing prevention agent solvent (Solv-4,5 equivalent)... 0.16 Polymer latex (Cpd-8)...0.10 6th
Layer (low sensitivity green sensitive layer) Silver bromide spectrally sensitized with green sensitizing dye (ExS-4)
...0.04 gelatin
...0.80 magenta coupler (
ExM-1, 2, 3 equivalent)...0.11 Anti-fading agent (equivalent amount of Cpd-9, 26)...0.15 Anti-staining agent (10, 11, 12 I3)
near:7:I ratio)...0.025 force puller dispersion medium (Cpd-6)...0.05 coupler solvent (
Solv-4,6 equivalent)...0.15 7th layer (high sensitivity green sensitive layer) Silver bromide spectrally sensitized with green sensitizing dye (ExS-4)
...0.10 gelatin
...0.80 magenta puller (ExM
-1, 2, 3 equivalents)...0.11 Anti-fading agent (Cpd-9, 26 equivalents)...0.15 Anti-staining agent (Cpd-10, 11, 1213 at 10%
=7=7:1 ratio)...0.025 force puller dispersion medium (Cpd-6)...0.05 coupler solvent (
Solv-4,6 equivalent)...0.15 8th layer (middle layer) 9th layer (yellow filter layer) same as the 5th layer Yellow colloidal silver (particle size 100)...0.
12 Gelatin...0.07 Anti-color mixing agent (Cpd-7)...0.03 Gelatin...0.60 Yellow coupler (ExM-1,2 equivalent)...0.30 Anti-fading agent ( Cpd-14) ...0.10 Stain inhibitor (Cpd-5,15 in a 1:5 ratio) ...0゜007 Coupler dispersion medium (Cpd-6) = -0.05 Coupler solvent (Solv -2) -0,10 13th layer (ultraviolet absorption layer) Gelatin...1.00 Ultraviolet absorption layer (Cpd-2, 4, 16 equivalent)...0.50 Color mixing prevention agent (Cpd-7, 17 equivalents)...0.03 Dispersion medium (Cpd-6)...0.02 Ultraviolet absorber solvent (Solv-2, 7 equivalents)...0.0
8 Anti-irradiation dye (Cpd-18, 19, 20, 21, 27 at 10:10
:13:15:20 ratio) Color mixing inhibitor solvent (Solv-4,5 equivalent)...0.1
0 Polymer latex (Cpd-8)...0.07 1st
0 layer (intermediate layer) 11th layer same as 5th layer (low sensitivity blue sensitive layer) Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) ...0.07 gelatin
...0.80 yellow coupler (
ExY-1,2 equivalent)...0.35 Anti-fading agent (Cpd-14)...0.10 Anti-staining agent (Cpd-5,15 in a 1:5 ratio)...0.007 Power puller dispersion medium (CPd-6)...0.05 Coupler solvent (Solv-2)...0.10 12th layer (high sensitivity blue sensitive layer) Blue sensitizing dye (ExS-5,6) Silver bromide spectrally sensitized with...0.15...0.05 14th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0.1
μ) ...0.03 Acrylic modified copolymer of polyvinyl alcohol ...0.01 Equivalent amount of polymethyl methacrylate particles (average particle size 2.4μ) and silicon oxide (average particle size 5μ)・0.05 gelatin
...1.80 gelatin hardening agent (H-
1, H-2 equivalent)...0.18 15th layer (back layer) Gelatin...2.50 Ultraviolet absorber (Cpd-2, 4, 16 equivalent)...0.50 Dye ( Equal amounts of CPd-18, 19, 20, 21, 27)
...0.06 16th layer (back protective layer) Equivalent amount of polymethyl methacrylate particles (average particle size 2.4μ) and silicon oxide (average particle size 5μ) ...0.05 Gelatin
...2.00 gelatin hardening agent (H-
1, H-2 equivalent)...0.14 Each photosensitive layer contains CP D-22 as a nucleation accelerator.
4.5 x 10-' moles were used per mole. Furthermore, each layer contains Alkanol XC (Dupon) as an emulsification and dispersion aid.
and sodium alkylbenzenesulfonate, succinate ester and Magefac F- as coating aids.
120 (manufactured by Dainippon Ink Co., Ltd.) was used. Silver halide and colloidal silver containing layers contain stabilizers (Cpd-23,
24, 25) was used.

In each photosensitive layer, a compound of N-■-16 was used as a nucleating agent in an amount of 4.5.times.10@-6 per mole of silver.

Sample No. 1 was produced in this way.

xS xS xS xS xS Cpd Cpd xS pd pd pd pd pd −←CH2 CH → 1- CONHC4Hq(t) n-100~1000 p d-7 pd −←CH2 CH→m.

C00CzHs pd pd pd Cpd-14 Cpd Cpd-16 anq(L) cp d-20 cP d-21 cp d-22 Cpd Cpd Pd-19 LJ3K )U3Δ pct Cp d-24 cp d-25 Cpd pd XC-1 XC XM XM XC-3 XM-1 XY-1 ;) Resyl phosphate 5olv-5 dibutyl phthalate 5olv-6 trioctyl phosphate 5olv-7 di(2-ethylhexyl)phthalate H-11,2-bis(vinylsulfonylacetamide)
Ethane H-24,6-dichloro-2-hydroxy-1,3,5
-) Lyazine Na salt emulsion A in place of EM-1, -1, A in place of EM-2
Comparative sample A was prepared in the same manner as sample No. 1 except that the sample No. -2 was changed.

Wedge exposure for 0.01 seconds or 1 second for sample No. 1 and A (3200K, halogen lamp, 1OCMS
) was given. Thereafter, processing step A as described later was performed, and the resulting image density was measured. The measurement results are shown in Table 1.

Table 1 * Exposure time Sample Nα1 of the present invention was preferred because the sensitivity change was smaller than that of comparative sample A when exposed for 0.01 seconds and 1 second. At the same time, the gradation change was also small and preferred.

Processing step A Color development 135 seconds 38°C Bleach-fixing 40〃 33〃 Washing with water (1) 40〃 33〃 Washing with water (2) 40〃 33// Drying 30〃 8ol/ Methyl-4-aminoaniline sulfate Potassium carbonate 30 .0g Fluorescent brightener (diaminostilbene type) 1.0g D-sorbitol Naphthalene sulfonate Natriram formalin Condensate Ethylene diamine Tetrakismethylene phosphonic acid Diethylene glycol Benzyl alcohol Potassium bromide Benzotriazole Sodium sulfite N,N-bis(carboxymethyl)hydrazine D -Glucose triethanolamine N-ethyl-N-(β-methanesulfonamidoethyl)-3 0.15g 0.15g 1.5 g 12゜13゜Oo 0゜2゜6゜m1 5mI! .

0g 03g 4g 4g 2.0 g 6.0 g 6.4g Town Z job □ Ethylenediamine tetraacetic acid 2 sodium 4. Oglium dihydrate ethylenediaminetetraacetic acid Fe (1) 70. 0
g.Ammonium dihydrate ammonium thiosulfate (700g/jri 180ml!
Ensulfinic acid for pml 20.0g Sodium bisulfite 20.0g 5-mercapto-1,3,4-0.5g Triazole ammonium nitrate 10.0g Amberlite IR-120B) and OH type anion exchange resin (Amberlite I, R-400
) to reduce the concentration of calcium and magnesium ions to 3 mg/1 or less, followed by 20 mg of sodium isocyanurate dichloride.
#2 and 1.5 g of sodium sulfate #2 were added. The pH of this liquid was in the range of 6.5 to 7.5.

Example-2 Emulsions EM-3 and 4i After the formation of each core grain, emulsion EM except that PAg was adjusted without desalting and the core was chemically sensitized.
-1 and 2 were produced in the same manner.

Emulsions A-3 and 4i were each treated with T without desalting after core grain formation.
'Emulsion EM except for adjusting Ag and chemically sensitizing the core.
-1 and 2 were produced in the same manner.

Samples No. 2 were prepared in the same manner as Sample No. 1 except that emulsion EM-3 was used in the high-speed layer and emulsion EM4 was used in the low-speed layer. Similarly, emulsion A-
Comparative samples No. 3 and B were prepared in the same manner as sample No. 1 except that emulsion A-4 was used in the low-speed layer.

Samples No. 2 and B were exposed to light in the same manner as in Example-1, and the same results were obtained.

Example 3 As a nucleating agent, a compound of N-If-10 was added to each photosensitive layer in place of a compound of N-1-16 at a concentration of 4.5×10 per mole of silver.
Example 1 was repeated and the same results were obtained, except that mol of -S was added.

Example-4 Samples No. 1 and A of Example-1 were exposed at temperatures of 15°C and 35°C. Exposure was given under the conditions of 10 CMS of a halogen lamp at 5400 Hz for 1 second. Thereafter, processing step A was performed, and the relative sensitivity of the resulting images was measured and is shown in Table 2.

Table 2 Sample No. 1 of the present invention was preferable because the change in sensitivity due to temperature change during exposure was smaller than Sample A of the comparative example.

(Effects of the Invention) The photosensitive material of the present invention does not lose sensitivity when the exposure time changes, that is, when exposed for a long time at low illuminance.
Furthermore, the minimum image density does not increase and the change in gradation is small. Further, the photosensitive material of the present invention has a small change in sensitivity even if the temperature during exposure changes.

Procedural amendment 1999 (Monday)

Claims (1)

[Claims] A direct positive photographic light-sensitive material having on a support at least one photosensitive layer containing an internal latent image type silver halide emulsion which is not previously fogged, the internal latent image type silver halide emulsion consisting of at least two layers. It has a core/shell structure, and the core has a bromide ion concentration of 5.0×10^-^4~2.
A direct positive photographic light-sensitive material characterized by being chemically sensitized under conditions of 0x10^-^2 mol/l.